7 Distillation

Distillation is the technique of preferential separation of the more volatile component(s)from

the less volatile ones in a feed solution by partial vaporization of the feed followed by
condensation. The vapor produced is richer in the more volatile component(s).The
distribution of the components in the two phases is governed by the vapour-liquid
equilibrium relationship.Only partial separation of the components can be achieved in this
way.In order to have a larger degree of separation,multistage contact between the vapour and
the liquid phases is arranged in a suitable device called a 'distillation column'(for
example,a tray column or tower described in Chapters 1 and 5).The most important parts of a
distillation unit as illustrated in Figure 7.1 are:
(a)a column having trays or a packing and suitable internals (discussed in Chapter 5),(b)a
reboiler,and(c)a condenser.The feed enters at a suitable point of the tower.The reboiler,
normally heated by steam,partially vaporizes the liquid received from the bottom of the
column. The vapour flows up through the trays or through the packing in the column,leaves
at the top and enters into an overhead condenser.A part of the condensate is withdrawn as the
top product and the rest is fed back into the column as refux which flows down the trays or
the packing. An intimate contact between the downflowing liquid and the upflowing vapour
occurs on the trays or on the packing surface.Exchange of mass takes place between the liquid
and the vapour phases.The more volatile components move from the liquid to the vapour
phase and the less volatiles move in the reverse direction—from the vapour to the liquid
phase.As a result,the concentrations of the more volatiles gradually increase in the vapour
as it goes up,and the concentrations of the less volatiles increase in the liquid phase as it
flows down the column.In this way,a higher degree of separation of the more volatiles from
the less volatiles is achieved. The top product drawn from the condenser is rich in the more
volatiles.The bottom product has a high concentration of the less volatiles and only a small
amount of the more volatiles.The more the number of trays(or the depth of packing)and the
more the reflux ratio(it is defined in
Figure 7.1),the better is the separation.A distillation column described above performs the job
of 'fractional distillation',i.e.separation of a feed into two or more products differing in boiling
points or boiling ranges.Distillation is the most mature,albeit energy-intensive,technique of
separation of liquid mixtures in small to large capacities.Columns as big as 10 m in diameter and
having 150 or more trays have been reported to be in operation.

319
 3
320 Chapter 7 Distillation Vapour
4

F:Feed(liquid,vapour or a
2 mixture of liquid and
Reflux D vapour) D:Distillate or top
F product (it
Feed is rich in the more volatiles)
5 W:Bottom product (it is rich in
Steam the less volatiles)
Liquid
1:The column
Condensate
2:The feed preheater*
w+
3:Condenser for the overhead
vapour 4:Reflux drum
5:Reboiler(for partial vaporization
of the bottom liquid)

*The hot bottom product maybe

used to preheat the feed for energy

Figure 7.1 Schematic of a typical distillation column.

Distillation,which is one of the oldest mass transfer operations,is reported to have

been invented in Alexandria(Egypt)in the first century AD.The early use was in the
production of alcoholic beverages.The history of distillation has been described by
Forbes(1948).
It will be useful to distinguish between distillation and evaporation since in the latter
operation also,the components in solution are separated by volatilizing some of them.The major
difference is that in evaporation a solution containing a volatile solvent and a non-volatile solute
(or a solute having a very low volatility)is separated by vaporizing out a part or whole of the
solvent.Examples are:evaporation of a sugar solution(sugar:a non-volatile solute;water:a
volatile solvent), evaporation of a glycerol solution(glycerol:a solute having negligible
volatility;water:a volatile solvent).But in distillation,the components (at least two of
them)have reasonable volatility. Example:distillation of aqueous ethanol (both ethanol and
water are volatile,but ethanol is more volatile).
Distillation is the most common mass transfer operation in the process
industries,particularly the organic process industries.The function of distillation may be
separation of products from a mixture (example:separation of aniline and nitrobenzene in
the process of manufacture of aniline),recovery of a product (example:recovery of ethanol
from its solution in water in the process of manufacture of alcohol),or increasing the purity
of a product (example:drying of commercial benzene for the removal of traces of water present
in it).Distillation is again the most important operation in a petroleum refinery.A petrochemical
complex also uses a large number of distillation columns.Sometimes,distillation may be used in
conjunction with a few other mass transfer operations (Stichlmair and Fair,1998).For
example,in an acrylonitrile plant,the product is separated from the reaction mixture by
absorption in water.The aqueous solution of acrylonitrile leaving the absorption tower is
separated in a distillation column to produce acrylonitrile of desired purity.Similarly,the
extract and raffinate streams from an extraction column(discussed in Chapter 8)may be
further separated in a distillation column depending upon the difference in volatility of the
components(example:an aromatics extraction unit in a petroleum refinery).Because of its
importance and wide use in separation of mixtures,distillation is called
 Vapour-Liquid Equilibrium 321

'the workhorse of chemical industries'.Despite the advent of newer and advanced separation
processes,distillation still remains the most widely used separation technique of liquid mixtures and
solutions(Fair,1988;Kunesh et al.,1995).The estimated cost of annual worldwide throughput
of distillation columns was 524 billion dollars about ten years ago as reported by Porter (1995).
A few common examples of applications of fractional distillation are cited in Table 7.1.Here we
shall briefly discuss the basic principles of distillation calculations and design.There are a
few excellent books that deal with the topic
elaborately(Billet,1985,1995;Kister,1989,1992; Stichlmair and Fair,1998).

Table 7.1 A few examples of separation of liquid mixtures by distillation

Feed/Components Industry/Plan Product

Crude petroleur Refinery Various petroleum products
Ethylene oxide/Water Petrochemical Ethylene oxide
Acrylonitrile/Water Acrylonitrile
Styrene/Ethylbenzene Styrene
Benzene/Ethyl Ethylbenzen
benzene/others Propylene
Propylene/Propane
EthanolWater Fermentation/Distillery Ethano
Acetic acid/Acetic anhydride Acetic anhydride plan Acetic anhydride
Air Air separation plant Nitrogen,Oxygen,Argo
n
Aniline/Nitrobenzene Aniline plan Aniline

7.1 VAPOUR-LIQUID EQUILIBRIUM

Separation of a mixture by distillation is based on equilibrium distribution of the components

between the liquid and the vapour phases.A knowledge of vapour-liquid equilibrium is therefore
essential for understanding the principles of distillation.Consider an aqueous solution of ethanol
taken in a closed vessel like the one shown in Figure 4.1.The solution is boiled for some time
and the vapour along with air in the space above the liquid is expelled through a valve so that
the vessel now contains molecules of ethanol and water only.The valve is now closed and the vessel
is put in a constant temperature bath.What do we expect to happen?Given sufficient time,the
system reaches equilibrium and the liquid and the vapour compositions as well as the total pressure
in the vapour space(i.e.the total pressure exerted by the solution)attain unique values.Now the
vessel is taken out of the bath,some amount of ethanol (or water)is pushed into it and the vessel
is again maintained at the same temperature in the bath.The system will attain a new equilibrium
state,i.e.it will have a different set of liquid and vapour concentrations and a new total pressure
in the vapour space.Under a given set of conditions,the equilibrium vapour composition is related
to the liquid composition,This is what is called the vapour-liquid equilibrium (VLE).
But what is meant by 'a given set of conditions'?The answer is given by Gibb's phase
rule (discussed before in Chapter 4)expressed as
F=C-P+2 (7.1)
In the above example of equilibrium in the ethanol-water system,the number of
components, C=2;the number of phases,P=2(the vapour and the liquid phase).So F =2 and
the system
322 Chapter 7 Distillation

has two degrees of freedom.The total number of parameters and variables is four—
temperature, total pressure,liquid composition and vapour composition.Since the number
of degrees of freedom(F)is2,two of these four quantities need to be fixed to define the
system in equilibrium. Thus if temperature and pressure are fixed,the liquid and the vapour
compositions will be automatically fixed (i.e.there can be only one set of liquid and vapour
compositions for which the total pressure exerted in the vapour space is equal to the
given pressure at the given temperature).Similarly,if the temperature and the liquid
composition are fixed,the total pressure and the vapour compositions will be automatically fixed
if the system is in equilibrium.Extension to a multicomponent system is not difficult.
Vapour-liquid equilibria constitute the physical basis of separation of a mixture by
distillation. The higher concentration of the more volatile component(s)in the vapour phase
compared to the liquid phase makes separation by distillation possible (see the x-y data for
the methanol-water system given in Example 7.15).Accurate VLE data are essential for reliable
design of a distillation column.If the experimental data are not available (this happens
frequently for multicomponent systems),a suitable predictive method (e.g.UNIFAC
method)can be adopted for computation of equilibrium data.Now we shall describe a simple
experimental setup for the determination of vapour-liquid equilibrium in the laboratory.This
will be followed by a description of common types of equilibrium relationships exhibited by
various liquid mixtures.

7.1.1 Experimental Determination of Vapour-Liquid Equilibrium(VLE)

Different types of experimental setup have been devised for the measurement of composition
and temperature/pressure of liquid and vapour phases in equilibrium.The basic functions of an
equilibrium still are to continuously vaporize a liquid mixture,condense all the vapour in a
condenser (using a suitable coolant)and recycle the condensate to the still or the boiling
flask.This kind of apparatus is called a 'liquid-recirculation still'.After equilibrium is
reached,a sample of the liquid is drawn from the still and analyzed to determine the liquid
composition (x,mole fraction). A sample of the condensate(which has the same composition as
that of the vapour)is analyzed to get the composition of the vapour at equilibrium+(y*,mole
fraction).Experiments are repeated with liquid mixtures of different compositions to generate
the vapour-liquid equilibrium data (x-y*data)covering the entire range of composition of
the binary (O≤x≤1).
An early version of the device used for this purpose is the 'Othmer still'devised by
D.F. Othmer as early as in 1928.Various modifications of this apparatus have been suggested
from time to time—for example,Colburn still,Gillespie still,Scheeline and Gilliland
still,etc.Two common sources of error in the experiments are:(i)superheating of the liquid (the
thermocouple/ thermometer indicates a wrong boiling temperature of the liquid mixture as a
result);(ii)heat loss from the still or the boiling flask causing partial condensation of the vapour
before it leaves the boiling flask.A modified version of the Gillespie still (Yuan and
Lu,1963)which is free from these problems is described in Figure 7.2.
A liquid mixture is taken in the boiling flask (B)which is provided with an internal
electric heating coil (H)within a glass sheath(G).The liquid-vapour mixture flows through the
vertical tube P(sometimes called 'Cottrell pump')and enters the equilibriation chamber (E)in
which the vapour and the liquid phases get separated and reach equilibrium.The liquid flows
to the liquid

+A star (*)is often used to indicate the equilibrium value;x andy refer to the more volatile in a binary.
 Vapour-Liquid Equilibrium 323

Figure 7.2 Schematic of a modified Gillespie still.B:boiling flask or 'still';H:intemal electric heater;G:glass sheath of
the heater;P:Cottrell pump;E:equilibration chamber;R,:liquid receiver;C:total condenser of a vapour;Rz:condensate
receiver; T:thermometer orthermocouple.

receiver (R₁)and the vapour flows to the condenser(C).The condensate is collected in another
receiver(R₂).Since all the vapour flowing into the condenser is condensed (it is a 'total
condenser'),the composition of the vapour and that of the condensate are equal.The boiling flask
(B),the equilibrium chamber (E)and the liquid receiver (R₁)are well-insulated.(If the insulation
is not good,condensation of a little vapour may occur in E and R₁causing 'rectification'of the
vapour.As a result,the vapour will be more enriched in the more volatiles than it should be at
'equilibrium').The liquid from R and the condensate from R₂continuously overflow and
get recycled back to the boiling flask through the connecting tubes as shown in Figure 7.2.The
still is operated for a sufficiently long time to reach equilibrium.Samples of the liquid and
of the vapour(condensed in the receiver R₂)are collected by opening the stop cocks and then
analyzed to find out the equilibrium compositions of the phases.The temperature in the
equilibrium chamber is measured by inserting a thermocouple or a thermometer in the
thermowell,T.The temperature indicated at equilibrium is equal to the bubble point of the
liquid and also equal to the dew point of the equilibrium vapour.(It is to be noted that if
the boiling temperature is measured by inserting a thermometer in a thermowell in the boiling
flask,there may be an error because of the superheat of the liquid.)A suitable arrangement for
maintaining the pressure in the still is made if it is operated at a pressure different from the
ambient pressure.

The apparatus described above is useful to measure the 'constant pressure'equilibrium data.
With some modifications,it can be used to measure 'constant temperature'equilibrium—
when the total pressure,in addition to the equilibrium liquid and vapour concentrations,is
measured at a given constant temperature.
324 Chapter 7 Distillation

7.1.2 Constant Temperature or Constant Pressure Binary Equilibria

By repeating the above experiment with liquid mixtures of various compositions,we can collect
the T-x-y*data for a system.If the boiling temperature is plotted versus the liquid composition
x,we get the 'bubble point curve'.A plot of the temperature versus y*,the equilibrium vapour
composition,gives the 'dew point'curve.The bubble and dew point curves for binary mixtures
of cyclo-pentane(A)and benzene(B)at 1 atm total pressure are shown in Figure 7.3(a).Both the
liquid and vapour phase concentrations (x and y*)of cyclo-pentane (the more volatile)are plotted
along the horizontal axis and the temperature is plotted along the vertical axis.The equilibrium
diagram(x-y*diagram)is shown below the T-x-y*diagram in which x is plotted along the
horizontal axis and y*along the vertical axis [Figure 7.3(b)].A two-dimensional representation

Bubble or dew
point,c

(a)

100%B
0

(b) y*

Figure 7.3 (a)Bubble and dew point curves,and (b)equlibrium diagram of cyclo-pentane (1)-benzene (2)system at 1 atm.
[Myers,Ind.Eng.Chem,48(1956)1104.]
 Vapour-Liquid Equilibrium 325

of T-x-y or x-y data is possible only for binary mixtures.For a three-component system,such
data may be represented by surfaces in a three-dimensional space or in the tabular form.
On a horizontal line segment,say LV in Figure 7.3(a),the abscissa of the point L gives
the concentration of A in the saturatedt liquid phase(x),and that of the the point V gives
its equilibrium vapour-phase concentration(y*);LV is called a 'tie line'.The lines
LV,MN,M₁Nl, and L₁V₁in the figure are also tie lines.
Let us imagine that a small amount of a liquid mixture having a mole fraction x (a subscript
is not generally used to denote the concentration of the more volatile in a binary mixture)of cyclo-
pentane and the rest benzene is taken at a constant pressure of 1 atm in a vessel fitted with a
'frictionless piston'and heated gradually.The temperature and composition of the liquid are given
by the point G in Figure 7.3(a).When its temperature reaches the point M,it starts boiling and
the composition of the initial vapour is given by the abscissa of the point N,which is the other
end of the tie line through M.It is seen that y*>x;i.e.the vapour is richer in A,the more volatile
species in the mixture.As heating proceeds,more and more vapour is generated (we assume that
all the vapour generated remains in the vapour space above the liquid at a constant pressure).The
mole fraction of the more volatile component A in the residual liquid decreases and the boiling
point of the liquid continues to increase along the T-x curve.The last droplet of liquid to vaporize
has a composition and boiling point given by the point Mi.When all the liquid is vaporized,the
accumulated vapour must have a composition equal to that of the initial liquid.No further heating
is done and the final state of the vapour (as given by its temperature and composition)is given
by the point N₁on the vertical line through G.However,if further heating of this vapour (which
is now saturated)is done,its temperature will only rise along the vertical line GH(this is
superheating of the vapour).The line Tg-M₁-L-Ll-TA is the bubble point curve;Tg-Ni-N-
V- V₁-T₄is the dew point curve.The bubble and the dew point curves meet at the points
Tg(the boiling point of pure B at the given pressure)and at T₄(the boiling point of pure A).
Similarly,if some amount of superheated vapour,whose state is represented by the point
H₁ is taken in a vessel fitted with a frictionless piston and is gradually cooled while
maintaining a constant pressure of 1 atm,condensation starts when the vapour temperature
drops to the point V.The composition of the first droplet of liquid formed is given by the
point L(the other end of the tie line through V).As condensation proceeds,the vapour
composition changes along VV₁ and the composition of the condensate follows LLi.When the
entire vapour is condensed and the liquid is cooled,we reach a point Gi vertically below H₁in
the subcooled liquid domain.The boiling point of pure B lies vertically above the point
x=0(x=0 means pure B).Similarly,TA occurs vertically above x =1.
The region below the bubble point curve Tg-M₁-M-L-L₁-TA represents a single liquid
phase; the region above Tg-N₁-N-V-V₁-T₄represents a single vapour phase.A point in
the region enclosed by these curves represents a mixture of liquid and vapour.Any such
mixture (given by the point F in Figure 7.5(a),for example)splits into a liquid and a vapour
phase in equilibrium given by the ends of the tie line LV through the point F.
Let the amount of the two-phase mixture taken be also denoted by F kmoltt at a
concentration zp.It splits into a liquid phase of amount L kmol(concentration =x)and an

+Aliquid at its bubble point is called a saturated liquid';a vapour at its dew point is a saturated vapour':
+tThis practice of representing a stream and its flow rate or amount by the same notation is pretty common
in the study of mass transfer operations.
326 Chapter 7 Distillation

equilibrium vapour phase of amount V kmol (concentration =y*).Now we may write the
following mass balance equations [refer to Figure 7.5(a)].
Overall mass balance: F=L+V (7.2)
Component A balance: Fzp=Lx +Vy* (7.3)
Eliminating F from Eqs.(7.2)and (7.3), g
(L+V)zr=Lx+Vy

→ (7.4)

Thus,the amounts of liquid and vapour produced after phase separation of the mixture F
can be calculated using Eq.(7.4).This equation is sometimes called the Lever-arm Rule.It is
useful in the calculation of flash vaporization,calculations involving liquid-liquid and
solid-liquid
extraction,etc.
8
Figure 7.3(b)shows the equilibrium
P
diagram on the x-y plane.It can be ob- x-P
7
tained directly by plotting the experimen- 0
P(mm0 Liqu
tal x-y*data(note that both x and y*vary Hg)
from 0 to 1).It can also be drawn from 6 F Two-
the bubble point and dew point curves, ( phase
following the procedure indicated in the 4 regio 叶
figure.The point Q on the x-y*curve 0
0
corresponds to the tie line LV on the L y*-P
T-x-y diagram.Because y*>x,the 30 V
0 curv
equilibrium line lies above the diagonal C

(at any point on the diagonal,x =y).The

x, 100
kind of data given in Figure 7.3 represent
1.
the equilibrium data collected at constant
pressure.
0
Equilibrium data can also be collected
at constant temperature.If so,the total
vapour pressure P exerted by the solution 0
( y
Equilibriu
at equilibrium depends upon its composi- m x-
tion.At a lower concentration of A(i.e.at 0 Q P
a higher concentration of the less volatile
species B),the mixture will exert a lower Diagonal
0
total vapour pressure.Typical plots of
such data,x-P and y*-P,are shown in
0
Figure 7.4(a).A horizontal line such as 0.0 0.2 0.4 0.6 0.8 1.0

LV is a tie line.The terminals (the x

points L and V)indicate the liquid and Figure 7.4 (a)Bubble point pressure(x-P andy*-P),and
vapour phase concentrations of A under (b) equilibrium(x-y)diagrams for dichloromethane-1,2-
equilib- rium.The liquid,the vapour and dichloroethane system at 40°C.[Davies et al.J.Soc.Chem.Ind.
the two- phase regions are (Lond),68(1949) 26.]
demarcated in the
 Vapour-Liquid Equilibrium 327

figure.The region below the curve represents the 'superheated'vapour;the region

above represents the ‘subcooled’liquid and are the vapour pressures of
the pure liquids at the given temperature).If an amount of superheated vapour at the state
given by the point C is compressed isothermally,it starts condensing as it reaches the point V
and the first droplet of liquid formed has a composition given by the point L.On further
compression,more vapour condenses and the composition of the accumulated condensate liquid
changes along LE and the composition of the vapour changes along VE'.At a pressure
corresponding to the point E,the vapour condenses completely.Now the liquid composition is
the same as the composition of the original vapour.If the pressure is raised further,the liquid
may be considered 'subcooled'. The equilibrium compositions corresponding to the tie line LV
is represented by the point QP on the x-y diagram in Figure 7.4(b).The two-phase region on a
T-x-y or P-x-y plot narrows down with increasing tepmerature and pressure and eventually
disappears at the critical point.The details of these phenomena are available in standard texts
on thermodynamics.

7.1.3 The Raoult's Law

Raoult's law which describes the vapour-liquid equilibria of ideal solutions,has been
discussed in Section 4.3.1.Equation(4.1),which is the expression for Raoult's law,is
written below [Eq.(7.5)]for both the components A and B to give the equilibrium partial
pressures of the components in a binary liquid mixture.If x is the mole fraction of A in the
binary solution,that of B is(1-x)

and (7.5)
The total pressure: (7.6)
Here p and pf are the equilibrium partial pressures of A and B in the vapour;PX and Pb are
the vapour pressures of A and B at the given temperature.The mole fraction of A in the
vapour is given by

(7.7)
Equation(7.7)can be used to calculate the vapour-liquid equilibrium data(x-y*)for an ideal
binary mixture.The procedure to calculate the equilibrium concentrations as well as the
bubble point and the dew point at a constant total pressure P,is described below.

(a)Find the vapour pressures and of A and B at a temperature

T(TA<T<Tg). (b) The total pressure P being known,calculate x from Eq.(7.6).
(c) Calculate y*from Eq.(7.7).
The procedure is illustrated in Example 7.1.The constants of the Antoine equation for
vapour pressure of some selected liquids are given in Table 7.2.

Table 7.2 Constants of the vapourpressure relation(Antoine equation)

Compound BP (C) A' B' C'

(Contd.)
 Vapour-Liquid Equilibrium 327
Acetaldehyde 20.5 16.6006 2532.41 234
Acetic acid 258.46
118 18.47233 4457.83

(Contd.)
328 Chapter 7 Distillation

Table 7.2 Constants of the vapour pressure relation (Antoine equation)(Contd

Compound BP(C A' B' C'

Acetone 56.2 16.39112 2787.5 229.67

Acetonitrile 16.90395 3413.1 250.48
81.5
Acrylonitrile 2782.21
77.5 15.92847 222
Ammonia -33.4 17.51202 2363.24 250.54
Aniline 184.5 16.67784 3858.22 200
Benzaldehyde 1369.460
179 6.73163 177.081
Benzene 80 15.9037 2789.01 220.79
n-Butane -0.5 15.68151 2154.9 238.74
n-Butanol 3367.12
117.6 17.62995 188.7
iso-Butane -11.7 15.77506 2133.24 245
iso-Butano 108 18.02933 3413.34 199.97
Butyl acetate 126 3293.66
16.4145 210.75
Carbon disulphide 2585.12
46 15.77889 236.46
Carbon tetrachloride 76.5 2790.78
15.8434 226.46
Chlorobenzene 3485.35
131.5 16.4 224.87
Chloroform 16.017 2696.25
61.2 226.24
Cyclohexane 2778
80.5 15.7794 223.14
Cyclohexano 5200.53
161 19.23534 251.7
Cyclohexanone 3677.63
155.5 16.40517 212.7
Cyclopentane 2589.2
49.2 15.8602 231.36
1-4-Dioxane 101.5 17.1151 3579.78 240.35
Dichloromethane 17.0635 3053.08
40 252.6
Djethyl ether 16.5414 2847.72
34.5 253
Diethylamine 2434.73
55.5 15.73382 212
Ethanol 18.68233 3667.70 226.1
78.3
Ethyl acetate 16.35578 2866.6
77 217.9
Ethyl benzene 16.04305 3291.66
136 213.8
Ethylamine 7.3862 1137.300
16.5 235.85
Formic acid 15.9938 2982.45 218
100.5
Furfural 15.14517 2760.09 162.8
162
n-Hexane 15.9155 2738.42
69 226.2
n-Heptane 2911.32
98.5 15.877 226.65
Methanol 18.61042 3392.57
64.5 230
Methyl acetate 16.58646 2839.21
57 228
16.42172 3485.35
Nitrobenzene 131.5 224.84
Nitrogen 15.3673 648.59
-195.8 270.02
n-Octane 15.9635 3128.75
126 209.85
Oxygen 15.06244 674.59
-183 263.07
1-Octanol 7.18653 1515.427
195 156.767
15.8365 2477.07
n-Pentane 36 233.21
15.9614 3183.67
Phenol 159.5
180

(Contd.)
 Vapour-Liquid Equilibrium 329
Table 7.2 Constants ofthe vapour pressure relation (Antoine equation)(Contd)
Compound BP(C A' B' C'
n-Propano 97.2 17.8349 3310.4 198.5
iso-Propano 82.2 20.4463 4628.95 252.64
Propane -42 15.7277 1872.82 250
Pyridine 115 16.1520 3124.45 212.66
Styrene 135 15.94618 3270.26 206
Tetrahydrofuran 66 16.11023 2768.37 226.3
Toluene 110.6 16.00531 3090.78 219.14
Trichloroethylene 87 15.01158 2345.48 192.73
Triethylamine 89 15.7212 2674.7 205
o-Xylene 134.5 7.00154 1476.393 213.872
2-)Kylene 129.2 6.99052 1453.430 215.307
Water 100 18.5882 3984.92 233.43

Antoine equation:In ;P%in mm Hg.0in ²C

EXAMPLE 7.1 (Calculation of bubble point,dew point and equilibrium data for an ideal binary
mixture) Cyclo-pentane(A)and benzene(B)form nearly ideal solutions.

(a) Using the vapour pressure equation given in Table 7.2 (and assuming ideal
behaviour), prepare the bubble point,the dew point and the vapour-liquid equilibrium
curves for this binary at 1 atm total pressure.
(b) If one kilomole of a two-phase mixture having 42 mole%A at 68°C is allowed and
1 atm total pressure is allowed to separate into a liquid and a vapour phase at 1 atm
total pressure,calculate the amounts and compositions of the two phases.
(c) Consider an equimolar mixture of A and B at 600 mm total pressure.(i)What is the bubble
point of the mixture and the composition of the initial vapour?(ii)If a small quantity
of the mixture is slowly vaporized in a closed vessel and the vapour remains in contact
and in equilibrium with the liquid,calculate the composition of the last drop of the liquid.
(d) If an equimolar mixture of the compounds has a bubble point of 100°℃,calculate
the total pressure exerted at that temperature at equilibrium.
Solution

(a)The bubble and dew points of mixtures of different compositions remain within 49.2℃
(boiling point of pure cyclo-pentane at 1 atm)and 80°C(boiling point of pure benzene at 1 atm).
The total pressure remains constant at 1 atm(=760 mm Hg).The vapour pressure of a
component is explicitly given as a function of temperature.In order to compute the T-x-y data,
it is convenient to begin with a temperature and to calculate the corresponding liquid and
vapour compositions at equilibrium.A sample calculation is shown below.
Take T=70℃.In PA=15.8602-2589.2/(231.36+70) → PN =1434 mm Hg
In P&=15.9037 -2789.01/(220.79+70)→ Pb=551 mm Hg
Using Eq.(7.6),total pressure,P=760 mm Hg =x(1434)+(1-x)(551)→x =0.237
330 Chapter 7 Distillation

Therefore,at T=70℃ and P=760 mm Hg,the mole fraction of A in liquid at equilibrium

is x =0.237.
Mole fraction of A in the equilibrium vapour,y*=x(PA/P)=(0.237)(1434)/760 =0.447
So the bubble point of a solution having 0.237 mole fraction of A at 1 atm total pressure
is 70℃.This is also the dew point of a vapour having 0.447 mole fraction of A.
The bubble and dew points of liquids and vapours of other compositions are similarly
calculated and plotted in Figure 7.5(a).The calculated x-y*data are plotted in Figure 7.5(b).The
experimental x-y*data are also shown on the same figure.It is seen that the deviation from
ideal behaviour is small.The system is nearly ideal.

(b)The state of the feed (68℃;1 atm;zr=0.42)is represented by the point F that lies in
the two-phase region in Figure 7.5(a).Now the mixture is allowed to separate into a liquid
and a vapour phase at equilibrium.Draw a horizontal line through F that meets the bubble
point curve at L and the dew point curve at V.The abscissa of the point L(x)gives the
composition of the liquid;that of the point V(y*)gives the composition of the equilibrium
vapour.From Figure 7.5(a), we get x=0.294,y*=0.521.

Bubble point(Ta),°C; Dew

point(To)°c

(a)

y
(

Figure 7.5 (a)The calculated T-x-y'data(Raoult'slaw)for cyclo-pentane-benzene mixtures,and (b)the experimental x-y*
data from Mayers,Ind.Eng.Chem.48(1956)1104.
 Vapour-Liquid Equilibrium 331

To calculate the amounts of the liquid and vapour phases produced on phase
separation,use the following material balance equations.Total amount of the mixture is F=1
kilomole.
F=L+V→ 1=L+V and Fzr=Lx+Vy*→(1)
(0.42)=L(0.294)+V(0.521) Solving the preceding material balance equations,
Moles of liquid,L= |0.555 kmol and moles of vapour,V= 0.4
(c)Consider an equimolar mixture of the components (i.e.x =0.5)at 600 mm Hg total pressure.
(i)If the bubble point is 0,using Eq.(7.6)and the given vapour pressure equations,we
can
write

Solving this equation,the bubble point of the equimolar mixture at 600 mm Hg pressure is

0= 54°
At 54°℃,the vapour pressures of the individual compounds are:
PN=885.7 mm Hg; Pb=315.3 mm Hg
From Eq.(7.7),the composition of the initial vapour,
y*=PAx/P=(885.7)(0.5)/600 = 0.738 mole fraction
(ii)Composition of the last drop of liquid remaining: When all the liquid is vaporized
except a tiny drop of it,the vapour composition is virtually the same as that of the initial
liquid, i.e.y₄=0.5,yg=0.5.In other words,the equimolar vapour containing A and B is at
its dew point.Let us first calculate this dew-point temperature.
If x is the mole fraction of A in the last drop of the liquid (which is in equilibrium with
the vapour of y =0.5),then
Partial pressure of A in the vapour =Py₄=PAxA→(600)(0.5)=300 =PKxA
Similarly,the partial pressure of B in the vapour,
Eliminating x₄from the above two equations, .Putting
the expressions for, and. (the vapour pressure equations)and solving for θ,we have
θ=61.4℃.
Atθ=61.4°C,PN=1114 mm Hg and Pg =411.3 mm Hg.
Then the liquid composition,x₄=Py₄/PA=(600)(0.5)/(1114)=0.27

The last drop of liquid contains 27 mole%of cyclo-pentane(A).

(d)Vapour pressures of the components at 100°℃ are:
PN=3120.2 mm Hg; Pg=1350.5 mm Hg
The equilibrium total pressure exerted above an equimolar mixture at 100℃ is given by

P=P{xA+P}(1-xp)=(0.5)(3120.2)+(1350.5)(1-0.5)= 「2235.3 mm Hg
[Note:The problem can also be solved using the K-values of the components;see Section 7.1.6]

7.1.4 Deviation from Ideality and Formation of Azeotropes

Qualitative criteria of ideal behaviour of a solution have been listed in Section 4.3.1.As a
matter of fact,most solutions do not exhibit ideal behaviour.In other words,they show
deviations from
332 Chapter 7 Distillation

ideality.Deviations may be of two types—positive deviation and negative deviation.A liquid

mixture exerting an equilibrium total vapour pressure more than that calculated by Eq.(7.6)is
said to exhibit a positive deviation from ideality'.If the total vapour pressure is less than that
calculated from Eq.(7.6),the deviation is called a 'negative deviation'.
Two extreme cases of deviation from ideal behaviour lead to what are called azeotropes.If
there is a large positive deviation from ideality and the vapour pressures of the components A
and B are not much different,the total pressure curve may pass through a maximum at a certain
liquid concentration.A liquid mixture of such character and composition is a constant
boiling mixture'+and is called a minimum boiling azeotrope.The x-P and y*-P curves touch
at the azeotropic composition(at the azeotropic point x =y*);the x-T and y*-T curves pass
through a common minimum.This is why such an azeotrope is called minimum boiling.The
equilibrium curve(x-y*)crosses the diagonal line at the azetropic composition.The equilibrium in
a minimum boiling binary azeotropic system is shown in Figure 7.6.

Equilibrium
pressure

(a)

(b)

Figure 7.6 Isothermal vapour-liquid equilibrium diagram of a minimum-boiling azeotrope (ethanol-benzene,40C):(a)bubble

point pressure,and (b)equlibrium diagrams.

+A constant boiling mixture'generates vapour of a composition equal to that of the liquid.So the
liquid composition and the boiling temperature remain the same even if a part of the liquid is boiled
out.Such a mixture cannot be separated by ordinary distillation.
 Vapour-Liquid Equilibrium 333

Similarly,if the deviation from the ideal behaviour is negative and large,the partial
pressures of the individual coefficients are less than the ideal values.The plots of the total
pressure against the liquid and the vapour compositions at a constant temperature pass
through a common minimum at the azeotropic point [Figure 7.7(a)].The corresponding x-
y*diagram is shown in Figure 7.7(b).An azeotrope exhibiting such behaviour is called
maximum boiling because the boiling temperature at the azeotropic point is maximum if the
total pressure is held constant.

Total pressure (P), mm

Hg

(a) 1.0γ

0.8 x,y

0.6
y
0.4|

0.2
Q₁
0.00.0

Fo₂ Azeotropic point,x=y*

0.2 0.4 0.6 0.8 1.0

x
(b)

Figure 7.7 Isothermal vapour-liquid equilibrium diagram of a maximum-bolling azeotrope,acetone(A)-chloroform(B)at 55°C.

7.1.5 Relative Volatility

Relative volatility of a component A in a mixture indicates the ease of its separation from
another component B.It is defined as the concentration ratio of A to B in the vapour divided by
the same
ratio in the liquid phase.It is usually denoted by a.For a binary mixture,

(7.8a)

→ (7.8b)
334 Chapter 7 Distillation

If A is the more volatile component in the mixture,a is larger than 1(this is not true over
the entire range of concentration if the system is azeotropic).Using Eqs.(7.5)and (7.7),the
relative volatility a(=aAB)in an ideal binary solution can be expressed in terms of the vapour
pressures of the components,i.e.

te mio of apourpresars of And (7.9)

In a multicomponent mixture,the relative volatility of component i with respect to component

j is given by

(7.10)

The quantity ai gives a measure of the degree of enrichment of component i in the vapour
compared to component j when a liquid mixture is partially vaporized.Its definition has been
extended to other equilibrium separation processes as well.In mass transfer operations like
extraction,membrane separation,etc.a quantity similar to a is called the separation factor.

7.1.6 Equilibrium in a Multicomponent System

Separation of multicomponent mixtures rather than binaries is much more common in the
chemical process industries.Experimental VLE data for most multicomponent mixtures are not
available and have to be computed by using the available equations or correlations.The
job becomes pretty simple if we have an ideal multicomponent system so that Raoult's
law is applicable.Hydrocarbons of a homologous series form nearly ideal solutions.For
the ith component in an ideal solution,we can write

yjp=i=yPY amd (7.11)

(7.12)
→

where,P”=vapour pressure of component j at the given temperature

At a given temperature,the vapour pressures of the components,P""s are known.Therefore,
for a particular liquid composition(i.e.given for given values of xj,x₂,…,Xn),the
vapour compositions(yi,y₂.…,yn)can be calculated.Noting that aj =PYIP',Eq.
(7.12)can be rewritten as

(7.13)
 Vapour-Liquid Equilibrium 335

Once the equilibrium vapour phase mole fractions are known,the partial pressures and
the total pressure can be calculated from Eq.(7.11).
For hydrocarbon mixtures,a quantity called equilibrium vaporization ratio(denoted by
K; for the ith component)is extensively used for VLE computation.It is defined as

(7.14a)

Distillation calculations,including the bubble and dew point calculations,can be done using
the K-values,if available.The DePriester chart [Figures 7.8(a)and (b)]may be conveniently used
to obtain K-values for lower hydrocarbons at different temperatures and pressures.

Figure 7.8(a) DePriester chart-hightemperature range.

336 Chapter 7 Distillation

Figure 7.8(b) DePriester chart-low temperature range.

The computation of the bubble point,the dew point and equilibrium in a multicomponent
mixture involves an iterative approach. We describe here a technique using the equilibrium
vaporization ratio,K(more about this quantity for real solutions is given in the Appendix).
Bubble point calculation: In an n-component mixture,let us select the rth component as the
'reference component'.The relative volatility of the ith component with respect to the rth is given
as

Therefore, (7.14b)
 Vapour-Liquid Equilibrium 337

In a bubble point calculation problem,the liquid composition is known and the total pressure
is given.We start with an assumed temperature and calculate the vapour pressures or K-values
of all the components.Then we can calculate the values ofyi=K;x;(=x;PYIP if the solution is
ideal). At the bubble point,the sum of the yi's should be unity,i.e.

(7.15a)

The boiling point of the reference substance may be taken as the initial guess.The values
of K;(i=1,2,.…r,.…,n)and air are calculated at this temperature and put in Eq.[7.14(b)]
to get a revised value of K,.We use this revised value of K,to determine the second approximation
to the bubble point.Computation is repeated till Eq.[7.14(b)]is satisfied to the desired degree
of accuracy.The computational procedure is illustrated in Example 7.2.

EXAMPLE 7.2 (Calculation of the bubble point of an ideal multicomponent mixture) Calculate
the bubble point of an ideal solution containing 20 mole%n-pentane(1)and 40 mole%each of
n-hexane(2)and n-heptane(3)at 1.5 bar total pressure.Use the vapour pressure equation
given in Table 7.2.
Solution
Step I: Calculate the average molecular weight of the mixture.
Since M₁=72,M₂=86,and M₃=100,Mav =(0.2)(72)+(0.4)(86)+(0.4)(100)=88.8.
This is close to the molecular weight of n-hexane.We select n-hexane as the reference
component.
Step 2: Calculate the boiling point of the reference component(i.e.n-hexane)at the given
pressure(1.5 bar =1125 mm Hg).From the Antoine equation,
In(1125)=15.9155-2738.42/(θ+226.2)→θ=82℃ →T=355 K

Take this temperature as the first approximation of the bubble point of the mixture.Calculate
the relative volatility of the other components—n-pentane (1)and n-heptane (3)—with respect
to the reference component,i.e.n-hexane(2).
At 355 K,vapour pressure of n-pentane,
In Pǐ=15.8365-2477.07/(82 +233.21)→PY=3.8604 bar
Vapour pressure of n-heptane,
In Py=15.877-2911.32/(82 +226.65)→P³=0.6066 bar
Since the solution is ideal,α₁2=P|IP2=3.8604/1.5 =2.5736;α₃₂=0.6066/1.5 =0.4044
Now use Eq.[7.14(b)].
338 Chapter 7 Distillation

Step 3: We have to recalculate the whole thing taking the above 'revised value'of K..
K=PZ/P;P=1.5 bar;i.e.0.9289 =PZ/P=P²/1.5
→ PZ=(0.9289)(1.5)=1.3934 bar =1045.4 mm Hg
Recalculate the boiling point of the reference component,n-hexane(2),at 1.3934 bar pressure
In(1045.4)=15.9155-2738.42/(0+226.2)→=79.5℃ →T=352.5
K Vapour pressures of the other two components at this temperature (352.5 K)are:
n-pentane:PY=3.625 bar; n-heptane:Pg=0.5586 bar
K-values are:K₁=3.625/1.5=2.4167; K₂=K,=0.9289; K₃=0.5586/1.5 =0.3724
Step 4: Check if the recalculated K-values satisfy Eq.[7.15(a)].

This is good enough.Another cycle of calculation may be done if still better accuracy is desired.
Dew point calculation: For the calculation of the dew point of a vapour of known
composition,i.e.known y;'s,we may start with an assumed value of the dew point,and obtain
the vapour pressures(or K-values)of all the components at this temperature.Since the total
pressure is given,we can calculate the mole fractions of the components in the liquid
phase, x;=y;/Kj.(=y;P/P),if the solution is ideal).If the assumed temperature is the correct dew
point, the sum of x's must be unity.The following equations may be used for an efficient
iterative computation.

(7.15b)

One of the components is selected as the reference component and the boiling point of the
reference component is taken as the initial guess of the dew point of the vapour mixture.The
vapour pressures and the values of air of all the components are calculated at this assumed
temperature and substituted in Eq.[7.15(b)].A revised value of K,and the corresponding tempera-
ture are then obtained.This is the second approximation to the dew point.The computation
is repeated till the desired accuracy is achieved.The procedure is illustrated in Example 7.3.

EXAMPLE 7.3(Calculation of the dew point of an ideal vapour mixture) Calculate the dew
point of a vapour containing 15 mol%n-butane(1),15 mol%n-pentane(2),20 mol%cyclo-
hexane(3),20 mol%n-hexane(4)and 30 mol%n-heptane(5)at 1.5 bar total pressure.Raoult's
law applies.Use Table 7.2 to calculate vapour pressures of the components.
Solution

Step I: Calculate the average molecular weight of the vapour mixture.The molecular weights
of the individual components are:M₁=58,M₂=72,M₃=84,M₄=86,and Ms =100.
Average molecular weight,
Mav =(0.15)(58)+(0.15)(72)+(0.20)(84)+(0.20)(86)+(0.30)(100)=83.6
 Vapour-Liquid Equilibrium 339

This is close to the molecular weight of cyclo-hexane(3).Take this as the reference

component. Calculate the boiling point of cyclo-hexane(3)at 1.5 bar pressure (=1125 mm
Hg =given
total pressure)using the vapour pressure equation,
In(1125)=15.7794+2778/(θ+223.14)→T =367.5 K
Take 367.5 K(94.3°℃)as the first approximation of the dew point of the mixture.
Step 2: Calculate the vapour pressures of the other components at the assumed bubble
point, 367.5 K.
n-Butane: InP”(1)=15.68151-2154.9/(94.3+238.74)→P(1)=9985.8 mm Hg=13.31 bar
Similarly, P'(2)=5.211 bar; P(4)=2.122 bar; P”(5)=0.8978 bar
The relative volatilities(with respect to the reference component,cyclo-hexane)are:

α₁₃=P”(1)/ =8.873;α₂₃=P”(2)/P”(3)=5.211/1.5 =3.474;

P”(3)=13.31/1.5 =1.415;αs₃=P”(5/P°(3)=0.8978/1. =0.5985
α43=P(4)/P~(3)=2.122/1.5 5

rom Ea a1n
→

Now K₃=P”(3)/P →0.9027 =P(3)/1.5

→ P”(3)=(0.9027)(1.5)=1.354 bar (=1016 mm Hg)
From Antoine Eq.for cyclo-hexane (3),
In(1016)=15.7794-2778/(0+223.14)→T=363.8 K

Step 3: Take T=363.8 K(=90.6°C)as the second approximation to the dew point of
vapour mixture.Calculate the vapour pressures of the other components at this temperature.
n-butane:In P”(1)=15.68151 -2154.9/(90.6+238.74)→P(1)=12.3772 bar
Similarly,at T=363.8 K,P(2)=4.7802 bar;P(4)=1.417 bar;P(5)=0.5924 bar.
Now calculate the K-values of all the components at T =363.8 K.
K₁=P”(1)/P=12.3772/1.5 =8.2514
K₂=P”(2)/P=4.7802/1.5 =3.187
K₃=P”(3)/P=1.354/1.5 =0.9027
K₄=P(4)/P =1.9188/1.5 =1.279
Ks =P^(5)/P=0.8021/1.5 =0.5347

Step 4: Use these K-values to check if Eq.7.15(b)is satisfied.

 Vapour-Liquid Equilibrium 339
So Eq.7.15(b)is satisfied.The bubble point is 363.8 K.Another iteration may be done
if further accuracy is desired.
340 Chapter 7 Distillation

7.1.7 Equilibrium in a Nonideal System

Equilibrium in a real system cannot generally be represented by Raoult's law or the Henry's
law*.At equilibrium,the fugacities of the component i in the vapour and in the liquid phase are
equal,i.e.
fY=f! (7.16a)
The two fugacities are given by
fY=φY y;P (7.16b)
f|=x;φ{P=x;Yf" (7.16c)
where
φ”=the fugacity coefficient
Yi=the activity coefficient of component i in solution
f?=fugacity of component i at standard state.
For low-to-moderate pressures,the fugacity at standard state can be approximately taken
as the vapour pressure of a component at the prevailing temperature,i.e.
f{=x;Y;P} (7.16d)
Thus at a equilibrium
φYy;P=x;Y;PY
(7.17) Here PY is the vapour pressure of component i at the given temperature.For a known
liquid composition(i.e.known x;),the activity coefficient γ;can be calculated using a suitable
equation (for example,the Wilson equation)or technique(e.g.UNIFAC).If the pressure is
'low',the vapour phase may be considered‘ideal'(φ”=1)and the corresponding vapour
phase composition can be calculated directly from Eq.(17.17).If the pressure is above
moderate,non- ideality of the vapour-phase has to be taken into account and the fugacity
coefficient φ"of the component has to be calculated using a suitable equation of state.Since
φ"depends upon the vapour composition(i.e.y;)an iterative approach is necessary.This is
illustrated in the Appendix.
In the following discussion we shall explain and illustrate the principles of distillation either
assuming a solution to be ideal or using experimental vapour-liquid equilibrium data.This will
be done in order to make the presentation simple and easily understandable.However,for
problems involving non-ideal solutions,either experimental equilibrium data or that
calculated using fugacity and activity coefficients of the components should be used.For
obvious reasons, experimental multicomponent equilibrium data available in the literature are
scanty and calculated equilibrium data are almost invariably used in process design.

7.2 ENTHALPY-CONCENTRATION DIAGRAM

A change in the composition of a phase during distillation is accompanied by a change in
its enthalpy.Enthalpy-concentration diagrams of liquid and vapour phases in equilibrium are
useful in distillation calculation.For a given temperature T and concentration x of a liquid,the
molar enthalpy H,can be calculated using the following equationt.
HL=CpsMa(T-To)+△H₅ (7.18)
”Henry's law describes a real system only at low concentrations.In a sense,this law is also a kind of
idealization. +We take the following steps to get a solution of specified composition.The components are
mixed at the reference temperature.The enthalpies of the pure components are zero at the reference
temperature.The only heat effect occurs due to the release of the heat of solution.The mixture is then heated to
the required temperature.
 Enthalpy-Concentration Diagram 341

where
H₁=molar enthalpy of the solution at temperature T,in kJ/kmol
Cps=specific heat of the solution,in kJ/kg:K
Maw =average molecular weight of the solution
T₀=reference temperature
△H₅=heat of solution at the reference temperature To,in kJ/kmol.
Since the heat of mixing of the vapour is negligible,we can use the following equation++to
calculate the molar enthalpy of the saturated vapour Hy at a given temperature T and
concentration y*.
Hy=y*M₄[CpA(T-To)+λ₄]+(1-y*)Mg[cpg(T-T₀)+λg] (7.19)
where
CpA,CpB=specific heats of the pure liquids A and B,in kJ/kg-K
A₄,λg=heats of vaporization of A and B at temperature T,in kJ/kg.
The calculation of enthalpies of solutions and vapours is illustrated in Example 7.4.

EXAMPLE 7.4(Calculation of enthalpy-concentration data) Enthalpy-concentration

data have
to be calculated for acetone(A)-water(B)system at 1 atm total pressure.The integral heat
of solution(at 15°℃)at different concentrations,the specific heats of solutions and the x-y*data
are given below(x,y*=mole fractions of acetone in solution and in the equilibrium
vapour respectively).
Temperature, X y* △H₈
Cps
θ (C) (kcal/kmol) (kcal/kg·K)
56.5 1.0 1.0 0 0.54
57 0.95 0.963 0 0.56
57.5 0.90 0.935 -10.55 0.56
58.2 0.80 0.898 -23.88 0.61
58.9 0.70 0.874 -41.11 0.66
59.5 0.60 0.859 -60.3 0.70
60 0.50 0.849 -83.56 0.75
60.4 0.40 0.839 -121.5 0.80
61 0.30 0.83 -171.7 0.85
62.2 0.20 0.815 -187.7 0.91
66.6 0.1 0.755 -159.7 0.96
75.7 0.05 0.624 -106.8 0.98
91.7 0.01 0.253 -22.2 1.0
100 0.0 0.0 0 1.0

The other relevant data:average specific heat of liquid acetone,cpA =0.57 kcal/kg-K;
average specific heat of water,Cpb =1.0 kcal/kg·K;heat of vaporization of acetone,
λ₄=125.8-0.252(θ-50)kcal/kg;θ=temperature in ℃;average heat of vaporization
of water,λg=550 kcal/kg
Solution
The enthalpy-concentration data can be calculated by using Eq.(7.18)for a solution and
Eq.(7.19)for a vapour.We select a reference temperature,T₀=15℃(at which the integral
heats
of solution are given).Sample calculations for a solution and for the equilibrium vapour are shown.

t+It is assumed that the individual components are heated to the temperature T from the reference
temperature To,followed by vaporization and mixing of the vapours.
342 Chapter 7 Disillation

Consider a solution having 20 mole%acetone(T =62.2℃),i.e.xA

=0.20.Molecular weights:acetone-58;water-18.Average molecular weight of the
solution,Mav=(0.20)(58)+ (0.80)(18)=26.From Eq.(7.18),
H₁=CpsMa(T-T₀)+△H₅=(0.91)(26)(62.2 -15)-187.2 =
929 kcal/kmol solution
Calculate Hyfrom Eq.(7.19)at 62.2°C (composition of the equilibrium vapour:yf=0.815,
given)
Hv=y₄M₄LCp₄(T-T₀)+λ₄]+(1-y₄)Mg[cpg(T-T₀)+λg]
=(0.815)(58)[(0.57)(62.2 -15)+{125.8-(0.252)(62.2 -
50)}] +(1-0.815)(18)[(1)(62.2 -15)+550]
9056 kcal/kmol vapour

The enthalpy values at other concentrations have been calculated.Some of the values are
given below.The enthalpy values have been plotted in Figure 7.9(a)
x 1.0 0.90 0.80 0.60 0.20 0.10 0.05 0.01 0.0
y* 1.0 0.935 0.898 0.859 0.815 0.755 0.625 0.253 0.0
H₁ (kcal/kmol) 1300 1297 1294 1248 929 930 1083 1390 1530
Hy(kcal/kmol) 8500 8722 8812 8916 9056 9259 9659 10,754 11.250

The typical x-Ht and y*-Hy curves (system:methanol-water)are also shown in Figure
7.9. A point in the region below the x-Ht curve represents a liquid(a point on the x-Ht
curve represents a saturated liquid,i.e.a liquid at its bubble point).A point in the region
above the y*-Hy curve represents a vapour(a saturated vapour if the point is on the y*-Hy
curve).A point, say F,in the region between the two curves represents a two-phase vapour-
liquid mixture.The mixture tends to separate into a liquid and a vapour phase at equilibrium
represented by the points W and D on the 'tie line'through the point F [comparable to the tie
line LV in Figure 7.3(a)]]. The amounts of the liquid and vapour phases can be determined by
the Lever-arm Rule,Eq.(7.4). The line IJ is another tie line.The point R on the(x-y*)diagram
[Figure 7.9(b)]drawn below the H-x-y"diagram corresponds to the tie line WD;the point Q on the
equilibrium diagram corresponds to the tie line IJ on the enthalpy diagram.
Similarly,let us take two solutions whose states (given by the enthalpies and compositions)
and amounts are both represented by M and N.The solutions are mixed to produce another
solution having its state and composition represented by the point P [Figure 7.9(a);here the point
P represents a stream by composition as well as by flow rate and should not be confused with
total pressure].Following the nomenclature used before,we may write the material and enthalpy
balance equations as given below.

Total material balance: M+N=P (7.20)

Component A balance: (7.21)
MzM+ NzN =Pzp
Enthalpy balance: MHM+NHN=PHp (7.22)
Here z stands for the concentration of the species A in a phase and H is its molar
enthalpy (the notation z,instead of x,has been used because the phases represented by the
points M and N may be two-phase mixtures in the general case).
 Enthalpy-Concentration Diagramn 343
15000
kcal/kmol
y*-Hrcurve P N₀
M
D
10000 J

Tie lines
H,H
(a)△(H y
5000
Ff A(Hp)₁
x-HL curve
W

0 ly*
1.0 x,y*

9
0.8

(b) 0.6
y*
R」 Equilibrium
0.4 curve (x,y*)

0.2

0.0
0.0
0.2 0.4 0.6 0.8 1.0
x

Figure 7.9 (a)Enthalpy-concentration(x-y*-H),and (b)equilibrium diagrams for the methanol (1)-water(2)system

[Henley and Seader,1982].▲—enthalpy of liquid;→—enthalpy of vapour.

Eliminating P from Eqs.(7.20)and (7.21), (7.23)

Similarly,eliminating P from Eqs.(7.20)and (7.22), (7.24)

→ (7.25)

The left-side of Eq.(7.25)gives the slope of the section NP and its right-side gives that of
MP [Figure 7.9(a)].So the points M,N and P are collinear.The relation among the
points M,N and P may be viewed in another way as well.If we have a mixture represented by
the point P(in respect of both state and amount),and we remove a part of it represented by the
point M (again in respect of both state and quantity),the part of P left behind should have
enthalpy and composition represented by the point N.
After this brief introduction to the relevant physico-chemical principles,we shall
now discuss the principles of the more important distillation operations.
344 Chapter 7 Distillation

7.3 FLASH VAPORIZATION(ALSO CALLED FLASH DISTILLATION)

If a sufficiently hot liquid mixture is throttled into a vessel,a part of it will vaporize.The
vapour produced will be richer in the more volatile component(s)and thus partial separation
of the desired component(s)will be achieved.This is called flash vaporization or equilibrium
vaporiza- tion.A schematic sketch of a flash vaporization unit is shown in Figure 7.10.The
feed is first heated in a heat exchanger under pressure and then led to a flash drum by throttling
where partial vaporization of the feed occurs under reduced pressure.The vapour leaves the
drum at the top
and is condensed to get the top product.The
fraction having a higher concentration of the less
volatiles leaves the drum as a liquid bottom prod-
uct.Liquid droplets are formed when a part of the
liquid flashes into a vapour vigourously.The flash
drum should have internals like baffle plates in
order to reduce 'entrainment'of liquid droplets in
the outgoing vapour stream.Pressure in the drum
is suitably adjusted.It is often assumed that the
liquid and vapour streams leaving the flash drum
are in equilibrium(the process is also called equi-
librium vaporization).But the phases may not
reach equilibrium in reality.Flash vaporization is a
single-stage distillation operation.However,the
bottom product(or even the condensed top
product)from the flash drum may be heated and
Figure 7.10 Schematic of a flash distillation unit.
flashed again in a second unit to get a
purer product.

7.3.1 Flash Vaporization of a Binary Mixture

We start with a binary mixture of the components A and B.If the flow rate,the composition,
and enthalpy of the feed,the condensed top product (or distillate)and the bottom liquid product
are denoted as (F,zp,Hp),(D,xp+,Ho),and (W,xw,Hw),respectively,and Q is the rate of supply
of heat to the heat exchanger,we may write the following material and energy balance equations
for a steady-state equilibrium vaporization unit.
Total material balance: F =D+W (7.26)
Component A balance: Fzr=Dxp+Wxw (7.27)
→ (D+W)zp=Dxp+Wxw (7.28)
Enthalpy balance: FHp+Q=DHo+WHw (7.29)
Eliminating F from Eqs.(7.26)and(7.29)and using Eq.(7.28),we have

(7.30)

+The vapour leaving the flash chamber is condensed into a liquid.So its composition is denoted by
xp.The subscript ‘D'stands for the distillate.
 Flash Vaporization(Also Called Flash Distillation) 345

Binary flash vaporization problems can be solved by graphical construction and the above
equation is extremely useful for this purpose.Vapour-liquid equilibrium data and also the
enthalpy-concentration data are required for the graphical construction and calculations.The
cold feed (if the feed is below its bubble point under the given pressure,it is called cold feed)
is represented by the point F,on Figure 7.11(a)under Example 7.6.The feed passes through the
heat exchanger and receives an amount of heat energy Q.The state of the hot feed is
represented by the point F that lies in the two-phase region of the H-x-y diagram.It flashes
into a vapour and a liquid phase upon throttling into the flash drum.The enthalpy and the
composition (in terms of mole fraction of A)of the vapour and the liquid streams,denoted by
the points D and W,are obtained by drawing the tie line through F.The point F'(zr,zr)is
located on the diagonal on the x-y plot [see Figure 7.11(b)under Example 7.6],and the point
P is located on the equilibrium curve such that the slope of the line F'P is-W/D by virtue of
Eq.(7.30).The line F'P is,in fact, the operating line'for the single-stage flash vaporization
process.
By using the enthalpy and equilibrium curves,the amounts and the compositions of the two
products can be calculated for a given feed for the given rate of heat supply,Q.Alternatively,
if the fraction of feed to be vaporized is specified,the required rate of heat supply Q can be
calculated.In the above analysis,we have tacitly assumed that the flash vaporization represents
an ideal stage.The analysis can be easily extended to the case of a real stage of given stage
efficiency.The stage efficiency typically ranges between 0.8 and 1.0.
Single-stage flash calculations are illustrated in Examples 7.5 and 7.6.

EXAMPLE 7.5(Binary fash distillation) A mixture of 40 mol%benzene and 60 mol%toluene

is being flash-distilled at a rate of 10 kmol/h at 1 atm total pressure.The liquid product
should not contain more than 30 mol%benzene.Calculate the amounts and the compositions
of the top and the bottom products.The relative volatility of benzene in the mixture is
2.5.Solve analytically as well as graphically.
Solution
Refer to Figure 7.10.
Algebraic solution
Total material balance: F=D+W; given:F=10,zp=0.4→ 10=D+W (i)

Benzene balance: Fzp=Dxp+Wxw

Given:xw=mole fraction of benzene in the bottom product =0.3
→ (10)(0.4)=Dxp+W(0.3) i.e. 4=Dxp+(0.3)W (ii)
In equilibrium flash distillation,the distillate(vapour)and the bottom products (liquid)are in
equilibrium,i.e.xp and xw are in equilibrium,and are related through the relative volatility
as
follows:

(iii)

4.61
Equations (i),(ii)and(iii)can be solved for
the three unknowns to
get:
D= W=
5.39 mol/h 0.517
346 Chapter 7 Distillation

Graphical solution
The equilibrium line is plotted using the given value of the relative volatility [see Eq.7.8(b)].

ie.
The point F(zr,zr),i.e.(0.4,0.4)is located on the diagonal,and the vertical line through
xw=0.3 meets the equilibrium line at P(0.3,0.52).The slope of the line FP equals
(-W/D).Calculations are left as a small exercise problem.

EXAMPLE 7.6(Calculation of the energy requirement in binary flash vaporization) Fifty kmol
of 35 mole%aqueous solution of acetone at 25°C is heated and flashed in a drum at 1 atm
pressure when 35%of the liquid is vaporized.Using the enthalpy-concentration data
of Example 7.4,calculate (a)the amounts and the concentrations of the vapour and liquid
products, and(b)the heat supplied to the feed.
Solution
(a)Let F(=50 kmoles;zr=0.35)be the moles of feed,and W and D be the moles of liquid
and vapour products.Fraction of liquid vaporized =0.35.Therefore,
DIF=D/(W+D)=0.35 → WID=1.86

(i)Locate the point F'(zp,zp)on the x-y diagram drawn below the enthalpy-
concentration diagram in Figure 7.11(b)and draw a line F'P of slope-WID=-1.86 through the
point F'which meets the equilibrium curve at P.
Concentration of acetone in the liquid product,xw= 0105 ;that in the(condensed)vapour

product,xp= 0.765

We have W+D= and W(0.105)+D(0.765)=(50)

(0.35) 18.56 kmol
→
50 31.44
kmol

(b)Draw the tie line WD on the enthalpy-concentration diagram corresponding to the point
P.A vertical line through F'meets WD at the point F [see Figure 7.11(b)].The coordinates
of the
point F are (zr,Hr+QIF).
From Figure 7.11(b),Hp+QIF=4000 kcal/kmol
Average molecular weight of the feed is 32.The integral heat of solution is taken as △H=
-145 kcal/kmol and cps=0.825 kcal/kg.K(interpolated from the data of Example
7.4).Taking a reference temperature of 15℃,the en thalpy of the feed(x₄=0.35;temp.,T
=25℃)is
Hp=(0.825)(32)(25-15)-145 =119 kcal/kmol

→
119+Q150=4000→Q=| 1.94×10⁵kcal =required heat input
 12000
y-Hy
10000 D
8000
Flash Vaporization(Also Called Flash Distillation) 347
6000
(a)
4000

x-Hr
Enthalpy FnzpHp+Q/F
(H,H),kcalkmol
2000
400 、

0上 W
x,y
1.0- F
0.8
xp=0.765
Equil.diagram Pk
(x,y*)
0.4
0.6 (b) y
F”(zzp)
Slope =-W/D=-1.86
rp=0.105
0.0 ·
0.0 0.2 0.4
x
0.2

0.6 0.8 1.0

Figure 7.11 (a)Enthalpy-concentration,and (b)equilibrium diagram of acetone-water system at 1 atm pressure.

7.3.2 Multicomponent Flash Distillation

We shall now analyze flash vaporization of an n-component mixture.For simplicity,we assume

that vapour-liquid equilibrium of the multicomponent mixture can be quantitatively described
by K-values (see Section 7.1.6).The material balance equations for the component i are given
below (the notations are the same as in the previous section;an additional subscript i is used to
denote the ith component).

Total material balance: F=D+W (7.31)

Component i balance: Fz=Dxpi+Wxwi (7.32)
348 Chapter 7 Distillation

Eliminating F from Eqs.(7.31)and (7.32),

(7.33)*

Putting xwi=yp;/K;[see Eq.(7.14a)]and simplifying,

→ (7.34)

The above equation can also be written for xwi by putting yoi =K;xwr

(7.35)

If we define a vaporization ratio (it is the ratio of the moles of liquid to the moles of
vapour produced on phase separation)as f=WID,we may write

(7.36)

If the temperatures of the flash drum and the feed composition are known,K's can be
calculated from the vapour pressure equations (or the De Priester chart,Figure 7.8),and
Eq.(7.36)can be solved by using any suitable numerical technique to calculate f,i.e.the
fraction of liquid vaporized on flashing (see Example 7.7).
It is rather simple to determine if a mixture would at all flash into two phases.We may
specify the following conditions in this regard.

(7.37)

(7.38)

If the above two inequalities are satisfied,the mixture would separate into two phases
under the given conditions.

EXAMPLE 7.7(Multicomponent flash distillation) We have a mixture of 25 mol%n-hexane(1),

40 mol%n-heptane(2)and 35 mol%n-octane(3)at 400 K and 2 bar total pressure.Will
the mixture separate into two phases?If so,calculate the amounts and the compositions of
the liquid and the vapour products.Assume the solution to be ideal.See Table 7.2 for the
Antoine constants.
Solution
Vapour pressure of n-hexane(1)at 400 K (=127°℃):
In P(1)=15.9155-2738.42/(127+226.2)=3490 mm Hg =4.652 bar

*Since the vapour generated on flashing is completely condensed,the composition of the condensate is the
same as that of the vapour (xpr=yoi).
 Flash Vaporization(Also Called Flash Distillation) 349

Vapour pressures of the other two components are:P”(2)=2.177 bar and P”(3)=1.05 bar.
If we assume ideal behaviour,the vaporization equilibrium constants are:
K₁=P(1)/ =2.326
P=4.652/2.0 [The K-values can also be obtained from Figure 7.8.]
K₂=1.0885;K₃=0.52
5
Composition of the mixture:z₁=0.25; z₂=0.4; z₃=0.35.
Now.

Since the conditions of existence of two phases [Eqs.(7.37)and (7.38)]are satisfied,the

mixture will split into two phases.The fraction of vapour is to be calculated by solving Eq.
(7.36),
i.e.

The solution of the above equation gives the vaporization ratio,f=0.812.

Taking F=1 kmol=D+Wandf=W/D=0.812,W and D can be easily calculated.The
compositions of the liquid and vapour products can be obtained from Eqs.(7.34)and
(7.35).
A simpler technique of flash calculations was suggested by Eubank et al.(2000).If ζ is
the fraction of the feed vaporized in the flash chamber,

(7.39)

From Eqs.(7.35),(7.36)and (7.39),

(7.40)
→

It is easy to establish that dylaξ<0 for positive values of ζ(in fact,ζ lies between 0 and
1).So Eq.(7.40)has a unique solution within .The root of Eq.(7.40)can be obtained
by a numerical technique like the Newton-Raphson"method.It is interesting to note that for a

See the Appendix for more about the solution of Eq.(7.40).

350 Chapter 7 Distillation

ternary mixture,Eq.(7.40)reduces to a quadratic algebraic equation.If we put the data of

Example 7.7 in Eq.(7.40),we get

The vaporization ratio,f=(1-ζ)/ξ=(1-0.552)/0.552 =0.812.

7.4 STEAM DISTILLATION

When a solution boils,the mole fraction of a component A in the vapour(y*)depends upon

its mole fraction in the liquid(x).If the solution is an ideal binary,the vapour phase mole
fraction of A is given by Eq.(7.7).However,if the components A and B are not miscible,their
mixture
exerts a total vapour pressure which is equal to the sum of the vapour pressures of the individual
liquids at the given temperature.So the bubble temperature of such a mixture is lower than
the boiling point of either A or B.This property of an immiscible liquid mixture forms the
basis of
steam distillation.
Steam distillation is a separation process in
which live steam is blown through a liquid containing
a com- ponent A(usually having a low volatility and
low solu- bility in water)when A vaporizes
slowly(depending upon its vapour pressure at the
operating temperature) and leaves with the
steam.The compound A is the target compound
which we want to recover in a rea- sonably pure
state.The mixture to be separated may contain
traces of a non-volatile impurity or it may be a
mixture of A and another compound C which is
essentially non-volatile.In some cases steam distilla-
tion is similar to steam stripping.The schematic of a
steam distillation unit is shown in Figure 7.12.The
feed is taken in the distillation vessel or still through
which live steam is sparged at the bottom.The
Figure 7.12 Schematic ofa steam distillation unit.
vapour containing the vaporized product A as well
as steam is led to a condenser.If A has only little
miscibility
with water,the condensate forms two layers(a layer of the target material A and another of
water)and can be easily separated to recover the product.Some loss of heat occurs from the
distillation unit.Energy is also required for heating the feed to its bubble point and for
vaporization of A.A steam coil may be provided in the still to make up such energy requirements
and to avoid condensation of the live steam.Steam distillation may be conveniently used in the
following cases:
· Separation of a high boiling material from a solution.Examples:decolourization/
deodorization of vegetable oils,recovery and purification of essential oils
● Separation and purification of hazardous and inflammable substances like turpentine
· Separation of a thermally unstable substance from a mixture
 Steam Distillation 351

· Separation of volatile impurities from waste water.Examples:removal of ammonia,

volatile organic compounds(VOCs)like halogenated hydrocarbons from waste water.
We consider the following two important cases of calculation of steam requirement for a
steam distillation process.Case 2 is discussed after Example 7.8.
Case 1:The substance A is immiscible with water.The feed contains A and traces of non-
volatile impurities.
Let PY be the vapour pressure of A at the operating temperature,Pg be the vapour
pressure of water(B=water),and P be the total pressure.Since A(the target compound)and
B(water) are essentially immiscible,the total pressure is the sum of the individual vapour
pressures (here the partial pressure of a substance is the same as its vapour pressure).

P=PA+PB → .

If m₄moles of the substance is volatilized out by putting in mg moles of steam,and if

the system operates at equilibrium,we may write

(7.41)
→

However,if the system does not operate at equilibrium,the partial pressure of A will be less than
its vapour pressure.To take into account such a deviation,we define a factor called
vaporizing
efficiency E of the product such that the partial pressure of A in the steam i
phase Equation(7.41)then becomes

(7.42)

The vaporization efficiency usually ranges between 0.6 and 0.9.Equation(7.42)can be used to
calculate the steam requirement for a desired separation.

EXAMPLE 7.8(Simple steam distillation) Geraniol (CloHigO)is an essential oil of commercial

value.It is conventionally purified by steam distillation.A pilot scale unit is charged with
0.5 kg of crude geraniol containing a small amount of non-volatile impurities.Live saturated
steam at 105°C is passed through the still at a rate of 20 kg/h.Calculate the distillation time
assuming that geraniol is immiscible with water.Neglect condensation of steam.The
vaporization efficiency is 0.8.Vapour pressure of water at 105°℃ is 1.211 bar and that of
geraniol(A)is given by
In PA=21.1-7217/T; PM is in mm Hg and T in K.

Solution
From the given equation,vapour pressure of geraniol at 105℃,PA=7.48 mm
Hg. Vapour pressure of water at 105℃(given),
PB=1.211 bar =(1.211/1.013)(760)=908.7 mm Hg
Molecular weight of geraniol,M₄=154.1;moles of geraniol in the feed,m₄=0.5/154.1
= 3.244×10-3 kmol.
352 Chapter 7 Distillation

Use Eq.(7.42)to calculate the moles of steam required,

=0.493 kmol =(0.493)(18)=8.874 kg steam

Steam rate =20 kg/h. Time required =8.874/20 h = 26.6 min

Case 2:The feed is a mixture of A and C;C is an essentially non-volatile substance.A and
C form an ideal solution and are immiscible with water.
Let us start with a feed containing mai moles of A [here the subscript i means initial,and
fmeans final]and mc moles of C.At the operating temperature,the vapour pressure of A is PA
and that of steam is Pb.Since C is non-volatile,mc remains constant.We need to calculate the
amount of steam required to reduce the number of moles of A from mai to m₄r.The
vaporization
efficiency is E.
If the moles of A in the still at any time t is m₄,its mole fraction in C is

(7.43)

Partial pressure of A in the vapour is:P₄=Ex₄PN

If ring is the rate of supply of steam,the rate of volatilization of A may be written as

(7.44)

Substituting for x₄from Eq.(7.43)in Eq.(7.44),rearranging and integrating from t =0,m₄=

mAi to t=t,mA=mAp

(7.45)

Example 7.9 illustrates the theoretical principles discussed above.

EXAMPLE 7.9 (Steam distillation of a substance from a mixture)Thirty kilograms of

crude citranellol (C10H₂oO),an essential oil,is to be purified by steam distillation.The material
contains 20 mass%of the essential oil and the rest constitute non-volatile impurities of average
molecular weight 260.Assuming Raoult's law to apply,calculate the rate of steam supply for
the recovery of 90%of the oil if the batch time is 2 hours.It is estimated that 2%of the inlet
steam condenses to make up the heat losses from the still and also to supply sensible and
latent heat to the oil. The operating temperature is 105°C and the vaporization efficiency is
75%.Vapour pressure of citranellol(A)can be calculated from the equation:In PA(mm
Hg)=21.33-7241/T.
 Batch Distillation(Also Called Differential Distillation or Rayleigh Distillation) 353

Solution
Use Eq.(7.45).Vapour pressure of citranellol at 105°C(calculated from the above equation),
PN=8.8 mm Hg.Total mass of the crude product =30 kg with 20%of the oil.Mol.wt.of the
oil =156.1.

Mass of oil =(30)(0.20)=6 kg =6/156.1 kmol =0.03842 kmol =m₄i

Mass of non-volatile impurities =24 kg =24/260 kmol =0.0923 kmol =mc
90%of the oil is to be recovered.
Moles of the oil left, mAr=(0.03842)(0.10)=0.003842 kmol
Vapour pressure of water(B), Pj=908.7 mm Hg
Vaporization efficiency, E =0.75
Total pressure, P=908.7+8.8=917.5 mm Hg
Putting the values of different quantities in Eq.(7.45),

Heat loss =2%→Actual steam requirement =34.32/0.98 =35 kmol =630 kg

The batch time,t =2 h.Steam rate,mg=35/2 =17.5 kmol/h =315 kg/h

7.5 BATCH DISTILLATION(ALSO CALLED DIFFERENTIAL

Condenser
DISTILLATION OR RAYLEIGH DISTILLATION)

In batch distillation,the feed is charged to the stillpot to which

heat is supplied continuously through a steam jacket or a Vapour
steam coil.As the mixture boils,it generates a vapour
Receiver
richer in the more volatiles.But as boiling
Stillpot
continues,concentrations of more volatiles in the liquid 0 o
decrease.It is generally assumed that equilibrium 0
vaporization occurs in the still.The vapour is led to a
0 o
condenser and the condensate or top product is collected Steam
in a receiver.At the beginning,the condensate will be
pretty rich in the more volatiles,but the concentrations of
the more volatiles in it will decrease as the condensate
Steam condensate
keeps on accumulating in the receiver.The condensate
is usually withdrawn intermittently having products or cuts
of different concentrations.Batch distillation is used
when the feed rate is not large enough to justify installation
of a continuous distillation unit.It may also be used when Figure 7.13 Abatch distilation setup.
the
constituents greatly difer in volatility.Two cases of batch distillation are discussed below.Batch
354 Chapter 7 Distillation

distillation with reflux will be dealt with in Section 7.7.The schematic of a batch distillation
setup is shown in Figure 7.13.

7.5.1 Batch Distillation of a Binary Mixture

Theoretical analysis of batch distillation is based on a'differential mass balance'because the

liquid and the vapour phase concentrations of the components change continuously as distillation
proceeds.Let,at any moment,the number of moles of liquid in the still be L having a mole
fraction x of the more volatile component (i.e.A)and let the moles of accumulated condensate
be D.Concentration of the equilibrium vapour is y*.Over a small time,the change in the amount
of liquid in the still is dL and the amount of vapour withdrawn is dD.The following differential
mass balance equations may be written:

Total material balance: -dL =dD (7.46)

Component A balance: -d(Lx)=y*dD (7.47)
→ -Ldx=y*dD+xdL=y*dD-xdD=(y*-x)dD (7.48)

Equation(7.46)means that the total amount of vapour generated must be equal to the
decrease in the total amount of liquid (note that dL is inherently negative and a negative sign is
used in this equation so that it is consistent with respect to sign).Similarly,Eq.(7.47)means that
loss in the number of moles of A from the still because of vaporization is the same as the
amount of A in the small amount of vapour generated.
Putting dD=-dL in Eq.(7.48)and rearranging,

(7.49)

If distillation starts with F moles of feed of concentration xp and continues till the amount of
liquid reduces to W moles (composition =xw),the above equation can be integrated to give

→
(7.50)

Equation(7.50)is the basic equation of batch data distillation and is called the 'Rayleigh equation'.
If the vapour-liquid equilibrium data(x-y*)are available in a tabular form,the right side of
Eq.(7.50)can be evaluated graphically.If an algebraic relation between x and y*is available,
analytical integration may be possible.For example,if the relative volatility a of A in the binary
mixture is constant (as it happens in the case of an ideal solution),the relation between x and
y*may be obtained from Eq.[7.8(b)].Substituting for y*from Eq.[7.8(b)]in the right-side of
Eq.(7.50),the integration can be performed to have

(7.51a)
 Batch Distillation(Also Called Differential Distillation or Rayleigh Distillation) 355

The integral can be expressed in an alternative,and sometimes more convenient form

(7.51b)
Equation(7.51)involves four quantities—F,W,xp,and xw.If any three of these are known,the
remaining one can be calculated.The average composition(ypav)of the accumulated distillate
(D)can be obtained by a simple material balance.
Fxp=Dyp,av+Wxw and F=D+W (7.52)

EXAMPLE 7.10(Simple batch distillation) A charge of 50 kmol of a mixture of

benzene and chlorobenzene having 55 mol%of the less volatile is to be batch-distilled.
(a)If 25 moles of the solution is vaporized and condensed as the distillate,calculate the
concentration of the accumulated distillate.(b)If the concentration of the accumulated
product is found to be 72 mol%benzene,calculate its amount.The relative volatility of
benzene in the mixture is 4.15.
Solution
Use Eq.[7.51(b)].Given:moles of feed,F=50 kmol;feed concentration,xp=1-0.55=0.45.
(a)Distillate,D=25 kmol,and W=25 kmol;ypav(=xp)=?Putting the values in
Eq.[7.51(b)],

solving,we get xw=0.218

Material balance:Fxp=Wxw+Dypav →(50)(0.45)=(25)(0.218)+(25)yprav

→ ypyay =0.682
Composition of the distillate collected,xp =ypsav = 0.682
(b)Given:ypav =xp=0.72;D=?
Total material balance,50 =D +W;benzene balance,(50)(0.45)=Wxw+D(0.72)

From the above two equations,

Substituting in Eq.[7.51(b)],

Solving, xw=0.309; W=(13.5)/(0.72-0.309)=32.85

Amount of distillate, D=F-W=50-32.85 = 17.15 kmol

EXAMPLE 7.11 (Batch distillation with gradual addition of the feed) Sixty kilomoles of a
mixture of benzene and toluene containing 60 mol%benzene is to be separated by batch distillation.
A still that can hold 20 kmol of the mixture is available.It is planned to start distillation with
a charge of 20 kmol and to add the rest (i.e.40 kmol )to the still continuously over a
period
356 Chapter 7 Distillation

of one hour.It is possible to maintain a constant rate of heat supply to the still by steam coils
so that the rate of vaporization becomes the same as the rate of addition of the feed mixture
to the still.Calculate the amount and concentration of the composited distillate that woul d be
obtained at the end of an hour.Relative volatility of benzene in the mixture is 2.51.

Hints: LetF=kmol feed initially charged with a benzene concentration,xp;F'=the hourly

rate of addition of the mixture to the still;x=mole fraction of benzene in the liquid in the still
and y*=mole fraction of benzene in the vapour generated at any time t.Since the rates of addition
and vaporization are the same,moles of liquid in the still remain constant at F.An instantaneous
material balance gives

The above equation means that the rate of accumulation of benzene in the still is the difference
between the rate of its addition with the incoming feed and the rate of removal with the vapour.
Rearranging and integrating the above equation,

The integral is of the form:

Putting the values of the different quantities in the integrated equation,we have

2t=-0.4254-0.9414x-0.9756 In(1.604x-0.6);t=1 hour →x =

0.49

The concentration of the composited distillate can be found by material balance,xp = 0.695
We may consider a situation that a large quantity of feed is available and the distillation can
be continued for a long time,i.e.

At t= ,In(1.604x-0.6)→-~→ 1.604x-0.6=0→x=
0.374

This is the concentration of the liquid in the still at a large time.The corresponding vapour phase
concentration of benzene is 0.6.This indicates that at large time steady state is attained and
the vapour leaves at the rate and concentration as that of the feed entering the still.

7.5.2 Batch Distillation of a Multicomponent Mixture

Consider L moles of a solution containing components 1,2,.…,n at mole fractions xj,xz,…,Xμ.
So the number of moles of the individual components in the solution are:

L₁=Lxj; L₂=Lx₂; … L₁=Lx (7.53)

 Batch Distillation (Also Called Differential Distillation or Rayleigh Distillation) 357

For simplicity we assume the solution to be ideal.The relative volatility ai;of the component i
with respect to another component jis taken as a constant.Further,we shall take component
j as the base or 'reference component'with respect to which the relative volatility of any
other component in the mixture is defined.The differential mass balance equations for
components i and j become

For the component i: -dL₁=-yg;dL (7.54)

For the component j: -dL;=-yb;dL (7.55)

→ [from Eqs.(7.53)to (7.55)]

Integrating from the initial to the final state,

(7.56)
This equation can be written for all possible pairs with the component j as common to get

(7.57)

condition x₁+x₂+x₃+…+xn=1,can be used to solve a

Equation(7.57)together with
the multicomponent batch problem.

EXAMPLE 7.12(Multicomponent batch distillation) A mixture of 0.3 kmol n-pentane (1),

0.3 kmol n-hexane (2)and 0.4 kmol n-octane (3)is batch distilled at 1 atm pressure to remove
90%of n-pentane.Calculate the amount and composition of the distillate.Take the K-values
from the DePriester chart,Figure 7.8(b).

Solution
The initial number of moles of the components are:(L1)m=0.3,
(L₂)m=0.3,and(L₃)m=0.4.These are also the mole fractions of the components at the
beginning.('in’=initial;fi’=final).Initial bubble point temperature of the mixture is 64°C(the
calculations are not shown here;this may be obtained by following the procedure of Example
7.2 and using the K-values given in Figure 7.8).
Amount of n-pentane removed =90%of 0.3 kmol =0.27 kmol.Pentane remaining =0.03
kmol =(L₁)i.Taking n-hexane as the reference component,the working equation [Eq.
(7.57)] can be written as

(i)

If a₂i and az₃are known,the final amounts of components 2 and 3 in the mixture can
be easily calculated.The values of a at the beginning can be obtained at 101.3 kPa and 64℃
(the initial bubble point)using the K-values from Figure 7.8(b).However,as boiling
continues,the more volatile components are preferentially removed and the bubble point of the
liquid gradually increases.The K-values and relative volatilities also change as a result.
358 Chapter 7 Distillation

An approximate method of calculation uses the average values of a over the boiling
point range.For this purpose,the final boiling temperature is guessed and the relative
volatilities (azi and az₃)at this temperature are found out.The steps are given below.
(i) The initial bubble point temperature,the K-values and the a-values are determined.
(ii) The final temperature is guessed.The K-values and a-values are determined at
this temperature.
(iii) The arithmetic mean values of a are determined.The final number of moles of
the components are calculated from Eq.(7.57)or Eq.(i).
(iv) The final bubble point is now calculated.The values of a at this temperature are
determined.The mean a-values and the number of moles(Li/s)are recalculated
from Eq.(i).The procedure can be repeated for better accuracy,if necessary.
At 101.3 kPa(1 atm)and 64℃,K₁=2.3,K₂=0.87,K₃=0.144 [from Figure 7.8(b)]
α₂₁=K₂/K₁=0.87/2.3=0.378;α₂₃=K₂/K₃=0.8710.144 =6.04
Assume a final boiling temperature(when 90%of n-pentane is removed)of 95°C.At this
temperature,
K₁=4.65,K₂=2.03 and K₃=0.45→α₂₁=2.03/4.65=0.437 and a₂₃=4.51
Average values of a:
α₂₁=(0.378+0.437)/2 =0.407 and α₂₃=(6.04 +4.51)/2 =5.27
Putting these values of a in Eq.(i),
(L₂)n=(L₂)m/(10)(10407)=0.1175kmol;(L₃)h =0.335kmol
Check for the assumed final temperature of 95 ℃ :
Total number of moles at the end =0.03 +0.1175+0.335 =0.482
Liquid composition:
x₁=0.03/0.482 =0.0623; x₂=0.1175/0.482 =0.245;x₃=0.333710.482
=0.6927

So the assumed final temperature of 95°C is a bit too high.Because the component 2(n-
hexane) is the reference component,its revised K-value is taken as

K₂=(K2₉sc)/1.0987 =2.03/1.0987 =1.85

The corresponding temperature [from Figure 7.8(b)]is 91°℃.The K-values for components
1 and 3 at this temperature are:

K₁=4.4,K₃=0.39; a₂₁=1.85/4.4=0.42,a₂₃=1.85/0.39 =4.74

Average α-values are:
αz₂₁=(0.378+0.42)/2 =0.4; C₂₃=(6.04 +4.74)/2 =5.4
 Continuous Multistage Fractionation of Binary Mixtures 359

The values of (Li)r are recalculated.

(L₂)i =(L₂)n/(10)(0.4)=0.1194 kmol; (L₃)n =0.3373 kmol
These values are pretty close to the previous estimates.The total moles of the final liquid are:

Mole fractions: 0.03+0.1194+0.3 =0.4867

373 =0.0616
x₁=0.03/0.4867 =0.2466
x₂=0.12/0.4867
x₃=0.692

So the estimate of the final temperature (91°C)is good enough.

Number of moles of distillate =1.0 -0.4867 = 「 0.5133 kmol

Composition:
(x₁)o=(0.3 -0.03)/0.5133 = 0.526

(x₂)p=(0.3 -0.12)/0.5133 =
0.351

(x₃)o=[ 0.123

7.6 CONTINUOUS MULTISTAGE FRACTIONATION OF

BINARY MIXTURES

Separation of a volatile liquid mixture to relatively pure products is very often done in a
continuous fractionating column.A packed or a tray tower can be used,the choice
depending upon several factors.Understandably,a continuous column is much more
effective than multistage flash distillation or batch distillation.In this section we shall discuss
the basic design principles of a continuous tray tower for the distillation of a binary mixture.
A tray column and the flow rates and the concentrations of the vapour and the liquid phases
at different trays are schematically shown in Figure 7.14(a).For the sake of simplicity,we discuss
here the basic principles of fractionation of a binary liquid mixture.The feed (it may be a liquid,
a vapour or a two-phase mixture containing components A and B;A is the more volatile
component)enters the column at a suitable location.The liquid stream flows down the column
from one tray to the next lower tray;the vapour stream flows up bubbling through the liquid on
the trays.The vapour from the top tray is condensed and the condensate is collected in a reflux
drum.A part of this liquid is drawn as the top product and the other part is fed back to the
top tray(the top tray is marked tray no.1)as reflux.The top product contains the more
volatile component A and a little of the less volatile B.The liquid from the bottom tray goes to
a reboiler where it is partly vaporized,the vapour is fed back to the tower and the liquid part is
continuously withdrawn as the bottom product.The bottom product is rich in the less volatile
component B and has only a small amount of A in it.An intimate contact between the liquid
and the vapour phases occurs on a tray,facilitating rapid exchange of mass between
them.Transport of the more
360 Chapter 7 Distillation

volatile component A occurs from the liquid to the vapour phase,while transport of the less
volatile B occurs from the vapour to the liquid phase.Thus,a distillation column involves
counter- diffusion of the components(not necessarily equimolar).As the vapour flows up,it
becomes progressively richer in A.Similarly,the liquid becomes richer in the less volatile B
as it flows
down the column.

Figure 7.14(a) Material and energy balance envelopes in continuous distilation.

In the section of the column above the feed point,the concentration of the more volatile
is larger than that in the feed.This means that the vapour is enriched or 'purified'by
discarding the less volatile component B into the downflowing liquid.So the section of the
column above the feed tray is called the rectifying or enriching section.In the section of the
column below the feed tray,the more volatile component is removed or stripped out of the
liquid (by the process
of counterdiffusion,of course)to get a relatively pure B at the bottom.So this section is called
the stripping section.
Now we shall deal with the basic principles of design of a trayed distillation tower.We
shall first describe the more important variables,parameters and factors involved in the
design.
· The flow rate,composition and state of the feed. The state of the feed may be
described by its temperature,pressure,phase,etc.The feed may be a liquid,a vapour,
or a mixture of liquid and vapour (i.e.a two-phase mixture).
· The required degree of separation.The degree of separation is mainly determined by
the requirement of quality or purity of the products drawn from the
column.Example: Oxygen(bottom product)and nitrogen(top product)are the product
streams from a
 Continuous Multistage Fractionation of Binary Mixtures 361

liquid air distillation column.Nitrogen must be of very high purity(~99.99%)if it is

to be used for creating an inert atmosphere (blanketing),for example,for a special
welding job.A high purity oxygen is required for steel making (>99%)or for the partial
oxidation of naphtha(>98%)in a fertilizer plant.But oxygen of lesser purity (about
90%)is good enough for medical purposes.The higher the required degree of
separation,the more is the number of trays and the more expensive will be the tower.
· The reflux ratio and the condition of the reflux. The ratio of the reflux fed back to the
top tray and the top product withdrawn is called the reflux ratio(L₀/D).This is
an important design parameter.A specified degree of separation can be achieved
with a lesser number of trays if the reflux ratio is increased.The condition of reflux
means whether the reflux is a saturated liquid or a subcooled liquid.
· The operating pressure and the allowable pressure drop across the column.The
operating pressure also determines the temperature of the column.The pressure drop
for the vapour flow depends upon the type,the number and the hydraulic design of the
trays. Pressure drop becomes a more important factor if a column is run at a low
pressure.
· Tray type and column internals. The efficiency of separation(given by the tray
efficiency)is largely determined by these factors.
In a column design problem for continuous multistage distillation,the rate,the composition
and the state of the feed are given.The design engineer has to select the operating conditions
(these may be sometimes specified in the problem also),the reflux ratio,the tray type and the
column internals,and has to determine the number of trays.He has also to design the column,
the tray,the column internals(see Chapter 5)and the auxiliaries like the reboiler and the
condenser.It must be kept in mind that the design variables and parameters are interrelated.If
a few of them are given or selected,the rest can be determined.Sometimes the number of
trays may be known and the engineer has to check if it is suitable for achieving a desired
degree of separation of a mixture.For example,we may have a problem of determining if
an existing column containing a fixed number of trays of a particular design can be used for
the separation of a given feed at a given rate.In this case the reflux ratio and the operating
conditions are the important quantities to be calculated in order to ascertain if the existing
column is at all suitable for the purpose.
Counter-transport of the components A and B takes place on each tray of a fractionating
column.The molecules of the more volatile component leaving the liquid phase absorb latent heat
of vaporization.Also,transport of the less volatile component from the vapour to the liquid
phase causes its condensation accompanied by release of latent heat.So the mass transfer
of the components between the vapour and the liquid has associated thermal effects(this
has been indicated before in a simple problem on non-equimolar counterdiffusion,Example
2.5).The solution of a distillation problem involves the solution of mass and energy balance
equations over the trays and over the column.We develop here the relevant equations over
three sections of a column and also over the whole device.
Pictures of a few distillation columns in one of the major petrochemical complexes in
India are shown in Figure 7.14(b).
362 Chapter 7 Distillation

Figure 7.14(b) Afew distilation columns in Haldia Petrochemicals Limited (India).

7.6.1 Material and Energy Balance Equations

The determination of the number of trays is based on steady-state material and energy balance
equations over the envelopes shown in Figure 7.14(a).A subscript is used with the flow rate,
enthalpy and concentration terms to indicate the tray from which it originates.The notations L
and V denote the liquid and the vapour flow rates above the feed tray;L and V denote the same
quantities below the feed tray.Thus V,is the molar flow rate of vapour leaving the nth tray;HLn
is the molar enthalpy of the liquid leaving the nth tray.The rate of reflux to the top tray is Lo;
the suffix ‘0'signifies that the stream is as if coming from the 'hypothetical'Oth plate above the
top tray(the top tray is tray no.1).The rate at which heat is removed from the overhead
condenser (the condenser heat load)is Qc.The rate of heat supply to the reboiler (the
reboiler heat load)for vaporizing a part of the liquid leaving the bottom tray is Qg.The feed
rate to the column is F having a mole fraction zr of the more volatile.The distillate (xp=mole
fraction of A,the more volatile,in the distillate)is removed from the reflux drum at a rate
of D mole/h;
 Continuous Multistage Fractionation of Binary Mixtures 363

the bottom product leaves the reboiler at a rate W and the mole fraction of A in it is xw.We define
a reflux ratio(also called the external reflux ratio)as

(7.58)

Consider envelope 1(enclosing the condenser and the refux drum)in Figure 7.14(a).
Total material balance: V₁=Lo+D=RD+D=D(R+1 (7.59)
) total input total output
Component A balance: V₁y₁=Lo₀Xo +Dxp (7.60)
input of A output of A

Energy balance: (7.61)

From Eqs.(7.59)and (7.61),

D(R+1)Hv₁=L₀Ho+DHp+Qc
→ Qc=D[(R+1)Hv₁-RHLo-Hpl (7.62)

The condenser heat load Qc can be calculated from the above equation.
Now we consider envelope 2] (enclosing a part of the rectifying section and the condenser
in Figure 7.14(a)).
Total material balance: (7.63)
Vn+i=Ln+D
Component A balance:
Vn+1Yn+1=LXn+Dxp (7.64)
Energy balance: (7.65)
V+IHyn+I=LHLn+DH+Qc

Considering envelope 3 (enclosing a part of the stripping section and the reboiler),

Total material balance: Zm=V+1+W (7.66)

Component A Zm×m =Vm+1Ym+1+Wxw (7.67)

balance: LmHLm+Qg=Vm+1Hvm+I+WHw (7.68)

Energy balance:
(7.69)
Envelope 4 (enclosing the entire column,the condenser and the reboiler)gives
(7.70)
Total material balance: F=D+W (7.71)
Component A balance: Fzr=Dxp+Wxw
Energy balance: FHp+Q=DHD+WHw+Qc
A material balance and an energy balance equation are also to be written over the feed
tray. All the above equations together with the vapour-liquid equilibrium relationship can be
solved algebraically to determine the number of ideal trays required to achieve a specified
degree of separation of the feed.The oldest method of calculation that uses a tray-by-tray
approach is called the Sorel method(Sorel,1893).Many computational methods and
strategies have been devised over the years for multicomponent distillation
problems.However,a graphical procedure
364 Chapter 7 Distillation

can be conveniently used to determine the number of trays required for the separation of a
binary mixture.

7.6.2 Determination of the Number of Trays-the McCabe-Thiele Method

The McCabe-Thiele method developed in 1925 involves a graphical solution of the material
balance equations described in Section 7.61 together with the equilibrium relation or the
equilibrium data

Assumptions
The most important assumption underlying the McCabe-Thiele method is that the molar rate of
overflow of the liquid from one tray to another is constant over any section of the column.Thus,
Lo=L₁=L₂=…=Ln=L=constant in the rectifying section',and Lm =Lw+1=…
=Zv =L=constant in the 'stripping section'.The constant flow rates of the liquid (or
vapour)in the two sections differ by the rate of input of liquid (or vapour)feed to the column at
the feed tray.By virtue of the material and energy balance Eqs.(7.63)and (7.66),the molar
vapour rates in the respective sections also remain invariant.This assumption is called the
constant molar overflow(CMO).The assumption is obviously true when the molar heat of
vaporization of the mixture does not depend upon the composition or the temperature in
the column(example:a mixture of hydrocarbons not differing much in the molecular weight);for
many liquid mixtures the assumption is a good approximation.Lewis(1922)showed that the use
of the constant molar overflow assumption greatly simplifies the tray-by-tray calculation by
the Sorel method.If
constant molar overflow occurs,the mass exchange between the phases occurs in the equimolar
counterdiffusion mode.Tray-by-tray calculation for a ternary mixture is illustrated in Example 15.3.
Another assumption made in the following analysis is that heat loss from the column is
negligible.Let L and L represent the constant liquid flow rates,and V and V the constant vapour
flow rates in the rectifying and the stripping sections.Si nce the flow rates are constant,the
suffixes indicating the trays from which they come out have been dropped.It is to be noted that
if there is heat loss or gain,there will be accompanying condensation or vaporization within the
column,and the flow rates will vary along the column as a result.The major steps of the graphical
construction in the McCabe-Thiele method are to draw:(i)the equi librium curve using
the available data,(ii)the operating lines for the rectifying and the stripping
sections,and(ii)the steps between the equilibrium and the operating lines to find out the number
of ideal trays.

The rectifying section

Equation(7.63)that represents the material balance of component A over envelope 2 is

rewritten below.The reflux is assumed to be at its bubble point.

Vyn+i=Lxn+Dxp (7.72)
From Eq.(7.58),R=Lo/D=L/D;from Eq.(7.59),R+1=V/D

→ (7.73)
 Continuous Multistage Fractionation of Binary Mixtures 365

This is the equation of a straight line on the x-y plane with a slope R/(R +1)and an intercept
xp/(R+1)on the y-axis.Also the equation is satisfied by the point xn=xp,yn+l =xp.So the
straight line passes through the point (xp,xp)which is a point (say D)on the diagonal (see
Figure 7.15).Equation(7.68)is called the equation of the operating line of the rectifying section.
It is called an operating line because it relates the concent rations of the liquid and the vapour
phases leaving or entering a section.Usually the reflux ratio R and the distillate composition
xp are the known quantities (if the reflux ratio is not given,the designer has to select a
suitable value),and the operating line can be drawn.It is,however,easier to draw this line
through (xp,xp)with an intercept of xp/(R+1)on the y-axis [rather than using the
slope,R/(R +1)]. This is illustrated in Example 7.13 and Figure 7.15.A vertical length
segment between the operating line and the equilibrium line effectively stands for the overall
vapour phase driving force at the particular location in a column.

The stripping section

With the constant molar overflow assumption,the material balance for component A
over envelope 3]given by Eq.(7.67)can be rewritten as

Zxm=Vym+i+Wxw (7.74)

Putting V=L-W [from Eq.(7.66)],

(7.75)

This is the equation of the operating line for the stripping section.It has a slope of L/(L-
W) and passes through the point(xw,xw)which lies on the diagonal.This line is also
shown in Figure 7.15.
Similar to the reflux ratio defined for the rectified section,we may define a quantity
called the boil-up ratio,R,,for the stripping section.

(7.76)

EXAMPLE 7.13(Drawing the operating lines) A mixture of benzene and toluene

containing40
mole%benzene is to be separated continuously in a tray tower at a rate of 200 kmol/h.The
top product should have 95 mole%of benzene and the bottom must not contain more than 4
mole%of it.The reflux is a saturated liquid and a reflux ratio of 2.0 is maintained.The feed
is a saturated liquid (i.e.it is at its bubble point).Obtain and plot the operating lines for
the rectifying and the stripping sections on the x-y plane.What is the boil-up ratio?The
vapour- liquid equilibrium data at the operating pressure of 101.3 kPa are given below.

X 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y 0 0.21 0.38 0.511 0.627 0.719 0.79 0.853 0.91 0.961 1.0
366 Chapter 7 Distillation

Solution
Assume 'constant molar overflow'.Given:feed rate,F=200 kmol/h;feed composition,zr=0.4
mole fraction;top product composition,xp =0.95;bottom product composition,xw =0.04;
reflux ratio,R =2.0.
Total material balance [Eq.(7.69)]:

F=D+W → 200=D+W

Total benzene balance [Eq.(7.70)]:

Fzp=Dxp+Wxw → (200)(0.4)=D(0.95)+W(0.04)

Solving the above equations,we get D=79.1 kmol/h and W=120.9 kmol/h
R =L₀/D→2.0 =L₀/79.1
→ L₀=158.2; ; V₁=D(R+1)=(79.1)(2+1)=237.3,from Eq.(7.59).

Since the feed is a liquid,the vapour rate remains constant at V=V₁=237.3 kmol/h in
the rectifying section.
Flow rates in the stripping section: Since the feed is a saturated liquid,the liquid rate
increases by 200 kmol/h below the feed plate.However,the vapour rate remains constant
all through. Equilibrium line1.00 Local overall vapour- phase driving force
Liquid
^
y
flow rate,L=L+200=158.2+200=358.2;vapour rate,V =V =237.3

0.75
Operating line [slope =R/(R+1)]for the rectifying section,yn+1=0.667x,+0.317

Operating line for the stripping section,Jm+1=1.509xm-0.0204

0.25
Intercep 0.50
xp/(R+1)=0.317

-0.00l
0.00
x

0.25 0.50 0.75 1.00

Figure 7.15 The operating lines on the x-yplane.

Operaing liness rectifying setion.Eq.(7.73):

 Continuous Multistage Fractionation of Binary Mixtures 367

yn+1=0.667xn+0.317 (i)
Stripping
section,Eq.(7.75),

ym+1=1.509xm-0.0204 (ii)
Equations (i)and (ii)are the rectifying and stripping section operating lines respectively.
The equilibrium line is plotted on the x-y plane (Figure 7.15).The operating line (i)for the
rectifying section passes through the point D(xp,xp),i.e.(0.95,0.95)and has an intercept of
0.317.The line is shown in Figure 7.15.The stripping section operating line (i)passes
through the point W(xw,xw),i.e.(0.04,0.04)and has a slope of 1.509.This line is also shown
in the figure.

The boil-up ratio,

The feed line

As the feed enters the column,the liquid and vapour flow rates
undergo step changes depending upon the state of the feed (i.e.
upon how much liquid and vapour it has).We shall now write the
material and energy balance equations over the plate to which the
feed is introduced.Let us designate this plate by the suffix 'f.
The feed plate along with related flow,composition and enthalpy
terms are shown in Figure 7.16.
Total material balance:

F+L+V=L+V (7.77)
Energy balance: Figure 7.16 The feed plate.

FHp+LHLr₁+VHvfH=LHLy+VHvj (7.78)

If we assume that the change in the enthalpy of a phase as it passes through the feed plate
is small,we can write(omitting the subscript f),

HLf-i≈HLf≈HL
and
Hv+i≈Hvr≈Hv (7.7
Substituting the relations(7.79)in Eq.(7.78),

FHF+LHL+VHy=LHL+VHy
i.e. (L-L)HL=(V-V)Hv+FHr (7.8
368 Chapter 7 Distillation

From Eqs.(7.77)and (7.80),

(L-L)H₁=(L-L-F)Hv+FHp=(L-L)Hv+F(Hp-Hv)
→ (L-L)(HL-Hv)=F(Hp-Hv)

→ (7.81)

But L-L=increase in the liquid flow rate across the feed tray as a result of introduction of
the feed =rate of input of liquid with the feed.So q is the fraction of liquid in the feed.
On the basis of Eq.(7.81),the quantity q may also be attributed another physical significance.

(7.82)

If the feed is a liquid at its bubble point (saturated liquid),q=1;if it is a vapour at dew point
(saturated vapour),q=0.If the feed is a two-phase mixture of liquid and vapour,q represents
the fraction of liquid in it.So(1-q)gives a measure of the 'quality'of the feed.
The point of intersection of the two operating lines,rectifying section and stripping
section, must satisfy Eqs.(7.72)and(7.74).If the point of intersection is (x,y),
From Eq.(7.72), Vy=Lx +Dxp

From Eq.(7.74), Vy =Lx-Wxw

Subtracting the above equations and using Eq.(7.70),

(V-V)y=(L-L)x+(Dxp+Wxw)=(L-L)x+Fzp (7.83)

Now,dividing both sides of Eq.(7.77)by F,simplifying,and using the definition of q given by

Eq.(7.81),

(7.84)
Dividing both sides of Eq.(7.83)by F and using the above result,

-(q-1)y=-qx+zr → (7.85)

The above equation represents a straight line passing through (i)the point (Zr,zp)on the diagonal
(recall that zr is the overall mole fraction of A in the feed)and (ii)the point of intersection of
the operating lines.The line has a slope q/(q-1),where q is the quality of the feed as stated
before [Eq.(7.82)].Since the line given by Eq.(7.85)is completely described by the state
(quality)and concentration of the feed,it is called the feed line.
The stripping section operating line can be drawn by taking the help of the feed
line.The upper operating line and the feed line are drawn on the x-y plane and their point of
intersection is located.The line joining this point of intersection and the point(xw,xw)is
the stripping section operating line.The following characteristics of the feed line may be
noted(also see Example 7.14).
 Continuous Multistage Fractionation of Binary Mixtures 369

(a) If the feed is a saturated liquid,q =1;and the slope of the feed line is infinite.So the
feed line is a vertical line through (zp,zr).
(b) If the feed is a saturated vapour,q=0;and the slope of the feed line is zero.So the
feed line is a horizontal line through (Zr,Zr).
(c) If the feed is a mixture of liquid and vapour or a superheated vapour or a
subcooled liquid,the slope of the feed line can be calculated from the enthalpy data and Eq.
(7.81).
Drawing of feed lines under different thermal conditions of the feed is illustrated in Example 7.14.

EXAMPLE 7.14(Drawing the feed line for different feed conditions) A

mixture of benzene
and toluene containing 58 mole%benzene is to be separated in a continuous column
operating at 1 atm total pressure.Draw the feed line for the following feed conditions:
(a)saturated liquid,
(b)saturated vapour,(c)65 mass%vapour,(d)vapour at 120℃,and (e)liquid at 50℃.
The other relevant data are given as follows:Benzene:average specific heat of liquid =
146.5 kJ/kmol·K,of vapour=97.6 kJ/kmol·K;heat of vaporization =30,770 kJ/kmol.Toluene:
average specific heat of liquid =170 kJ/kmol·K,of vapour =124.3 kJ/kmol·K;heat of
vaporization =32,120 kJ/kmol.
Solution
The feed line is given by Eq.(7.85).To draw the line,we need to know the value of q.The
feed line must pass through the point F(zr,zr),i.e.(0.58,0.58)which lies on the diagonal
on the x-y plane.We consider the cases given.
(a)The feed is a saturated liquid.So,q =the fraction of liquid in the feed =1.
Therefore,the slope of the feed line =ql(q-1)=1/0 =.The feed line is a vertical
line through the point F.This is line I on Figure 7.17.

(b)The feed is a saturated vapour,i.e.q=0 and the slope of the feed line is zero.The feed
line is a horizontal line through the point F(line II).
(c)The feed is 65 mass%vapour.So on the average,the feed contains 35 mole%liquid
(in this case mass%and mole%can be used interchangeably).So q =0.35 and the slope of
the feed line =0.35/(0.35-1)=-0.538 and its intercept on the y-axis =-zp/(q-1)=-
(0.58)/ (0.35-1)=0.892.The line is drawn through the point(0.58,0.58)on the x-y plane
and is marked III on Figure 7.17.

(d)The feed is a superheated vapour at 120℃.In this case the value of q has to be
calculated from Eq.(7.81).The values of the enthalpy terms Hr,Hy and Ht are
required.In order to calculate the enthalpies,a reference state is to be selected.Using the
Antoine constants given in Table 7.2,the bubble point of a solution having 58%benzene can
be calculated (assuming that the solution is ideal).The bubble point is 90°℃(the calculation
of the bubble point is left as an exercise).We take pure liquids at 90℃ as the reference
state for convenience.The heat of solution(△H₅)is assumed to be zero.
Enthalpy of the liquid: For the solution at its bubble point (T=90℃),put To =90 and
△H₅=0 in Eq.(7.18)→HL=0.
 1.0T
V
370 0.8
Chapter 7 Distillation
Ⅲ

0.6 I
y=0.521 IV
0.892
Equilibrium F(0.58,0.58)
line
y

0.2
x=0.484 0.4
0.0
0.0 0.2 0.4
x

x: =0.58

0.6 0.8 1.0

Figure 7.17 Feed lines for diferent condtions of the feed:(1)saturated liquid,(ll)saturated vapour,(ll)two-phase
mixture, (IV)superheated vapour,and (V)subcooled liquid.

Enthalpy of the vapour: The mole fraction of benzene in the saturated vapour in
equilibrium with a liquid with x=0.58 is y*=0.78.Putting y*=0.78,T(vapour temp.)=90℃,
T₀(ref.temp.)=90℃,MAλ₄=30,770 kJ/kmol,and Mgλg=32,120 kJ/kmol in Eq.(7.19),the
enthalpy of the saturated vapour is
Hy=(0.78)(30,770)+(1-0.78)(32,120)=31,067 kJ/kmol
Enthalpy of the feed: We imagine that 0.58 kmol of benzene and 0.42 kmol of toluene are
vaporized separately at 90°C,the vapours are heated to 120°C and then mixed to get one
kmole of the feed.

Hp=[(0.58)(30,770)+(0.58)(97.6)(120 -90)]
latent heat sensible heat

+[(0.42)(32,120)+(0.42)(124.3)(120-90)]=34,601
latent heat sensible heat

Then.

To draw the feed line in this case,it will be more convenient to use the intercept on the y-axis,
i.e.

-Zp/(q-1)=-0.58/(-0.114 -1)=0.521
The feed line is marked IV on Figure 7.17.
 Continuous Multistage Fractionation of Binary Mixtures 371

(e)The feed is a subcooled liquid at 50°℃.We imagine that 0.58 kmol of benzene and 0.42
kmol of toluene are separately cooled from the reference temperature (To=90℃)to T
=50℃ and then mixed to get one mole of the subcooled feed.
The enthalpy of the feed,
H=(0.58)(146.5)(50-90)+(0.42)(170)(50-90)=-6240 kJ/kmol(the heat of mixi
is neglected).

From Eq.(7.85),the intercept on the x-axis =zplq =0.58/1.2 =0.58/1.2 =0.484.

The feed line is drawn through (0.58,0.58)with this intercept on the x-axis.It is marked
V on Figure 7.17.

Feed tray location and the number of ideal trays

The next step of graphical construction is to determine the number of equilibrium trays (or ideal
trays)required for a specified degree of separation(i.e.for specified values of xp and xw)and
to locate the feed tray.This is illustrated in Example 7.15 and Figure 7.18(a).The rectifying
section operating line DE is drawn through the point D(xp,xp)with an intercept xp/(R+1)on
the y-axis.If the feed is a saturated liquid,the feed line FN is a vertical line through the point
F(Zp,zr).The feed line FN intersects the rectifying section operating line DE at M.The
point W(xw,xw)is located on the diagonal.WM is joined to give the stripping section operating
line. The line WM,when extended,intersects the equilibrium curve at S",and the line
DE,when extended,intersects the equilibrium curve at S'.
The number of equilibrium trays is determined by step or staircase construction between the
equilibrium curve and the operating lines (see Example 7.15).The basis of such construction has
been described in Section 4.6.2.The point(xn,y,)lies on the equilibrium curve whereas the point
(xn,yn+i)lies on the operating line.Construction may start from either end,i.e.from D(the top
tray)or W(the bottom tray).When the feed line is crossed in course of construction,a
changeover from one operating line to the other is necessary.This means a transition from the
rectifying to the stripping section(or vice versa).For example,starting the stage construction
from the point D in Figure 7.18(a),we should make a changeover from the upper operating line
to the lower after tray number 5 from the top.The step construction should thereafter proceed
along the lower operating line MW.In this way we take the advantage of maximum possible
change in the concentration in each tray.So the sixth tray from the top is the optimum feed
tray. The stage construction(solid line)shows that the number of ideal stages required is
7.8.If the graphical construction does not give an integral number of trays (in fact,it rarely
does),it is customary to report the number of ideal trays as a mixed fraction.The idea behind
this is that the integral number of real trays is determined after considering tray
efficiency.Usually,the reboiler partly vaporizes the liquid from the lowest tray.Because
equilibrium vaporization in the reboiler is quite a reasonable assumption,the reboiler also acts
as a tray.So the number of ideal trays in the construction shown in Figure 7.18(a)is 7.8
including the reboiler;i.e.6.8 number of trays and a reboiler are required for the desired
separation.
The above discussion does not mean that the feed has to be introduced always on
the 'optimum feed tray'.Consider the staircase construction on Figure 7.18(b).The feed
is
372 Chapter 7 Distillation

deliberately introduced on the fifth tray from the top.So a changeover to the lower operating
line has been made at the fifth tray from the top,and construction has thereafter been done
along WMS",the stripping section operating line.The number of equilbrium trays required to
reach the point Wis 8,which is 0.2 ideal trays more than the previous case.This is expected
because full advantage of the driving force has not been exploited on a few trays.
However,a changeover from one operating line to the other is possible only in the section
S'S".When a new column is designed,the optimum feed tray location is used.But if an
existing column with a feed nozzle at a particular tray has to be considered for possible use to
separate a mixture,a changeover from one operating line to the other during staircase
construction should be done at the tray which is provided with a feed nozzle [see Example
7.15,part (d)].Complete construction of the steps will tell whether the existing column is
suitable for a particular service. If not,further calculations may be done with a different
reflux ratio before discarding the possibility of use of the available column.
It is to be noted that a liquid feed is introduced just above the feed tray,but a vapour feed
is introduced just below it.If the feed is a mixture of liquid and vapour,it is desirable that it is
separated into the vapour and the liquid phases first.The liquid part should enter the column just
above the feed tray and the vapour part just below it.However,this is not always done in
practice, and a mixed feed is often introduced as a whole over the feed tray.
If a high purity product is required,the graphical constructon of the trays may pose a
problem.The operating and the equilibrium lines may be too close at the top and the bottom region
to allow graphical construction.One way is to draw steps for these regions on separate
graphs drawn using expanded scales.Alternatively,the Kremser equation may be used
assuming the equilibrium line to be linear at low concentrations.Another technique of plotting the
equilibrium and the operating line for McCabe-Thiele construction has been suggested by
Ryan(2001).

EXAMPLE 7.15(Determination of the number of ideal trays) A stream of aqueous

methanol having 45 mol%CH₃OH is to be separated into a top product having 96 mole
%methanol and a bottom liquid with 4%methanol.The feed is at its bubble point and the
operating pressure is 101.3 kPa.A reflux ratio of 1.5 is suggested.(a)Determine the
number of ideal trays. (b)Find the number of real trays if the 'overall tray efficiency'is
40%.On which real tray should the feed be introduced?(c)Plot the temperature profile
along the column.(d)A column having twenty-two trays with a feed nozzle at tray number
13 from the top is available in the plant.The trays are presumed to be 40%efficient on the
average.Is this column suitable for the above separation?
The equilibrium and bubble point data for the methanol-water system at 101.3 kPa are
given below.
x 0 0.02 0.04 0.06 0.08 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 0.95 1.0
y 0 0.1340.23 0.3040.3650.4180.5790.6650.7290.7790.8250.87 0.915 0.958
0.9791.0
Temp.10096.4 93.5 91.2 89.3 87.7 84.4 78.0 75.3 73.1 71.2 69.3 67.6 66 65 64.5
Solution
The equilibrium data are plotted,the diagonal is drawn.Given:xp=0.96;xw=0.04 and zp=0.45.
The points D(0.96,0.96),W(0.04,0.04)and F(0.45,0.45)are located on the x-y plane.
 Continuous Multistage Fractionation of Binary Mixtures 373

(a)Number of ideal trays: The reflux ratio is R =1.5.The intercept of the rectifying section
operating line on the y-axis is xp/(R+1)=0.96/(1.5+1)=0.384.
The upper operating line is drawn through the point D(0.96,0.96)with an intercept of
0.384 on the vertical axis [Figure 7.18(a)].The extended operated line meets the y-axis at
E(intercept =0.384).The feed is a saturated liquid and the feed line is a vertical line through
F.The upper operating line meets the feed line at the point M.The points M and W are joined to
get the lower or stripping section operating line WM.Now the number of ideal trays is
determined by drawing steps between the equilibrium line and the operating lines DM and
WM,changing from the upper to the lower operating line as the feed line is crossed.The
number of ideal trays is 7.8.It is to be noted that the feed is to be introduced on the 6th
ideal tray.
(b)Number of real trays: The number of real trays is obtained by dividing the number of ideal
trays by the fractional overall tray efficiency(the given value is 0.4).The number of real trays
is 6.8/0.4 =17 real trays plus the reboiler which is assumed to act like an ideal stage.

Figure 7.18(a) McCabe-Thiele construction for the number of ideal trays.

(c)The temperature on the nth tray can be obtained from the values x,,yn and the given bubble
point data.The temperatures on the different ideal trays are given below.
n 2 3 4 5 6 7 8
0.913 0.853 0.773 0.667 0.575 0.35 0.15 0.0405
Xn
Temp 66 66.9 68 70 72.8 76.5 85 94
374 Chapter 7 Distillation

(d)This part is left as an exercise.Note that now the feed is introduced on the fifth ideal
tray from the top [see Figure 7.18(b)].

Figure 7.18(b) McCabe-Thiele construction for the number ofideal trays-the feed enters a pariculartray.

Analytical determination of the number of ideal stages—Smoker's equation

A simple but elegant equation was derived by Smoker(1938)to analytically determine the
number of ideal stages required for the separation of a binary mixture if the relative volatility is
constant and constant molar overflow(CMO)occurs.Smoker used a simple coordinate
transformation that ultimately led to a relation between the liquid concentrations on the top tray
and on the nth tray.Smoker's equation reduces to the Fenske equation in the limit R → .
Interested readers are referred to the original classical article or to Sinnott (Coulson-Richardson's
Chemical Engineering,Vol.6,Elsevier,2005,pp.512-515).Applications of Smoker's equation
have been discussed further by Jafarey et al.(1979).
Total reflux
If the liquid from the overhead condenser is totally recycled to the column,i.e.no distillate
is removed from the reflux drum(D=0),the column is said to run at total reflux'.The
reflux ratio becomes R=L₀/D=L₀/0=infinity.No product is drawn from the reboiler
either.All the liquid flowing to the reboiler is vaporized and fed back to the column.So,in a
column operating at total reflux under steady-state conditions,there should not be any flow
of feed into it.
At total reflux,the slope of the rectifying section operating line is [R/(R+1)]for R
→~, i.e.the slope of the line is unity and it passes through the point(xp,xp)on the
diagonal.Therefore,
 Continuous Multistage Fractionation of Binary Mixtures 375

the operating line coincides with the diagonal.So does the stripping section operating
line.The number of ideal stages is obtained by staircase construction between the equilibrium
line and the diagonal.This gives the theoretical minimum number of stages to achieve a given
separation.The construction is illustrated in Figure 7.19.Total reflux is very often used during
the startup of a column till the steady-state condition is reached.After this,continuous feed
flow and product withdrawal are started.

Fenske's equation

This equation can be used to theoretically calculate the minimum number of trays if the relative
volatility remains reasonably constant.Let Nm be the minimum number of trays in the column.
Besides,there is a total reboiler.If aw is the relative volatility of A at the reboiler temperature
and pressure,and xw and yw are the equilibrium liquid and vapour concentrations in the
reboiler, then by definition,

(7.86)

The vapour leaving the reboiler and entering the lowest tray(tray number Nm in this case)has
a mole fraction yw of the component A.The liquid leaving this tray has a composition
xwm.So the point(xvm,yw)lies on the operating line.Because the operating line coincides with the
diagonal at total reflux,xvm =yw.Putting this result in Eq.(7.86),

(7.87)

Applying the same procedure to the case of tray number Nm,

Similarly for tray number Nm-1,

[Note that the point(xvm-1,yvm)lies on the operating line which coincides with the
diagonal; therefore,xNm-1=yvm]
Continuing the procedure up to the top tray(where yi =xp),

i.e.
(7.88)

Here aay is the average relative volatility of the more volatile component.The above equation is
called Fenske's equation,which is useful for the calculation of the minimum number of trays.
376 Chapter 7 Distillation

EXAMPLE 7.16(Number of theoretical plates at total refux) A mixture of benzene and

toluene having 40%benzene is to be separated at a rate of 200 kmol/h into a top
product containing 95%benzene and a bottom product with 4%of it.It is a common practice
to run a column at total reflux for some time for the purpose of stabilization during
startup.Determine the number of ideal trays required for this separation if the column is operated
at total reflux (no feed input at this time).Also calculate the same using the Fenske equation if
the average relative volatility of benzene in the mixture is 2.5.Vapour-liquid equilibrium data
for this system at the operating pressure of 1 atm are also given in Example 7.13.
Solution
At total reflux,the reflux ratio is infinite (R=~)and the slope of the rectifying section operating
line is R/(R+1)=1.So both the operating lines should coincide with the 45°line
(i.e.the diagonal).Given:top product composition,xp=0.95;bottom liquid composition,xw
=0.04.
The equilibrium data are plotted on the x-y plane in Figure 7.19.The points D(0.95,0.95)
and W(0.04,0.04)are located1.0 on the diagonal.The number of ideal trays is obtained
by construction of steps between the equilibrium line and the diagonal,starting at one end
Equilibrium
(say at D)and terminating at 0.8
line
the other.The number of trays is 7.

0.6
F
0.4

0.2
y

W
0.0
0.0 xy

ZF Xp
0.2 0.4 0.6 0.8 1.0

Figure 7.19 Numberof plates for operation attotal reflux (the minimum number of plates).

Use of the Fenske equation: Put the values of xp,xw and aa(=2.5)in Eq.(7.88).The
total number of trays is

This is very close to the number of ideal trays determined graphically.One of the reasons of
the small difference is the assumption of an average value of the relative volatility.
Note: For operation at total reflux,sufficient amount of feed is charged into the reboiler
and flow of steam(to the reboiler)and of cooling water(to the condenser)are started.The entire
 Continuous Multistage Fractionation of Binary Mixtures 377

condensate is fed back as reflux.The rate,the concentration and the thermal state of the
feed are not relevant for a column operated at total reflux since there is no feed input at all.
Minimum reflux ratio
In Section 6.4,we discussed the method of determination of the minimum liquid rate for
gas absorption by identifying the pinch point for a given system.The determination of the
minimum reflux ratio for distillation is also based on identifying the pinch point.Let us refer to
Figure 7.20 in which the equilibrium curve and the feed line are shown;D(xp,xp)and
W(xw,xw)are the terminal points of the operating lines.For a particular reflux ratio
(Rj,say),DE₁is the enriching section operating line having a slope R₁/(R₁+1).It intersects the
feed line at the point Mi;WM₁ is the stripping section operating line.The ordinate of the point
Ei gives the intercept of the upper operating line on the y-axis.The number of theoretical trays
required is obviously finite.As the reflux ratio R₁decreases to Rz,the slope of the upper
operating line decreases,but the intercept increases,i.e.the point E₁moves to E₂(say).The
upper operating line is DMz;the stripping section operating line is WM₂;and they intersect
at Mz on the feed line.Now the driving force is less at all the points and the number of
theoretical trays will be more.If the reflux ratio is gradually reduced,a situation will appear
when the upper operating line DE₃intersects the feed line at the point M₃that lies on the
equilibrium curve.The driving force is zero at the point M₃ . It is the pinch point.The number
of theoretical trays required to achieve the given separation becomes infinite.This operating
line DMʒcorresponds to the minimum reflux ratio,bacause if the reflux ratio is further
reduced,the operating line will intersect the feed line at a point M4above the equilibrium
curve.This is impossible.To determine the minimum reflux ratio R.,for the kind of equilibrium
line shown in Figure 7.20,the steps given below should be followed.
(a) Locate the points D(xp,xp)and F(zr,zr)on the diagonal on the x-y plane.
(b) Draw the feed line through F from the known feed composition zr,and the feed
quality (given by q);locate the point M₃ .
(c) Join DM₃and extend to intersect the y-axis at Eʒ.Find out the ordinate of Eʒand
equate it to xp/(Rm+i).Calculate the minimum reflux ratio,R.

x
Figure 7.20 Operatinglines for changing reflux ratios and for the minimum reflux (Rm).
378 Chapter 7 Distillation

The above strategy fails for some other shapes of the equilibrium curve.Examples are shown
in Figure 7.21 and Figure 7.22.Because of the typical curvature,the pinch point does not occur
at the intersection of the feed line and the equilibrium curve.As the reflux ratio is reduced,at
a certain value of it the pinch point K occurs at the point of tangency of the rectifying section
operating line(Figure 7.21)or the stripping section operating line(Figure 7.22)and the
equilibrium line.The location of the point of tangency depends upon the shape of the equilibrium
line.This type of pinch point and the minimum reflux ratio can be determined only
graphically.
Example 7.17 illustrates the procedure.

Figure 7.21 Apinch point(K)on the operatingline fortherectitying section.

EXAMPLE 7.17 (Determination of the minimum reflux ratio) A binary

solution of60mol%
A and 40 mol%B is to be separated into a top product having 96 mol%A and a bottom
product with6 mol%A.The feed is a two-phase mixture containing 72%liquid.Determine the
minimum reflux ratio for this separation.The equilibrium data for the system at the
operating condition of the column are given below.
x 0 0.05 0.07 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.50 0.60 0.70 0.80 0.90 1.0
y 0 0.07 0.10 0.14 0.2050.29 0.39 0.55 0.67 0.75 0.86 0.93 0.96 0.98 0.99 1.0

Solution
Given:xp=0.96;xw=0.06;zF=0.60;fraction of liquid in the feed,q =0.72.
The equilibrium diagram is plotted and the points D(0.96,0.96),W(0.06,0.06)a nd F(0.6,
0.6)are located on the x-y plane (Figure 7.22) .The feed line is drawn through the point F
with an intercept of zr/q=0.6/0.72=0.833 on the x-axis.It meets the equilibrium line at the
point M.The points W and M are joined,but the corresponding line WM in the stripping section
cannot be an operating line since WM(shown as a dotted line)cuts the lower part of the
equilibrium line at two points.So the point M cannot be a pinch point.This happens because
the lower part of the equilibrium line is convex downwards.
To determine the true pinch point,we draw a tangent to the equilibrium line through the
point W.This line meets the feed line at the point Mi.Join DM₁and produce it to meet the y-
axis at
 Continuous Multistage Fractionation of Binary Mixtures 379

x
Figure 7.22 A pinch point on the operating line for the stripping section.

E.The point of tangency is K.If we make step construction starting at D,it is seen that as we
approach the pinch point K,the step size becomes progressively smaller,and it is not possible
t o reach K by drawing a finite number of plates.The situation corresponds to the minimum
reflux and DE is the rectifying section operating line for minimum reflux.If Rm is the minimum
reflux,
the ordinate of the point E is

0.56
=xp/(Rm+1)=0.96/(Rm+1)→Rm=(0.96/0.56)-1=0.174

Open steam
While separating an aqueous solution,if the residue or bottom product consists of water and
traces of the solute,sometimes it may be convenient to feed
live steam at the bottom of the tower.No reboiler is necessary.
The arrangement is shown in Figure 7.23.
The operating line equation for the rectifying section
remains the same as Eq.(7.73),but that for the stripping
section is obviously different.The material balance of
component A over the envelope shown in Figure 7.23 is
[assume that the inlet steam is saturated]

Lxm+V·(0)=Vym+l+Wxw (7.8 Open steam Bottom

Since there is no reboiler,L =W.Therefore, product
Lxm=Vym+i+Lxw Figure 7.23 A distillation column
using open steam.
380 Chapter 7 Distillation

→
(7.90)

Also,by definition,the point(xw,O)lies on the lower operating line.The determination of the

number of ideal plates in a column using open steam is illustrated in Example 7.18.When
open steam is used,one or two more ideal trays are required for a separation,but there is no
reboiler cost.
There may be other practical situations which are not covered in the above
discussion.Cases may arise when heat loss from the column wall may occur causing some
condensation of the vapour,or the overhead vapour may be partially condensed and the top
product may be with- drawn as a vapour.In any such case,the operating lines have to be
drawn on the basis of appropriate mass and energy balance equations.

EXAMPLE 7.18(Use of open steam in distillation) An aqueous solution containing 40 mol%

methanol is to be separated at a rate of 300 kmol per hour using open steam as the source
of heat energy.The top product must have 96 mol%methanol and the bottom product must
not have more than 4 mol%of it.The feed enters the column 50%vaporized.A reflux ratio of
2.25 is suitable.Determine(a)the equation of the stripping section operating line,(b)the
slope of the feed line,(c)the number of ideal plates required for this separation,(d)the
steam rate,and (e)the condenser heat load.The following enthalpy data for 96 mol
%methanol solution at 1 atm are available:saturated vapour,Hy=9725 kcal/kmol;saturated
liquid,Ht=1260 kcal/kmol (reference state:pure liquids at 15℃;see Example 7.4).
Hints: Given:reflux ratio,R=2.25;Top product concentration,xp =0.96.
Operating line for the rectifying section:intercept on the y-axis =xp/(R+1)=0.96/3.25=0.295
Feed line:q=fraction of liquid in the vapour-liquid mixture =0.5;feed concentration,
ZF=0.4

Slope of the feed line =q/(q-1)=0.5/(0.5-1)=-1

[this is the answer to part (b)of the problem]
Intercept of the feed line on the x-axis =-zr/(q-1)=-0.4/(0.5-1)=0.8

The stripping section operating line passes through W(0.04,0).

The equilibrium data [see Example 7.15]are plotted on the x-y plane and the diagonal
is drawn.The points D(0.96,0.96),W(0.04,0)and the feed point F(0.4,0.4)are located on
the x-y plane.The feed line is drawn through F with an i ntercept of 0.8 on the x-axis (it is
more convenient to draw the line using this intercept rather than the slope).The rectifying
section operating line is drawn though D with an intercept of 0.295 on the y-axis.This line
intersects the feed line at the point D₁.Join WDi which is the stripping section operating line.

Equation of the stripping section operating line,WDi:y=1.944x-0.0783[answer to part (a)].

Draw steps between the equilibrium line and the operating lines (we start from the end D)
changing from the upper to the lower operating line as the feed line is crossed.The number of

ideal stages is |7|[answer to part(c)].The graphical construction is left as an exercise.

 Continuous Multistage Fractionation of Binary Mixtures 381

In order to calculate the steam rate we have to use the following material balance equations.

Total material balance: F+V=D+W→300+V=D+W (i)

Methanol balance: Fzr+V(0)=Dxp+Wxw→(300)(0.4)=D(0.96)+W(0.04) (ii)
Liquid flow rate in the stripping section,L =W(because there is no reboiler).
Slope of the operating line of this section=L/V=WV =1.944 →V =0.514W (iii)
Solving Eqs.(i),(ii)and (iii),

D=108.6 kmol,W=394.3 and √=202.9 kmol/h =「3652 kg steam per hour

[Answer to part (d)];
The condenser heat load [part (e)]:The vapour (96 mol%methanol)leaving the top tray is
condensed to the saturated liquid.Condenser heat load
=V₁(Hv-H₁)=D(R+1)(Hv-HL)

=108.6(2.25
+1)(9725-1260)=2.987×10⁶kcal/h

Use of reflux below its bubble point

The vapour from the top tray may sometimes be condensed and then cooled below its bubble
point (subcooled)in the condenser.This is 'cold reflux'.On entering the top tray,the 'cold reflux'
reaches its bubble point very quickly.The required energy is supplied by condensation of some
of the vapour on the top tray.Thus,the vapour flow rate V,from the top tray will be less than
that at the lower trays,and the liquid flow rate L in the rectifying section(Figure 7.24)will
be
larger than the reflux Lo fed to the column from the condenser.As a result,the “internal reflux
ratio',R'(=L/D),will be greater than the 'external reflux ratio',R(=Ln/D).In order to calculate
the internal reflux ratio R',we need to know the liquid flow rate L.
If θ,is the temperature of the cold reflux,and 0,,is its bubble point,energy required
for heating the reflux,

where
Cpy=specific heat of the reflux (kJ/kg·°C)
M,=its average molecular weight (this is the same as that of the vapour from the top tray)
λ=latent heat of condensation of the vapour(kJ/kg).Then the internal liquid flow
rate,

R′=L/D (7.91)

The equation of the rectifying secton operaing line:

(7.92) The rest of the graphical construction is pretty much the same as described
before.This is
illustrated in Example 7.19.
382 Chapter 7 Distillation

Use of murphree efficiency in graphical construction of stages

One more case deserves attention.Trays are never ideal.As discussed in Chapter 6,tray efficiency
is an indicator of how good the mass transfer performance of a tray is.If an overall fractional
tray efficiency is given,the number of real trays is calculated by simply dividing the number
of ideal trays by the fractional tray efficiency.The Murphree tray efficiency Em is given as

(7.93)

Note that the actual enrichment of the vapour over the nth tray is
the theoretically possible enrichment is ,which is the vertical distance between the
operating line and the equilibrium line.A pseudo-equilibrium line is drawn(see also Section 6.8.2)
such that its vertical distance from the operating line is Em-times the distance between
the operating line and the equilibrium curve.Staircase construction between the pseudo-
equilibrium curve and the operating lines gives the number of real plates.This is illustrated in
Example 7.19.

EXAMPLE 7.19(Number of real trays-cold reflux;the Murphree efficiency is given)An

aqueous methanol having 45 mol%of the alcohol at 40℃ is to be separated into a top
product with 96 mol%methanol and a bottom stream with not more than 4%of methanol.The
vapour leaving the tower is condensed and cooled.The reflux is returned to the column at 50°℃
and the external reflux ratio is 2.25.It is required to determine(a)the number of real trays
for this separation if the Murphree efficiency is 60%,and(b)the heat duty of the reboiler
and of the condenser.
The following data are supplied:Enthalpy values(reference states—pure liquids at
0℃): saturated feed (45 mol%methanol,74°C):1390 kcal/kmol;saturated reflux(96 mol
%methanol, 66°℃):1253 kcal/kmol;saturated 'vaporized'feed (45 mol%meth anol):10,630
kcal/kmol;heat of vaporization of the top product(96%methanol):8470 kcal/kmol;cp of
water:18 kcal/ kmol°C,cp of methanol:19.4 kcal/kmol·°℃(average values over the
temperature range).
Solution
Enthalpy values of the 'cold'feed at 40°℃ and of the 'cold reflux'at 50°C are required for
the calculations.These can be obtained from the given enthalpies of the streams at
the'saturated' condition.For this purpose we need the heat capacities of these solutions.We
assume that the heat capacity of a solution is a linear function of its concentration.
Heat capacity of the feed (45 mol%methanol),
Cpr =(0.45)(19.4)+(0.55)(18)=18.62 kcal/kmol.°℃
Heat capacity of the reflux (96 mol%methanol),
Cpr=(0.96)(19.4)+(0.04)(18)=19.3 kcal/kmol.℃
The feed line: Enthalpy of the feed is 1390 kcal/kmol,if saturated(74°℃).Its value
at 40℃,Hp=1390-(18.62)(74-40)=757 kcal/kmol.
Similarly,the enthalpy of the 'cold reflux'(50℃),
H,=1253-(19.3)(66-50)=944.2 kcal/kmol

→
 Continuous Multistage Fractionation of Binary Mixtures 383

The intercept of the feed line on the x-axis =zrlq=0.45/1.068 =0.421.The feed line can be
drawn.

Internal refux ratio: This can be calculated from Eq.(7.91).The external reflux ratio,
R=L₀/D =2.25.

The intercept of the rectifying section operating line on the y-axis

=xp/(R'+1)=(0.96/3.33) =0.284.
Determination of the number of trays: Given:xp=0.96,xw=0.04,zF =0.45.The
equilibrium data are plotted on the x-y plane and the diagonal line is drawn.The points D(0.96,
0.96),W(0.04,0.04),and F(0.45,0.45)are located.The feed line is drawn through F with an
intercept of 0.421 on the x-axis.The operating line for the rectifying section is drawn through
the point D with an intercept
1.0 of 0.284.The feed line and the upper operating line meet at the
point E₁.The points WEquilibrium
and E line
are joined to get the lower operating line.The graphical
‘Pseudo'-equilibrium
construction is shown in Figure 7.24.
line0.8
N
0.6
y ME=0.6 MN
F
0.4
M/
E
0.2

W
0.2 0.4 0.6 0.8 1.0
x

0.0
0.0

Figure 7.24 McCabe-Thiele construction of real trays for a given Murphree tray eficiency.

The Murphree efficiency is given as 60%.We draw the 'pseudo-equilibrium line'which is

the locus of a point E located at 60%of the height of a vertical line segment MN between
the operating line and the equilibrium line.Now steps are constructed between the operating line
and the pseudo-equilibrium line (we started from the end D).The total number of real stages
=11

Multiple feed or product withdrawal

If two feeds of different compositions are to be treated in a column,each should normally be

introduced on the tray of matching composition.Similarly,a product stream of any intermediate
384 Chapter 7 Distillation

composition may be withdrawn from the appropriate tray.Withdrawal of side streams is done
frequently in refinery columns.Developing the equations of the operating lines and the
determination of the number of plates in such a column is discussed in Example 7.20.
A column with two feeds and one side stream is shown in Figure 7.25(a).We may consider
the column as consisting of four sections on the basis of the flow rates of the liquid and
the vapour phases.(As stated before,a section means a part of the column between two
input or output points.)The number of such sections in a column is one less than the total
number of input and output streams.The liquid and vapour flow rates vary from one section to
another.The operating line for each section has a different slope.So,there will be as many
operating lines as the number of sections.
Determination of the minimum reflux ratio for such a column is a bit tricky.The pinch
point may occur at the intersection of a feed line,or a side stream line,and the equilibrium
curve.If the equilibrium curve has any unusual curvature,a pinch point may have to be
found out by drawing an operating line that touches the equilibrium curve.

EXAMPLE 7.20(McCabe-Thiele construction—multiple feed and product

withdrawal) A distillation column receives two feeds:(i)200 kmol/h,80%liquid and
20%vapour,with 42.86 mole%methanol on the average;(ii)100 kmol/h,saturated liquid,with
17.65 mole%methanol. The top product must have a purity of 96.1 mole%and the bottoms
must not have more than 3.1 mole%of the alcohol.A liquid side stream having 66.67 mole
%methanol is to be withdrawn at a rate of 35 kmol/h.The reflux is returned to the top tray
as a saturated liquid at a reflux ratio of 2.0.(a)Determine the equations of the operating
lines.(b)Find the number of ideal trays required for the separation.(c)Identify the feed trays
and also the tray from which the side stream should be withdrawn.Vapour-liquid
equilibrium data at the operating pressure of 1 atm is given in Example 7.15.
Solution
Basis of calculation:1 hour operation.The column is sketched in Figure 7.25(a).Given:
Feed 1:F₁=200 kmol;feed 2:F₂=100 kmol;side stream,S=35 kmol.Reflux ratio,R
=2. A sketch of the column with the various streams is shown in Figure 7.25(a).There are
two feeds and one side stream.So,as discussed earlier,there are four operating lines of the
four sections of the column.In order to find out the equations of the operating lines,the liquid
and vapour flow rates in all the sections are to be calculated.The material balance
calculations are done first.

Material balance: Total material balance:

F₁+F₂=D+S+W→200+100=D+35+W (
Methanol balance: F₁Zr₁+F₂Zr₂=Dxp+Sxs+Wxw
→ (200)(0.4286)+(100)(0.1765)=(0.961)xp+(35)(0.6667)+(0.031)xw
→ (0.961)xp+(0.031)xw=84.3 (ii)
Solving Eqs.(i)and(ii),D =77.25 kmol/h;W=187.75 kmol/h.
The equilibrium diagram and the diagonal are drawn in Figure 7.25(b).The points
D(xp,xp), W(xw,xw),S(xs,xs),F₁(zr₁,zFi)and F₂(zrz,zr₂)are located on the x-y plane.
 Continuous Multistage Fractionation of Binary Mixtures 385

Figure 7.25(a) A distillation column with two feeds and one side stream withdrawal.

Operating lines: The liquid flow rate of Section I decreases by an amount of S =35 kmol
as the liquid enters Section II (because of side stream withdrawal).Because of addition of
the feed 1(which is 80%liquid and 20%vapour),the liquid flow rate increases by (0.8)
(2000)= 160 kmol/h in Section III,and again by 100 kmol/h in Section IV(because the
second feed is a saturated liquid).

The liquid rate in Section I,Lo =RD =(2)(77.25)=154.5.

(a)Vapour rate,V₁=V=(R+1)D=(2+1)(77.25)=231.75.This value remains
constant in Section I.
The flow rates of the streams in different sections and the equations of the operating
lines are given below.

Section Liquid rate Vapour rate Slope of the Equation of

operating the operating
line line
I L(I)=L₀=154.5 V=231.7
II L(II)=L(I)-S =119.5 5 L₀/ y=0.6667x+0.3
V=231. V=0.6667 203
III L(III)=L(II)+0.8F₁ -0.2F₁
75 L(II)/V=0.515 y=0.5156x
=119.5 +(0.8) V=231. -40 6
(200)=279.5 75 +0.421 Y = 1.4576r
L(III)/V=1.457
+ 0.0617
=231.7 6
IVL(IV)=L(III)+F₂ 5 y=1.9791x-0.03028
L(IV)/V=1.979
=191.7
=279.5 +100 =379.5 1
5
V=191.7
5

Some details of the calculations are given here.Operating line I starts at

D(xp,xp),i.e. (0.961,0.961)and has an intercept =xp/(R+1)=0.961/(2 +1)=0.3203.Its
equation is
y=0.6667x +0.3203.
Operating line II starts at the point E₁[see Figure 7.25(b)]having coordinates
(0.6667,0.7647) which is the point of intersection of the vertical 'side stream line',x=0.6667
and y=0.6667x + 0.3203.Also the operating line II has a slope 0.5156.Its equation is
y=0.5156x +0.421.
386 Chapter 7 Disillation

(Note:The 'side stream line'is vertical as the side stream is drawn as a saturated liquid.)

Figure 7.25(b) McCabe-Thiele construction of the number ofideal trays for muliple feed and product withdrawal.

Feed-1 has 80%liquid in it,i.e.q=0.8.Feed line-1 has a slope of q/(q-1)=-4.It

passes through(zFi,zri),i.e.(0.4286,0.4286)on the diagonal.Its equation is y=-4x+2.143.The
point of intersection of the feed line-1 and the operating line II is E₂(0.3813,0.6176).
The operating line III starts at E₂(0.3813,0.6176)and has a slope of 1.4576.Its
equation is y=1.4576x+0.0618.This line meets the feed line-2 (it is a vertical line since this
feed is a saturated liquid)at E₃.Join E₃W to get the operating line IV.
(b)The operating lines are drawn and the steps are constructed between the equilibrium
line and the four operating lines as shown in Figure 7.25(b).The number of ideal trays is
7.8

(c)From Figure 7.25(b),the side stream is drawn from tray no.4,the feed-1 enters the
tray no.5 and the other feed enters the tray no.7.

7.7 MULTISTAGE BATCH DISTILLATION WITH REFLUX

In single-stage batch distillation(Rayleigh distillation),the purity of the product is practically

governed by the concentration of the feed and the fraction distilled out.However,if a batch
of liquid is distilled in a multistage column with reflux,a significantly higher product purity as
well as higher fractional recovery of the product can be achieved.A schematic of a multistage
batch distillation unit is shown in Figure 7.26.
 Mulistage Batch Distillation with Reflux 387

In the theoretical analysis given below we assume

that:(a)constant molar overflow occurs,i.e.the
vapour rate V and the liquid rate L remain constant in
the column;(b)liquid holdup on the plates
is negligible;(c)although batch distillation is an
unsteady state process,we assume that pseudo-
steady state condition prevails;this means that the
liquid and the vapour concentration profiles in the
column at any moment are the same as the
steady-state profiles achievable under identical
conditions.
It is easy to understand that if the reflux ratio
is held constant,the distillate concentration will
decrease as the distillation proceeds.So the column
may be operated till the distillate quality remains
within the acceptable limit.This is called the
constant reflux operation.Alternatively,the reflux ratio Figure 7.26 Schematic of a multistage batch
is continuously increased so that the product distillation setup
concentration remains constant for some time.This
is called the variable
reflux operation.In practice,the constant reflux
operation is more common.

7.7.1 Constant Reflux Operation

Let the amount of liquid in the stillpot of the multistage unit at any moment be W mole at
a concentration xw.Over a small time,dD mole of distillate is withdrawn and the amount of
liquid in the stillpot decreases by dW mole.Following Eq.(7.47),
-d(Wxw)=xpdD → -Wdxw-xwdW=-xpdW (since dD =-dW) (7.94)

(7.95)
→

If W and W are the initial and final amounts of liquid in the stillpot,then on integration,

(7.96)

As distillation proceeds,xp and xw both keep on changing.This is shown in Figure 7.27(a)for

a batch column having two ideal trays and a stillpot(equilibrium vaporization occurs in
the stillpot).An operating line of slope =R/(R+1),for the constant reflux ratio R,is
drawn.Three stages are constructed starting from(xp,xp)on the diagonal.A value of
xw(xwr≤xw≤xwi) is reached at the end of three stages.A set of such operating lines are drawn
to yield a set of (xp,xw)values.The integral in Eq.(7.96)can now be evaluated
graphically.Of the four quantities—W,Wy,xwi,xwr—any one can be calculated by this way if
the others are known.The accumulated distillate composition can be found out by material
balance.

(7.97)
388 Chapter 7 Distillation

EXAMPLE 7.21(Batch distillation with constant refux)Forty kilomoles of an equimolar

mixture of benzene and chlorobenzene is to be batch-distilled at 1 atm total pressure in a
column consisting of a stillpot,two ideal trays and a total condenser.Reflux is returned to the
top tray as a saturated liquid and the reflux ratio is 1.0.Distillation is to be continued until the
benzene concentration of the liquid in the stillpot becomes 6 mol%.Calculate the amount and
purity of the collected distillate,the amount of liquid left in the stillpot,and the fractional
recovery of benzene.Liquid holdup on the trays is assumed to be rather small.Vapour-liquid
equilibrium data for the system are given below.
x 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 1.0
y 0 0.314 0.508 0.640 0.734 0.806 0.862 0.905 0.943 1.0
Solution
Here the batch still is operated at constant reflux.As a result,the concentration of the vapour
from the top tray will decrease gradually.Our procedure will be:(i)select a number of values
of xp on the diagonal and to draw the corresponding operating lines(since the reflux rate is
constant,the operating lines will be parallel);(i)for each value of xp,determine the value of
xw by drawing three stages(two trays and the stillpot)between the operating line and the
equilibrium line.Thus,we shall have a set of values of xp and xw within the concentration
range xwi =0.5 (initial)and xw=0.06(final).The integral in Eq.(7.96)can then be evaluated
graphically.
Reflux ratio,R=1.0;constant slope of the operating lines =R/(R +1)=0.5
The equilibrium line,the two operating lines and the graphical construction are shown
in Figure 7.27(a).The values of xp,xw and(xp-xw)-'obtained from the graph are as
follows:
Xp 0.95 0.90 0.85 0.80 0.75 0.70 0.65 0.60 0.50 0.40 0.30
Xw 0.50 0.35 0.28 0.245 0.205 0.175 0.15 0.135 0.105 0.090 0.056
(xo-xw)-l 2.222 1.818 1.754 1.802 1.835 1.905 2.0 2.151 2.532 3.226 4.10

(xp-xw)-¹is plotted versus xw in Figure 7.27(b)and the area under the curve from
xwy=0.06 to xwi =0.50 is 0.9065.

(x-dx)/

(a) (b)

Figure 7.27 (a)Parallel operating lines and three ideal stages for constant reflux batch distilation,and (b)graphical evaluation
of the integral in Eq.(7.96).
 Multistage Batch Distillation with Reflux 389

Also the initial amount of liquid,W;=40 kmol.From Eq.(7.96),

→
Wj=16.16 kmol and D=W;-W;=23.84 kmol
By benzene balance,we get the concentration of the accumulated distillate,(xp)av.
Use Eq.(7.97)to get

Amount of distillate collected =23.84 kmol],its purity = 80 mol%benzene

liquid left = 16.16 kmol

Fractional recovery of benzene =(23.84)(0.8)/(40)(0.5)= 0.95
4
EXAMPLE 7.22(Simple batch distillation,graphical/numerical evaluation of the integral)
Consider that the separation of the mixture in Example 7.21(40 moles feed with 50 mol%
benzene)is to be done in a simple batch distillation unit in which the vapour from the
stillpot is condensed to get the distillate(see Figure 7.13).If the amount of accumulated
distillate is the same as in Example 7.21,calculate the composition of the distillate and the
fractional recovery of benzene.Also,approximately calculate the ratio of the energy
requirements in the two cases.
Solution
The working equation is Eq.(7.50)which may be written in the form

Given:W;=40 kmol;D=23.84 (as calculated in Example 7.21);W=40-23.84 =16.16;x₁=0.5;

In(W;/W)=In(40/16.16)=0.9065;xr=?
A set of values of x is selected starting from x =0.5.The equilibrium vapour composition
y*is obtained from the plot of the equilibrium data.A plot of 1/(y*-x)versus x is prepared.The
value of x,is obtained from the plot such that the area under the curve is 0.9036.The
tabulated values are given below and the plot is shown in Figure 7.28.
x 0.50 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10
y* 0.81 0.773 0.734 0.69 0.64 0.581 0.508 0.415 0.314

1/(y*-x) 3.226 3.096 2.994 2.941 2.941 3.021 3.247 3.773 4.673

From Figure 7.28,xr=0.21 =concentration of the liquid left in the stillpot.The product
composition is obtained by material balance.

(40)(0.5)=(16.16)(0.21)+(23.84)(xp)av →(xp)av = 0.696

390 Chapter 7 Distillation

of benzene =(23.84)(0.696)/(40)(0.5)= (Compare with the

Fractional 0.83
recovery of 0.954 Example 7.21.)

1/(y*-x)

Figure 7.28 Graphical integration.

In Example 7.21,the reflux ratio was R =1.0.The total amount of vapour generated,
V=(R+1)(23.84)=(2)(23.84)=47.68,which is double the amount of vapour generated
in simple batch distillation.So the energy consumption is about twice the value of that in
Example 7.21.

7.7.2 Variable Reflux Operation

In a variable reflux operation,the reflux ratio is continuously increased in such a manner that
the distillate concentration remains unchanged despite the fall in concentration of the more
volatile in the stillpot.If dV,dL and dD are the changes in the rates of vapour flow,liquid
flow and distillate withdrawal,

dV=dL+dD (7.98)
→ dD=[1-(dL/dV]dV (7.99)
By material balance,

Wxw=Wxwi-(W;-W)xp [xp=constant] → (7.100)

Substituting for dD and W from Eqs.(7.99)and(7.100),in the material balance Eq.

(7.98)and noting that dD =-dW,

Total amount of vapour generated,

(7.101)
 Multistage Batch Distillation with Reflux 391

For a given number of ideal trays,a bunch of operating lines of different slopes(dL/dV =L/V
=slope of the operating line)can be drawn,and the plates can be constructed to get the xw
value. This allows graphical integration of Eq.(7.101)and calculation of any relevant
quantity. Example 7.23 illustrates a practical batch distillation problem with variable reflux.

EXAMPLE 7.23 (Batch distillation with variable reflux)Ten kilomoles of acetone has been
pumped by mistake into a storage vessel of ethanol containing 10 kilomoles of ethanol.It is
decided to separate the mixture by batch distillation.Ten mole%of al cohol in the top product
and 12 mole%acetone in the bottom product are acceptable.A column having six theoretical
plates,a reboiler and a condenser is available.The operation is to be carried out at
essentially atmospheric pressure and the reflux is to be returned at its bubble point.
(a)Calculate the amounts of top and bottom products.(b)What initial and final reflux
ratios should be used?(c)Determine the total moles of vapour to be generated to achieve
the separation.(d)If steam is supplied to the coils in the still at such a rate that 6 kmol of
vapour is generated per hour,calculate the time required for distillation.The vapour-liquid
equilibrium data for the acetone-ethanol system are given below.
x 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
y 0.16 0.25 0.42 0.51 0.60 0.67 0.72 0.79 0.87 0.93 1.00

Solution
(a) The quantities of the top and the bottom products can be calculated from material balances.
Total material balance:
F=D+W→20 =D+W; D=moles distillate;W=moles residue.

Acetone balance:
Fxp=Dxp+Wxw→(20)(0.50)=D(0.9)+W(0.12)

→ D= W= 9.74 10.26
(b)and(c) This is a case of operating a batch still with variable reflux.The concentration of
the more volatile (acetone)in the still decreases gradually.But the reflux ratio has to be increased
continuously until the bottom liquid concentration(xw)drops down to 12 mol%acetone
while seven ideal trays (six plates and a reboiler)are fitted between the operating line and the
equilibrium line.The overhead vapour concentration should always be 90 mol%acetone.The
steps are:

(i) Draw the equilibrium line on the x-y plane.

(ii) Locate the point (xp,xp)where xp =0.90.
(ii) Draw a bunch of operating lines emanating from(0.9,0.9)and having varying slopes.
(iv) In each case,fit seven ideal stages between the operating line and the equilibrium
line and determine the bottom concentration,xw.
(v) Using the(xp,xw)data as well as the slopes of the bunch of operating lines drawn,
evaluate the integral in Eq.(7.101)numerically to get the total moles of vapour
generated during distillation.
392 Chapter 7 Distillation

The equilibrium line and only two operating lines (DEi at the beginning of the operation,and
DE₂at the end;a few other operating lines were drawn for calculations but are not
shown)are shown in Figure 7.29(a).The graphical construction of seven ideal stages is also
shown.The calculated data for graphical evaluation of the integral in Eq.(7.101)are given
below.Graphical integration is shown in Figure 7.29(b).
dL/dV=(L/V) 0.733 0.787 0.833 0.905 0.919

0.5 0.335 0.21 0.13 0.12

23.4 14.7 12.96 17.75 20.3

The initial reflux ratio is R;=0.733

The area under the curve in Figure 7.29(b)is
and the6.04.
end reflux ratio is Rs=
Total quantity of vapour generated [Eq.(7.101)],

Vot =W(xp-xw)I=(20)(0.9 -0.5)(6.04)= 48.32 kmol

(d) Rate of vapour generation =6 kmol/h.Time of distillation =48.32/6 =

8.05 h

I(xw-xoP-
Xmy=0.12
7/3
₂
0.0'0.0 0.2 0.4 1.0

xy
(a) (b)

Figure 7.29 (a)Graphical construction of stages for variable reflux batch distillation(the two extreme operating lines only
are shown),and (b)graphical integration.

Another strategy of operation of a multistage batch distillation column,called the 'optimal

reflux' operation has been described by Divekar(1995).
 The Ponchon-Savarit Method 393

7.8 THE PONCHON-SAVARIT METHOD

This method was developed by Ponchon and Savarit independently in 1921-22.It is a more
rigorous method and is free from the assumption of 'constant molar overflow'.So the use of
this method is suggested if the enthalpy of a stream appreciably depends upon its
composition. The Ponchon-Savarit method is also a graphical method of solution of the
material and energy balance equations as well as the equilibrium relation taken together.
The rectifying section: Refer to Figure 7.14(a).Consider the material and energy balance
Eqs.(7.64)and (7.65)taken over envelope 2:
(7.102)

[Note:Here we assume that the reflux may be a sub-cooled liquid (i.e.below its bubble
point) in general and zp is the mole fraction of the more volatile in it.]
The energy balance Equation(7.65)is rewritten as

(7.103)

Here Qa=Hp+QdD=thermal energy removed from the top section of the column per
mole of distillate.Putting D =V+I-L [see Eq.(7.63)]in the above equation,

(7.104)

[The quantity Ln/V+t is the internal reflux ratio.]

From Eqs.(7.102)and(7.104),

(7.105)

Refer to Figure 7.30 on which the liquid and vapour enthalpy-concentration curves (x-Ht and
y-Hv)are plotted.A point on this diagram represents the composition and enthalpy of a phase
(liquid,vapour or mixed),and we denote this point by a term that also represents the flow rate
of the particular phase (this convention has been used before).Thus,the point Ln represents the
liquid phase leaving the nth plate(and entering the(n+1)th plate)at a rate L,mole/h with enthalpy
HLn and concentration xn.
The right side of Eq.(7.105)is the slope of a line through the points(yn+i,Hyn+l)and
(zp,Qa),and the left side is the slope of a line through the points (xn,HLn)and(zp,Qa)on the
concentration-enthalpy plane.So the points (xy,H),(yn+1,Hyn+i)and(zp,Qa)are collinear.
The point (zp,Qa)can be viewed as a phase obtained by subtracting Ln from V+l(see the
discussion in the last para of Section 7.2).We represent this point by D'in Figure 7.30.The flow
rate of the phase D'is also denoted by D'=V+I-L..However,none of the phases can have
the concentration zp and enthalpy Qa=Hp+Qd/D.So this stream D'is a“fictitious stream”
defined solely for the purpose of graphical construction.
The point D(zp,Hp)and D(zp,Qa)are located on the enthalpy-concentration diagram,D'
lying vertically above D(because they have the same abscissa,zp).In Figure 7.30,the point
D
394 Chapter 7 Distillation
120 /m

90
y-Hy

V₇+I
"
/V60

3 W₂ lV₁
H·H30

x-H₁
o+
ZD L₁ L-1 L₂ L₁ Di
0.2
x,y
0.0 0.4 0.6 0.8 1.0

Figure 7.30 Ponchon-Savant construction for the rectifying section of a distilation column.

lies below the x-Ht curve.So,the reflux is a sub-cooled liquid here.If we put n =0 in
Eq.(7.105),it appears that the vertical line joining the points D and D'should intersect the
y-Hy curve at (yi,Hv)because these points are collinear.The point (yi,Hvi)is denoted by
V₁ according to our convention.The point L₁(xj,HLi)is now located by drawing a tie line
through V₁,because x₁and yi are in equilibrium for an ideal tray.Next,L₁D'is joined to get
the point V₂.The graphical construction now proceeds from one tray to the next.
Now we consider Eq.(7.104),again.Inverting both sides and putting n =0,

we note that Hto =Hp;V₁=Lo+D

(7.106)

If the reflux ratio is given,Eq.(7.106)can be used directly to locate the point D'.First the
point D(zp,Hp)is located from the known state(concentration zp,and enthalpy Hp).A vertical
line through zp intersects the y-Hy curve at Vi.Then obtain D'so that Eq.(7.106)is
satisfied.
The stripping section: The material and energy balance equations for the stripping section

(envelope3),Figure 7.14(a)are given by Eqs.(7.66)through(7.68).Putting W=Lm-Vm+I

from Eq.(7.66)in Eq.(7.67),
Zm×m=Vm+1Ym+1+(Zm-Vm+)xw (7.107)

→ (7.108)
 The Ponchon-Savarit Method 395

We may write the energy balance Equation (7.68)as

LmHm-Vw+1Hvm+1=WHw-Qg=W(Hw-QB/W)
→ ZHLm-V+Hxm+1=WQw;Qw =Hw-Q₈/W (7.10
Putting W=Lm-V+l,

(7.110)

From Eqs.(7.108)and(7.110), (7.111)

Extending the arguments put forward in the analysis of the rectifying section,we can say:
(a)The points Vm+l(Sm+1,Hym+i),Lm(xm,HLm),and W(xw,Qw),are collinear
(b)The point W'denotes a“fictitious stream”of concentration xw,enthalpy Qw=
Hw-Qg/W(=the rate of enthalpy removal at the bottom,per mole of the bottom
product),and flow rate W'=Lm-Vm+I.
Now,let us see how to proceed with the graphical construction of stages for the stripping section
(Figure 7.31).The points W(xw,Hw)and W(xw,Qw),are located on the enthalpy-concentration
plane.The output stream or the bottom product,W,leaving the partial reboiler is in equilibrium
with the vapour generated
140
in the reboiler and entering the bottom tray.If there is a total of N
trays in the column,we may call the reboiler the(N+1)th tray.So the flow rate as well as the
state 120
100
80
Vv+1
Kv
y-Hy
60 Vv-1
40
H" *-HL
LNI F V₁
Hy D
0+
0.0
20
x,y
·
y
VW"

0.5 ZD10

Figure 7.31 Ponchon-Savarit construction for the stripping section of a distillation column.
396 Chapter 7 Distillation

of the vapour from the reboiler is denoted by Vw+i;Vw+I should lie on the y-Hy curve at the
end of the tie line through W.The line connecting Vv+i and W'intersects the x-Hr curve at
Lv by virtue of the collinearity condition given by Eq.(7.111).The tie line through Lv identifies
Vw on y-Hy curve and thus the construction for trays in the stripping proceeds.

The feed line: The procedures of graphical construction of ideal trays for the rectifying
and for the stripping sections have been discussed above.However,a changeover from one
section to the other is necessary at the feed tray and for this purpose we have to draw the 'feed

line'.Consider the material and energy balance equations over envelope 4 of the column in
Figure 7.14(a)as given by Eqs.(7.69)through(7.71).Substituting for F from Eq.
(7.69)in Eq.(7.70),
(D+W)zp=Dzp+Wxw (7.112)

[Note:We use zp to denote the reflux or distillate concentration because these may be subcooled
liquids;the notation xp may be used if the streams are at bubble point.]

→ (7.113)
Similarly,from Eqs.(7.69)and (7.71),

(D+W)Hr+Qg=DHD+WHw+Qc
→ DHp+WHp=D(Hp+QclD)+W(Hw-Qg/W)

→ (7.114)
From Eqs.(7.113)and (7.114),

(7.115)
The above equation shows that the points W(xw,Qw),F(zp,Hr),and D'(zp,Qd)
are collinear.The intermediate point F(zr,Hr)denotes the state of the feed in terms of
composition and enthalpy.It lies on the line joining W'and D'.As stated before,W'represents
a fictitious stream of flow rate W'=Lm-Vm+I=W,and D'is another fictitious stream of flow
rate D'=V+i-L=D.

→ F=D+W=D'+W' (7.116)
So,F,a real stream,can be viewed as a stream obtained by mixing the two fictitious
streams W'and D'.The line W'D'is called the feed line.On the basis of graphical construction
described above,the steps to be followed for the determination of the number of ideal stages
are:

(a) We assume that the concentrations,the enthalpies,and the flow rates of the distillate and
the bottom product as also the reflux ratio are given(or sufficient data are supplied
for the calculation of these quantities by material and/or energy balance).Then the
points D and D'are located on the H-x,y diagram.
 The Ponchon-Savarit Method 397

(b) The feed point F(zr,Hr)is located.

(c)D'Fis joined and extended to meet the vertical line through W(xw,Hw)at the point
W'. (d)Construction of stages may proceed either from D'or from W'.A changeover
has to
be done after the feed line is crossed.The tray at which the changeover is made is
the feed tray.Construction proceeds till the other point is reached.
It is possible (and perhaps more convenient)to construct the stages on the x-y plane
rather than on the H-x,y plane.The steps of such construction are given below.
(a) Draw the equilibrium curve using separate axes below the H-x-y curves with
matching scales.
(b) Locate(Zp,zp)and(xw,xw)on the diagonal.
(c) It is obvious from Eq.(7.105)that any line emanating from D'(or W')intersects the
H-x and H-y curves at xn and yn+i respectively.The point(x,yn+i)is a point on the
operating line in the lower diagram(see Figure 7.32).Several lines are now drawn from
D'and W'and for each such line,the point (Xn,yh+i)is located on the x-y plane.All such
points are joined by two continuous curves.These two curves are the two
operating lines.Because the flow rates in any of the sections are not constant (since
constant molar overflow is not applicable),the operating lines are not
straight.Staircase construction between the equilibrium line and the operating lines
gives the number of ideal stages.The procedure is illustrated in Example 7.24.

Minimum reflux ratio(Rm)

If the reflux ratio is minimum,there must be a pinch point on the diagram.If a line through D'or
W'coincides with a tie line,the corresponding (x,y)values give the pinch point.The expression
for the reflux ratio given by Eq.(7.106)indicates that the smaller the distance V₁D'(or the
nearer the point D'is to the concentration axis),the smaller is the reflux ratio.For many liquid
mixtures this happens when the line D'W'coincides with the tie line through the feed point
(compare with Figure 7.20).But for some highly non-ideal mixtures,it so happens that a tie line
through a point other than F intersects the vertical line through zp at the smallest
distance.This gives the true pinch point.The minimum reflux ratio is calculated by Eq.
(7.106)once the point (D)min is identified.

EXAMPLE 7.24 (Determination of the number of ideal trays using the Ponchon-Savarit method)
An aqueous solution of ethanol (30 mass%ethanol)is to be enriched into a top product having
88 mass%alcohol.The bottom product must not contain more than 4 mass%alcohol.The
feed enters the column at 40°℃ at a rate of 5000 kg per hour.The reflux is at its bubble
point and the reflux ratio is 1.0.Determine(a)the number of ideal trays required using the
Ponchon- Savarit method and(b)the heat duty of the condenser and of the reboiler.The
enthalpy- concentration(kJ/kmol;reference states:pure liquids at 0°C)and the vapour-liquid
equilibrium data at the operating pressure of 1 atm are given below.
x,y 0 0.0417 0.0891 0.1436 0.207 0.281 0.37 0.477 0.61 0.779 1.0
H₁ 7540 7125 6880 6915 7097 7397 7750 8105 8471 8945 9523
Hy 48150 48250 48300 48328 4845 48450 48694 48950
48436 0 48631
398 Chapter 7 Distillation

X 0 0.00792 0.016 0.0202 0.0417 0.089 0.143 0.281 0.37 0.47

1 6 7
y 0 0.0850 0.1585 0.191 0.304 0.427 0.493 0.568 0.603 0.644
x 0.61 0.641 0.706 0.779 0.86 0.904 0.95 1.0
y 0.703 0.72 0.756 0.802 0.864 0.902 0.945 1.0
6
Given:enthalpy of the feed =4790 kJ/kmol.
Solution
Molecular weights:ethanol =46;water =18.The concentrations of the feed zr,the top and the
bottom products(xp and xw)in mole fraction units and mol.wt.of the feed Mp are given by

xp=0.7416; xw =0.01604

Feed rate,F =5000/22.02 =227 kmol/h

Total material balance equation:F=D+W=227 =D +W (i)

Ethanol balance:Fzp=Dxp+Wxw →(227)(0.1436)=D(0.7416)+W(0.01604) (ii)
Solving Eqs.(i)and(ii),D=39.9 kmol/h;W=187.1 kmol/h
Enthalpy values of the feed(Hp),the top and the bottom products (Hp and Hw):
Enthalpy of the feed at 40°C,Hp=4790 kJ/kmol (given).
The other enthalpy values can be obtained by interpolation of the given data.
Enthalpy of the top vapour(y₁=0.7416),Hv₁=48,680 kJ/kmol;enthalpy of the
distillate (xp=0.7416),Hp=8850 kJ/kmol;enthalpy of the bottom product,Hw =7380
kJ/kmol.
(a)Graphical construction of the number of ideal trays

(i) The given enthalpy-concentration data are plotted in Figure 7.32(a).

(i) The points F(zr,Hr)→(0.1436,4790),D(xp,HD) →(0.7416,8850),and
W(xw,Hw)→(0.01604,7380)are located on the enthalpy-concentration plane.
(ii)Next the difference point,△D(xp,Q4),is to be located;Qi is related to the reflux ratio
as given in Eq.(7.106).The reflux ratio is R =1.0 (given).

→ Q1=88,510 kJ/kmol;△D′→(0.7416,88,510)
(iv)A vertical line is drawn through the point W;△D'F is joined and extended to meet this
vertical line through W at △W'[△D'and △W’are the same as D'and W'in Figures 7.30
and 7.31].
(v) The number of ideal trays or stages can be determined by drawing tie lines and operating
lines (through△D')as described in Section 7.8.However,it is more convenient to adopt
the following procedure.
Draw a number of lines from the point △D'on the right side of the feed point F
[Figure 7.32(a)].Consider one such line △D'MM₁(M is on the saturated vapour line and
M₁is
 The Ponchon-Savarit Method 399

on the saturated liquid line).The abscissa of the point M₁(i.e.the liquid composition x)and
the abscissa of the point M(i.e.the vapour composition y)give the coordinates of the point
P on the x-y diagram drawn below the enthalpy-concentration diagram [Figure 7.32(b)].A set
of such points on the x-y plane are joined to get the operating line for the rectifying section.

AH
H

x
(b)
Figure 7.32 Construction of plates using the Ponchon-Savarit method:(a)enthalpy-conc.diagram,and (b)plate.

Similarly,a set of lines are drawn from the point △W'on the left side of the feed point F.
The points of intersection of such lines and the enthalpy-concentration curves are used to draw
the operating line for the stripping section on the x-y plane.Now steps are drawn between the
operating lines and the equilibrium curve on the x-y plane starting from the top or the bottom
end.The number of ideal trays is found to be 10|.The intersection of the operating lines
is crossed at tray number 7 from the top.So the 7th tray is the optimum feed tray.
400 Chapter 7 Distillation

(b)Calculation of heat duties of the reboiler and condenser: To calculate the condenser heat
duty,use the following equation:

Qa=Ho+QcID→88,510=8850+Qcl39.9→Qc=316×10⁶kJ/h
To calculate the reboiler heat duty,first use Eq.(7.115).

→
Qw=-13.068 kJ/h
Now use Eq.(7.109). Qw=Hw-Qg/W

→ -13,068=7380-Qg/187.1

→ Qo=[ 3.826×10⁶k

Total reflux

Here the reflux ratio is infinite and the points D and W'lie at infinity.So all the lines through
D'and W'are vertical lines.The construction involves drawing alternate tie lines and
vertical lines starting at V₁to obtain the number of plates at total reflux.This gives the minimum
number of plates too.However,it is easier to find it by drawing steps between the equilibrium
curve and the diagonal on the x-y plane.

Optimum reflux ratio

While designing a new column(or even for using an existing column)for a given separation,the
designer has to choose a reflux ratio.From the foregoing discussion,it is clear that the number
of plates required decreases as the reflux ratio is increased.The column height decreases as a
result.However,at a higher reflux,both the liquid and vapour flow rates are higher.This
increases the column diameter.But,on the whole,the cost of the column decreases with
increasing reflux ratio.On the other hand,a larger reflux ratio demands higher heat duty of both
the reboiler (more heat supply to the reboiler is necessary to maintain a larger supply of the
vapour)and the condenser (more heat is to be removed in the condenser).So the size,and
therefore the capital cost,of these equipment will be more.The operating cost will also be higher
because of larger heat duty of the reboiler and the condenser.So there are a number of
opposing factors that govern the different types of cost.A simplified approach to determine the
optimum reflux ratio is to plot the fixed cost of the equipment taken together and also the
operating cost versus the reflux ratio as shown in Figure 7.33.The plot of the total cost shows a
minimum which gives the optimum reflux ratio.
 Distillation in a Packed Tower 401

Reflux ratio,R

Figure 7.33 Optimum reflux ratio in distilation.

An important point needs attention in this context.The fixed cost has the unit of rupees,
dollars,etc.but the operating cost is based on unit time (rupee/year,dollar/year,etc.).How to
calculate the total cost,then?Without going into details,we can divide the fixed cost by the
estimated“life”of the equipment and then estimate the'total annual cost'.A more r ealistic
calculation should take into account the interest rate on various cost items,if necessary.In actual
practice,a reflux ratio of 1.2 to 1.5 times the minimum is common.

7.9 DISTILLATION IN A PACKED TOWER

Distillation of a liquid mixture in a packed tower

is preferred in the following cases:(a)vacuum or
low pressure operation,(b)low capacity or feed
rate,(c) small allowable pressure
drop,and(d)corrosive service.A packed tower for
distillation is essentially similar to the one used for
gas absorption.However, the tower should be provided
with a distributor for the feed at an appropriate
location(this is in addition to the distributor of the
reflux at the top),besides a condenser,a reflux
drum and a reboiler.

There are two methods for the determination

of the height of packing:(a)from the height
and number of transfer units(Hc and Ng)and
(b)from the HETP.To derive the design equations
for the calculation of the packed height based on Hg
and Ng, refer to Figure 7.34.Let us consider the
rectifying section first.Constant molar overflow is
assumed. The vapour and liquid flow rates Figure 7.34 Schematic ofa packed distilation tower.
remain constant
over a section.Let the flow rates(based on unit
402 Chapter 7 Distillation

cross-section of the tower)be V'and L'kmol/h·m².The individual mass transfer coefficient

are kf and ky,and the specific interfacial area is a.It is to be noted that equimolar
counterdiffusion of the components occurs.If N₄is the local flux at a height h from the
bottom of the packed section,we may write the following differential mass balance equations
for the more volatile component.
Vapour phase a.dh.N₄=d(V'y)=V'dy→kγa(y;-y)dh=V'dy (7.117)
Liquid phase: a.dh.N₄=d(L'x)=Ldx →kxā(x -x;)dh =L'dx (7.118)

Note that transport of the more volatile component occurs from the liquid to the vapour
phase and its concentration in the vapour as well as in the liquid phase increases with h.
Rearranging Eq.(7.117)and integrating over the rectifying section [from y=yr(at the feed point)
to y=y₁(top of the tower)],

一 (7.119)

Here h,is the packed height of the rectifying section.The value of Hc can be calculated if the
individual volumetric mass transfer coefficient,ksa,is known;Nc can be obtained by numerical
or graphical evaluation of the integral in Eq.(7.119).The interfacial vapour concentrations,y,
for a set of values of y(yr<y<yi)are required for the numerical integration.The procedure
described in Section 6.4.1 can be followed for this purpose.From Eqs.(7.117)and (7.118),we
can write

[Compare with Eq.(4.10)] (7.120)

The equation for the operating line for the rectifying section can be written for a given reflux
ratio,R.We take a point(x,y)on the operating line and draw a line of slope-ka/k,a;this line
meets the equilibrium curve at(x;,y;).If the individual coefficients remain constant over a section
(this is quite reasonable because the flow rates do not vary over a section),such lines
emanating from different points on the operating line are parallel.Thus,for a set of
points(x,y),the corresponding interfacial concentrations(x;,y;)required for integration can be
obtained.The procedure is illustrated in Example 7.25.
Similar design equations can be written for the height and the number of individual liquid
phase transfer units.

→ (7.121)
 Distillation in a Packed Tower 403

The packed height can also be determined using the overall coefficients (Kya and Kxa).The
design equations can be obtained by putting N₄=K;(y*-y)in Eq.(7.117)or N₄=K(x-x+)
in Eq.(7.118).

and (7.122)

We assume that the heights of overall transfer units,Hoc and Hol,remain reasonably
constant over the section.The number of overall gas-phase or liquid-phase transfer units are
to be determined by graphical integration.Corresponding to a point(x,y)on the operating
line,y* is the ordinate of the point vertically above it on the equilibrium curve;x*is the
abscissa of a point on the equilibrium line horizontally left to(x,y).Thus the values of y*for a
set of values of y(yr<y<yi)can be obtained and Nog can be evaluated graphically o r
numerically.
Mass exchange between the vapour and the liquid phases in distillation is mostly controlled
by the vapour phase resistance.Thus,for the sake of accuracy,it is advisable to calculate the
packed height using the 'gas-phase coefficient'.
Following the procedure described in Section 6.4.3,it is possible to combine the heights
of individual transfer units to obtain the height of an overall transfer unit.Thus,
Hoc=Hc+λHj; λ=mV'IL', (m=slope of the equilibrium line) (7.123)

It is obvious that the slope of the equilibrium line varies with composition.Even if Hc and Ht
remain constant over a section,Hoc and Hor are liable to variation.However,an average value
can be used.A similar procedure is used to determine the packed height for the stripping
section.

EXAMPLE 7.25(Determination of packed height of a distillation column)A mixture of

diethylamine(1)and triethylamine (2)containing 40 mol%of the higher amine is to be separated
in a packed distillation column(dia =0.75 m)at a rate of 2000 kg/h and at a total pressure
of 113.3 kPa.The top product should have 97 mol%of diethylamine and the bottom
product, 96 mol%triethylamine.The feed is at its bubble point and the reflux ratio used is
twice the minimum.The individual volumetric mass transfer coefficients are:
Rectifying section: k(ā =600 and K,a =170 kmol/h-m³
Stripping section: kxa =750 and k₂a =200 kmol/h·m³
The equilibrium data for the system at the given pressure are available [Bittrich,H.J.,and
E.Kruer:Z.Physik.Chem.(Leipzig),219 (3/4),1962,p.224].

x 0 0.02 0.104 0.227 0.342 0.424 0.522 0.79 0.923 0.969 1.0
y 0 0.052 0.231 0.451 0.60 0.674 0.755 0.91 0.978 0.988 1.0
Solution
Molecular weights:M₁=73.09;M₂=101.1
Average mol.wt.=(0.6)(73.09)+(0.4)(101.1)=84.3
Molar feed rate,F =2000/84.3 =23.72 kmol/h
404 Chapter 7 Distillation

Total material balance: F =D+W → 23.72 =D+W

Component 1 balance:Fzp=Dxp+Wxw →(23.72)(0.6)=D(0.97)+W(0.04)

Solving,D=14.3 kmol/h;W=9.42 kmol/h
The minimum reflux ratio,Rm=0.796 [this can be obtained by the usual procedure].

Actual reflux ratio(2 times the minimum),R =(2)(0.796)=1.592;vapour rate at the

top tray,V=D(R+1)=(14.3)(1.592+1)=37.06 kmol/h;reflux rate,Lo =DR =(14.3)
(1.592) =22.76 kmol/h.
The feed is a saturated liquid.Vapour rate in the stripping section,V=V=37.06;liquid
rate in the stripping section,L =L+F=22.76 +23.72 =46.48 kmol/h.
Rectifying section operating line:

Stripping section operating line: It passes through W(0.04,0.04)and the intersection of

the feed line(x=0.6)and the rectifying section operating line →y =1.255x-0.01
The number of gas-phase transfer units Nc can be obtained by evaluation of the integral in
Eq.(7.119).A set of values of (y;-y)is required for this purpose.
A set of lines of slope-ka/ka=-600/170=-3.75 are drawn between the operating line
and the equilibrium lines for the rectifying section to get a set of values of y and y;and hence
of y;-y.Similarly,another set of lines of slope-ka/kya =-750/200 =-3.53 are drawn
between the operating line and the equilibrium line for the stripping section.A few such lines
are shown in Figure 7.35(a)and several values of y;-y are given below.

=-k/k

/(y;-y)

E
0.6 0.8 1.0

x
y
(a) (b)

Figure 7.35 (a)Determination ofthe interfacial concentrations y;in a packed distillation column.A set of(dotted)lines of
slope k/k,is shown.Step construction for ideal trays is also shown.(b)Graphical integration.
 Notations 405

y 0.97 0.95 0.895 0.835 0.77 0.725 0.615 0.49 0.365 0.168 0.04
y; 0.99 0.977 0.935 0.885 0.828 0.792 0.713 0.625 0.495 0.263 0.07
1/(y;-y) 50 37.04 25 20.83 18.2 14.3 10.2 7.41 7.7 13.2 33.3

The integral for Nc is obtained by graphical integration as shown in Figure 7.35(b).The

areas under the curves are:

Rectifying section:Ng =5.02 units;stripping section:Ng =8.7 units

The values of Hc for both the sections are required in order to find out the column
height. It is to be noted that the vapour flow rates are the same in both the sections,but the
volumetric vapour phase mass transfer coefficients vary.The column dia is 0.75 m;its
cross-section is 0.442 m².
Vapour flow rate =V′=37.06/0.442=83.85 kmol/h-m²=V’(for the stripping section)

(H₆)ec=V'/k;a =83.85/170= 0.49m];(Ho)suip=V’/k;a =83.85/200 =「

0.42 m
Total packed height of the two sections =(0.49 m)(5.02)+(0.42 m)(8.7)= 6.1
Eleven theoretical plates are required for the separation as shown in Figure
7.35(a).The average height of a theoretical plate(HETP)for the packing under the given
conditions is
HETP=6.1/11=0.55 m

The concept of HETP(see also Chapter 6)is widely used in packed tower design.Experimental
data on the performance of a particular packing are sometimes expressed in terms of HETP rather
than the volumetric mass transfer coefficients.If the HETP value is known,the packed height
can be determined from the calculated number of theoretical trays required for the separation.
The diameter of a packed column is calculated from flooding considerations as usual.As the
flow rates differ in the two sections,it is advisable to estimate the diameter based on the larger
flow rates for a safer design.

NOTATIONS

CpA :specific heat of component A(liquid)

D :rate of withdrawal of the distillate at the top of a column,kmol/h
EM :Murphree efficiency,Eq.(7.93)
E
I :feed rate,kmol/h
Hc :height of a vapour-phase mass transfer unit,m
HL :height of a liquid-phase mass transfer unit,m
HL :enthalpy of liquid,kcal/kmol
Hy :enthalpy of vapour,kcal/kmol
H₅ :heat of solution,kcal/kmol
406 Chapter 7 Distillation

K; :equilibrium vaporization ratio of component i in a mixture,Eq.(7.14)

L
:liquid flow rate,kmol/h(in the rectifying section of a continuous column)
Z :liquid flow rate in the stripping section of a column,kmol/h
M₄ :molecular weight of component A
Nm :minimum number of trays (at total reflux)
PA :partial pressure of A in a vapour mixture,kPa/bar/atm
P
:total pressure,kPa/bar/atm
PA
:vapour pressure of pure component A
q
:a parameter indicating the quality of the feed,Eq.(7.82)
Q
:rate of heat input to the column/chamber,kcal/h
Qg
:heat load of the reboiler,kcal/h
Qc
:heat load of the condenser,kcal/h
R
:reflux ratio (=L₀/V)
T₄
:boiling point of pure component A
Tg
:boiling point of pure B;bubble point of a mixture
V
:vapour flow rate,kmol/h(in the rectifying section of a continuous column)
V
:vapour flow rate in the stripping section of a column,kmol/h
W
:rate of withdrawal of bottom product from a column,kmol/h
x
:liquid-phase mole fraction of a component (the more volatile component in a
binary) in a mixture
Xp
:mole fraction of the more volatile in the distillate
Xn
:mole fraction of the more volatile of a binary in the liquid leaving the nth
Xw
plate :mole fraction of the more volatile in the bottom product
y
:vapour-phase mole fraction of a component(the more volatile component in
a binary)in a mixture
y*
:vapour-phase mole fraction of a component in equilibrium with the liquid at
mole fraction x
yn
:mole fraction of the more volatile of a binary in the vapour leaving the nth
ZF
plate :mole fraction of the more volatile in a binary feed mixture
Zj,ZFi
:mole fraction of component i in the feed
α

2
:relative volatility,Eqs.[7.8(a)]and (7.10)
AA
:heat of vaporization of pure component A,kcal/kmol
 Short and Multiple Choice Questions 407

SHORT AND MULTIPLE CHOICE QUESTIONS

1.The relative volatility of A in a mixture with B is aAp=2.0.The equilibrium

vaporization ratio of B is Kg=0.7.(a)What is the value of agA?
(i)2.0 (ii)0.5 (iii)1.0
(b)What is the value of K₄?
(i)1.4 (ii)0.35 5 (iii)2.7
2.Consider equilibrium in the ternary system of benzene(1),toluene (2)and o-xylene (3).
Given:T=393 K,P=1.2 bar and x₃=0.2.Is the system completely defined?
3.What are the major sources of error in the experimental determination of vapour-liquid
equilibrium using a liquid recirculation type still?
4.(a)The overall mole fraction of benzene in a mixture of benzene and toluene is zr=0.3
at 1 atm total pressure and 95°℃.Then the mixture is
(i)a liquid
(ii)a vapour
(ii)a two-phase mixture.
(b)What is the minimum temperature at which a vapour of this composition can exist
at 1 atm total pressure?
(i)370 K (ii)376.8 K (iii)382.7 K
[Ideal solution;vapour pressure equation in Table 7.2]
5.Water (1)and formic acid (2)form a higher-boiling azeotrope.At 1 atm total pressure,
the azeotropic composition is x=0.409.Then which of the following is correct?
(i) α₁₂=1, atx=0.409
(ii) α₁z>1, atx=0.617
(ii)α₁₂<1,at x =0.803
(iv) α₁z<1 at x =0.205.
6.The relative volatility of A in a mixture of A and Bis aAp=1.5.What is the mole fraction
of B in the first droplet of liquid condensed from an equimolar saturated vapour
mixture of A and B?
(i)0.5 (ii)0.6 (iii)0.4
7.A binary totally miscible mixture forms a maximum boiling azeotrope at x=xa.Two sets
of equilibrium data points for the system are (xj,y)and (xz,)2).If
x₁<x₄<xz,identify the correct inequalities.
(i)x₁<y* (ii)x₂<y² (iii)yi>y
8.A given mixture of n-pentane and n-octane is heated and flashed when one mole liquid
having a mole fraction x=0.15 of n-pentane and two moles of vapour are generated.
At the temperature of the flash drum,the relative volatility of n-octane with respect
to n-pentane is 0.216.The solution is ideal.Calculate the composition of the original
mixture.
9.A mixture of compounds A and B forms a higher-boiling azeotrope at x=0.75 at 1 atm
408 Chapter 7 Distillation

total pressure.A solution of this composition has a bubble point T,and a vapour of the
same composition has a dew point Ta.Then:
(i)T>Ta (i)Tp=Ta ((ii)T<Ta
10. Consider a mixture of 40 mole%benzene (1),40%toluene (2)and 20%p-xylene
(3). The solution is approximately ideal.The following relative volatility values are
known at 1 atm total pressure:αiz=2.4 and a₃₂=0.43.Then(a)the value of a₃i
is
(i)0.18 ((ii)1.03(iii)53.58

(b)And the mole fraction of toluene in the equilibrium vapour at 100℃

is (i)0.688 (ii)0.2777 (iii)0.743
(c)Given the values K₁=1.67 and K₂=0.688,the value of Kʒis
(i)1.15 (ii)2.43 (iii)0.296
11.One mole of a solution of A and B(enthalpy =900 kcal/kmol;x =0.4)is mixed with
two moles of another solution of the components (enthalpy =1200 kcal/kmol,x
=0.8). Calculate the enthalpy and composition of the mixture.
12.A ternary solution of n-hexane (20 mole%),n-heptane (40 mole%)and n-octane may
be considered to be ideal.The equilibrium vaporization ratios
are:K₁=2.25,K₂=1.02, and K₃=0.6 at 1 atm total pressure.The solution is
(i) below its bubble point
(i) saturated
(i) above its bubble point.
13.A student was asked to do flash calculation of an ideal mixture of four components
having an overall composition(in mole fraction)of w₁=0.2,w₂=0.15,and
w₃=0.40. At the condition of the flash drum,the equilibrium vaporization ratios
were:K₁=2.1, K₂=1.02,K₃=0.6,and K₄=0.2.The student reported that 38 mole
%of the feed vaporized on flashing.(a)Was the calculation reasonably correct?
(b)What was the value of relative volatility a₄3?
(i)0.33 3 (ii)3.1 (iii)0.4
14. An essential oil,virtually immiscible with water,is steam-distilled by passing live
steam at 107°℃ through a mixture of the oil and water (one mol of the oil per 200 mol
water). The vapour pressure of water at 107°℃ is 1.3 bar and that of the essential oil is
6.55 mm Hg. How much steam is necessary to recover 80%of the essential oil?Neglect
condensation of steam.
15.What are the important factors that determine the selection of a batch distillation
column for the separation of a liquid mixture?
16.A mixture of benzene and p-xylene is batch distilled at atmospheric pressure.The
rate of heat input to the still is 4000 kcal/h.Individual heats of vaporization
are:benzene =
100 kcal/kg,p-xylene =85 kcal/kg,and the relative volatility of benzene in the
mixture is 5.6.Calculate the instantaneous rate of vaporization of p-xylene when the
liquid in the still has 40 mole%benzene in it.
17.One thousand kilograms of an equimolar mixture of benzene and nitro-benzene is
being separated by batch distillation.After an hour of operation,500 kg of the mixture
remains
 Short and Multiple Choice Questions 409

in the still.The operator takes a sample of the accumulated condensate and reports
that it has 70 mole%benzene in it.The relative volatility of benzene in the mixture
can be taken as 7.Is the reported concentration of the distillate reasonably accurate?
18. A quaternary solution is being distilled in a batch still.Over a period of time,30 mol
% of component 1 is distilled out.The following relative volatility values are
given:a₃1 = 0.2;α₂₃=1.8;α4₃=0.7.What fraction of component 3 is distilled out
over this period?
19. Given:xp=0.95,xw=0.05,α=2,zp=0.5 and the feed is
saturated.Algebraically, calculate the theoretical minimum slope of the rectifying
section operating line for distillation of the binary mixture.Does it differ from the
theoretical minimum slope of the stripping section operating line?
20. At a particular section of a packed distillation column,the bulk liquid concentration
in a binary mixture is x=0.7.Given:internal reflux ratio =0.9,α =2.5,Hc =0.42
m, H₁=0.15 m.What is the height of an overall vapour phase transfer unit,Hoc?
(i)0.52 (i)0.38 (iii)0.65
21.The stripping section operating line for a binary distillation problem is y=1.4x-0.02.
The relative volatility is a=2.6.On a particular tray the liquid composition is x
=0.2. What is the composition of the vapour leaving the tray if the Murphree tray
efficiency is 0.7?
(i)0.32 (ii)0.354 (iii)0.26
22.What happens if a column heated by open steam is operated at total reflux for a
long time?
23. The stripping section operating line of a distillation column receiving saturated
open steam for the separation of an aqueous solution is y=1.1x -0.022.
(a)If a=2.7,what is the bottom product composition?
(i)0.22 (ii)0.022 (iii)0.02
(b)What is the enrichment of the vapour across the bottom tray?
(i)0.052 (ii)0.022 (iii)0.011
24. A column receives saturated steam at the bottom for heat supply.If the feed
(zp=0.5) is a mixture of 40 mole%liquid and 60 mole%vapour,calculate the
slope of the stripping section operating line corresponding to the minimum
reflux.Given:α =2.6, and xw=0.03 mole fraction.
25. A column has to separate a mixture of A and B to yield a top product of xp =0.97
and a bottom product of xw=0.04.Calculate the minimum number of ideal trays
required to achieve this separation,Given:α₄g=1.8 at the bottom condition and
αAg =2.0 at the top condition.
26. The following concentrations of the vapour at two consecutive trays in the
rectifying section of a column have been measured:y₃=0.94 and y₄=0.925.The
equation of the operating line is y=0.6667x+0.32.The relative volatility at the liquid
composition on the third tray is a =1.85.Calculate the Murphree efficiency of the
tray.
27.A column receives a cold reflux',and the 'external reflux ratio'is 2.0.For each mole
410 Chapter 7 Distillation

of the cold reflux,0.05 mole of the vapour condenses at the top tray.What is the true
slope of the rectifying section operating line?
(i)0.677 (ii)0.5 ( (iii)1.0
28. A saturated equimolar mixture of vapours of A and B enters a partial condenser at a
rate of 1 kmol/h.The vapour leaves the condenser at a rate of 0.6 kmol/h.If the
relative volatility of B with respect to A is 0.3,calculate the composition of the vapour
and the liquid leaving the partial condenser.
29. A mixture(40 mole%vapour,the rest liquid)of aniline and nitrobenzene (80 mole
%aniline) is separated into a distillate having 98 mole%aniline and a bottom product
with 3 mole% aniline.The reflux ratio used is 2.2.(a)Determine the equations of the
operating lines and of the feed line.(b)Write down the same equations if the column
operates at total reflux.
30. A column is designed to operate at a reflux ratio of 1.3(saturated reflux).In actual
operation the reflux is well below its bubble point.What reflux ratio would you suggest
qualitatively?
(i)R>1.3 (ii)R<1.3 (iii)R =1.3
31.The equation of the rectifying section operating line for distillation of a mixture of A
and B in a packed column is y=0.6x+0.376.The relative volatility of A with respect
to B is a₄B=2.0.At a point in the rectifying section,x =0.8.Given:kfa =400
kmoll (m³)(h)(△x),and k'ā =170 kmol/(m³)(h)(△y).
(a)What is the reflux ratio?
(i)0.5 (ii)1.0 (iii)1.5
(b)What is the top product mole fraction?
(i)0.49 (ii)0.94 (iii)0.98
(c)What are the concentrations of the more volatile at the vapour-liquid interface?
32. A column for distillation of a mixture of A and B operates at total reflux.The liquid
concentration of the fifth tray from the top is x=0.4.If the relative voltality is αAg
= 1.8,what are the concentrations of vapour streams (i)entering the tray and
(ii)leaving the tray?
33. In order to reduce energy supply to a tray column for the separation of a binary
mixture of A and B,it is planned to retrofit it with the Intalox high performance
structured packing.The column receives a saturated liquid feed having 60 mol
%A.The top product purity is 98 mol%A and the relative volatility is a₄p=2.0.The
plant engineer suggests reduction of the reflux ratio from the present value of 1.8
to 1.5.Is the suggestion practicable?
34. If the relative volatility of A in a binary mixture of A and B is constant,show that
the product of the terminal slopes of the equilibrium curve(i.e.
[dy/dx]x=o·[dy/dx]x=i) is unity.
35. The relative volatility of A with respect to B is a₄g=2.At what concentration of
a mixture of A and B is the slope of the equilibrium line unity?
 Problems 411

36. For distillation of an equimolar binary mixture of A and B,the equations of the
operating lines are:
Rectifying section:y=0.663x +0.32
Stripping section:y=1.329x-0.01317
What is the condition of the feed?
37.A binary distillation column separating A and B is being operated at total reflux in
the startup period.The relative volatility of A with respect to B is aAn=2.0.If the
vapour entering the top tray has 95 mole%A,what is the mole fraction of A in the liquid
leaving the tray?
(i)0.95 (ii)0.5 (iii)0.475
38. Write down the equations of the operating lines of the column(that runs under
total reflux)described in Problem 37.
39. Prepare sketches of typical energy-concentration diagram of binary liquid and
vapour mixtures of A and B if constant molar overflow (i)occurs and (ii)does not
occur in the distillation column.Explain the sketches.
40. An aqueous solution of ethanol [30 mole%ethanol (1)and 70 mole%water (2)]at
75℃ exerts an equilibrium total pressure of 592 mm Hg.Given PY =661 mm
Hg,P2 = 289.5 mm Hg,η=1.765,and Yz=1.195,calculate the equilibrium
vaporization ratios
K₁and K₂

PROBLEMS

[Note:To calculate vapour pressures,use the Antoine equation constants given in Table 7.2.]
7.1(Equilibrium in a binary mixture)I Mixtures of n-hexane and n-octane form
essentially ideal solutions.(a)Prepare the bubble point,dew point and equilibrium
curves (T-x-y and x-y plots)at 1 atm total pressure.(b)Calculate the values of the
relative volatility of n-hexane and n-octane in mixtures containing 10 mole%and 90 mole
%hexane using vapour pressure equations given in Table 7.2.Do these values
suggest that the solutions may be ideal?(c)A solution of concentration x =0.2 is
slowly heated.What is the composition of the initial vapour formed if the total pressure
is (i)1 atm,(ii)2 atm? (d)If a vapour of composition as in part (c)(ii)above is cooled
at 2 atm total pressure and a differential amount of vapour is formed from the
condensate,calculate its composition.How can the quantities be calculated using the
T-x-y and x-y data?
7.2 (Bubble point/dew point calculation,ternary mixrture)³ Calculate the bubble point of
a mixture of 30%methanol,30%ethanol and 40%n-propanol (all in mole%)at 1 atm
total pressure.Also calculate the dew point of a vapour of the above composition at
1.5 atm total pressure.Assume ideal behaviour of the solution.
7.3(Equilibrium in a multicomponent heterogeneous system)³ A heterogeneous mixture
containing benzene (0.025 gmol),toluene (0.025 gmol)and water (0.05 gmol)is
heated slowly at 1 atm total pressure.The vapour generated remains in equilibrium
with the
412 Chapter 7 Distillation

liquid.Calculate (a)the temperature at which boiling starts,(b)the composition of the

initial vapour,and(c)the temperature at which vaporization is complete.
7.4(Binary flash distillation—yield vs composition)I Ethanol forms a nearly ideal
solution with iso-butanol and has a relative volatility 2.2.A heated feed containing
40 mole%ethanol and 60 mole%iso-butanol enters a flash drum at a rate of 50
kmol/h. Prepare a plot of the fractional yield of the distillate versus its
composition.What fraction of the feed should be vaporized in order to have a bottom
product containing not more than 10%ethanol?
7.5(Two-stage flash distillation)² Consider Problem 7.4 again.Now there is a second
flash drum that receives the bottom product from the first drum.If 60%of the feed
is vaporized in each drum,find the vapour and the liquid flow rates from each
chamber as well as their composition.
7.6(Two-stage flash distillation)³ A mixture of acetone and phenol (40 mass
%acetone) is flashed consecutively in a cascade consisting two flash drums at 1
atm.The feed enters at a rate of 3000 kg/h and half of it is flashed in the first flash
drum.The liquid from the first drum is heated and flashed again in the second
drum.What fraction of the feed entering the second drum should be vaporized so that
the residue contains not more than 1 mass %acetone?The vapour-liquid equilibrium
data of the acetone-phenol system are given below.
x 0.01 0.04 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 0.96 0.99
y 0.67 0.7760.8520.91 0.94 0.9620.98 0.99 0.991 0.994 0.997 0.9990.9996
7.7(Heat requirement for a simple flash distillation)²Components A and B form
approximately ideal solutions and the relative volatility is aAp =3.0.One kilomol of
a mixture(x=0.5)at 40°C is passed through a heat exchanger and then flashed to
get equal amounts of liquid and vapour products.The temperature in the flash drum is
80°℃. The molar specific heats are cpA=20 kcal/kmol,cpg =30 kcal/kmol.The
molar heats of vaporization are λ₄=1250 kcal/kmol,λg=1700
kcal/kmol.Calculate the heat absorbed by the liquid in the heat exchanger.
7.8(Use of enthalpy-concentration relations)I The molar enthalpies of saturated liquid
and vapour mixtures of A and B at 1 atm total pressure(reference temp.=5°℃)may
be expressed as:HL=9000+1000x kJ/kmol;Hy=35,000+8000y kJ/kmol.The
relative volatility is aAp=1.8.(a)Calculate the molar heats of condensation of
saturated pure vapours of compounds A and B at 1 atm.(b)We have one kmol of a
liquid (x =0.3, H₁=8500 kJ/kmol),and one kmol of a vapour (y=0.5,Hy=40,000
kJ/kmol).What is the condition of the liquid (subcooled,saturated or superheated)and
the condition of the vapour(saturated or superheated)?
7.9 (Ternary flash distillation)² A mixture of 38 mol%propane,22.5 mol%iso-butane,
and 39.5 mol%n-butane is flashed in a drum.If 50 mol%of the feed vaporizes,estimate
the compositions of the liquid and the vapour phases.The K-values at the given
conditions are as follows:Propane—1.42;iso-butane—0.86 and n-butane—0.72.
7.10(Bubble point of a heterogeneous mixture)² Liquids A and B are miscible in all
proportions and at all temperatures.The vapour pressure of B is given by
 Problems 413

In P;(mm Hg)=14.243-2570/(0,°C+232.5).At what temperature does an equimolar

mixture of A and B boil if the total pressure is 1.5 bar?Write down the Antoine
equation for A.
Neither A or B is miscible with water.If some water is added to the mixture,at
what temperature should it boil if the total pressure remains unchanged?The vapour
pressure relation for water is given in Table 7.2.
7.11(Binary batch distillation)' Ten kmol of a feed having 65 mole%benzene and
35 mole%toluene is batch distilled at 1 atm pressure.Calculate the moles of
distillate produced and the composition of the bottom product if distillation is
done until (a)75 mole%of the feed benzene leaves with the vapour;(b)the stillpot
contains 35 mol%benzene;(c)50 mole%of the feed is vaporized;(d)the
accumulated distillate contains 75 mole%of benzene.Take α =2.51.
7.12 (Partial condensation of a vapour)² The vapour(containing 85 mole%methanol and
15 mole%water)from the top tray of a methanol distillation column enters a partial
condenser at a rate of 70 kmol/h at 1 atm pressure.(a)If 70 mole%of the vapour
is condensed,calculate the composition of the uncondensed vapour.(b)If the
uncondensed vapour leaving the condenser has 91.5 mole%methanol in it,how much
condensate leaves the condenser per hour?The vapour-liquid equilibrium data are given
in Example 7.15.
7.13 (Steam distillation)' Two kg charge of geraniol (mol.wt.=154.1)is to be steam-
distilled at a temperature of 108℃.The steam is saturated and it is passed at a rate
of 50 kg/h.Calculate the time for distillation of 95%of the material.The
vaporization efficiency is 0.90.Vapour pressure at 108℃:water—1.34 bar;geraniol—
8.65 mm Hg.
7.14(Steam distillation in presence of an impurity)²Twenty kg charge containing
40 mass%of an essential oil (mol.wt.=170)and the rest a non-volatile impurity(mol.
wt.=282)having complete mutual miscibility but both immiscible with water,is
being steam-distilled.The steam supplied is saturated at 108°℃.Calculate the
rate of volatilization of the oil when 50%of it has been removed.The vaporization
efficiency
is 0.85.The vapour pressure of the substance at the given temperature is 6.5 mm Hg.
7.15(McCabe-Thiele construction for ideal trays)'A feed mixture of A and B(45 mole%
A and 55 mole%B)is to be separated into a top product containing 96 mole%A
and a bottom product having 95 mole%B.The feed is 50%vapour and the reflux
ratio is 1.5 times the minimum.What is the equation of the feed line?Determine the
number of
ideal trays required and the location of the feed tray.Given:aAg =2.8.
7.16(Use ofthe McCabe-Thiele method)I A mixture of di-and tri-ethylamines containing
55 mole%of the former is fed to a distillation column at a rate of 40 kmol/h.The
feed is at its bubble point.The column is to operate at atmospheric pressure and
the top product should not have more than 2.5 mol%of the less volatile.Also,not
more than 2%of the diethylamine in the feed should be allowed to leave at the
bottom.The reflux to the column is a saturated liquid.Determine(a)the minimum
reflux ratio,(b)the number of theoretical plates if the actual reflux ratio is 1.4 times
the minimum,(c)the slopes of the two operating lines,and (d)the number of
theoretical plates if the reflux
414 Chapter 7 Distillation

is a subcooled liquid at such a temperature that one mole of vapour is condensed

for twenty moles of reflux.The equilibrium data in terms of the more volatile are:
x 0.02 0.039 0.052 0.065 0.09 0.092 0.14 0.215 0.43 0.6010.782 0.853
0.932 0.985 y
0.0420.0850.1240.1530.2250.2430.3160.4490.6780.8020.9100.9480.
9700.993
7.17(Use of the McCabe-Thiele method)² Styrene,a tonnage organic chemical used in the
production of moulding resins and rubbers,is produced by catalytic dehydrogenation
of ethylbenzene followed by separation of the product by distillation.A fractionating
column receives an equimolar mixture of styrene and ethylbenzene at a rate of 120
kmol/h.The purity of the top product(ethylbenzene)and that of the bottom product
(styrene)must not be less than 98%and 99.5%respectively.Determine (a)the minimum
external reflux ratio,(b)the minimum number of ideal trays required for the above
separation,(c)the number of ideal trays and the feed-tray location if the actual reflux
ratio is twice the minimum and the feed is a saturated liquid,and (d)the vapour load
in the condenser.It will be convenient to use the Kremser equation to determine the
number ideal trays near the top and bottom ends.The column operates at 20 mm
pressure and the equilibrium data at this pressure are given below(x,y are for
ethylbenzene).
x 0.0 0.0555 0.07820.115 0.139 0.2405 0.2715 0.335 0.460 0.545 0.755 0.874
0.965 1.0 y 0.00.090 0.120 0.1620.2010.318 0.355
0.40550.5350.6300.8250.9100.9751.0 In industrial practice too,styrene is
purified by distillation under vacuum.How are the column parameters(diameter,tray
spacing,number of trays)affected if a mixture is distilled under vacuum rather
than at atmospheric pressure?
7.18(Calculation of the minimum refux)²A saturated vapour feed containing benzene
(30 mole%)and chlorobenzene is to be separated into a top product having 98 mol
% benzene and a bottom product having 99 mol%chlorobenzene.Calculate the
minimum reflux ratio algebraically.What is the corresponding boil-up ratio?The
relative volatility of benzene in the mixture is 4.12.
7.19(Effects of operating parameters on column performance)³ A distillation column
provided with a partial reboiler and a total condenser separates a mixture of A and B
to yield products of compositions xp(top)and xw(bottom).(a)How can the purity of
the distillate be increased without changing its quantity and without the addition of
extra trays?How is the purity of the bottom product affected as a result?(b)If the
rate of withdrawal of distillate is increased(without making any changes in the
reboiler heat input),identify the consequent changes.(c)If the pressure of the
saturated steam fed to the reboiler undergoes a step change and no other change
occurs to the parameters, how is the performance of the column affected?
7.20(Algebraic calculations for a tray column)² A mixture of 60 mole%A and 40 mole%
B is separated in a column to yield 96 mole%A as the top product.Also,97%of A
entering the tower must be recovered in the distillate.The feed is a saturated
vapour.The following concentrations have been measured by analyzing the liquid and
vapour samples around the 6th tray:x₆=0.55,y₆=0.72,y₇=0.63.(a)What is the
local value of the relative volatility of A with respect to B?(b)How many ideal
trays does the column have?Assume that the relative volatility remains constant.
 Problems 415

7.21(A stripping column having a given number of trays)³A saturated liquid mixture of
benzene and toluene having 70 mole%benzene is fed continuously at a rate of 40
kmol/h to the top tray of a column having six theoretical trays.There is no reflux at the
top.The rate of vapour generation in the reboiler is 30 kmol/h.Determine the
equation of the operating line and the rates and compositions of the product.(Note:This
column may be called a 'stripping column'.)
7.22(Algebraic calculation of the vapour/liquid concentrations in a tray column)³A
distillation column separates a saturated feed containing 25 mole%A and 75 mole
%B. The relative volatility is a₄b=2.51.The liquid concentration on the 5th tray is
xs=0.54. The distillate has 98 mole%A and the reflux ratio is 3.0.(a)Determine the
concentration of the vapour (i)entering the 5th tray from the top,and (ii)leaving the 5th
tray.(b)Which section of the column (rectifying or stripping)does the 5th tray belong
to?(c)Calculate the enrichment of the vapour across the 4th tray.(d)If 97%of A
present in the feed goes to the top product,calculate the moles of liquid vaporized in
the reboiler per mole of distillate and also the boil-up ratio.Assume that the trays are
ideal.Solve the problem algebraically (i.e.without any graphical construction).
7.23(High purity product;use of Kremser equation)³ An equimolar mixture of A and B
is to be separated in a tray tower.A top product having 95 mol%A is
acceptable. However,a very pure bottom product having not more than 0.1 mol%A is
required.The feed is liquid at its bubble point.A reflux ratio of 2.0 is suggested.The
relative volatility of A with respect to B is αAB=2.2.Determine the number of
ideal stages.
The graphical construction of stages is difficult at low concentration and an algebraic
method is convenient.Use the McCabe-Thiele method to make stage construction
up to about 5 mol%of A.Then use the Kremser equation to determine the number of
trays required to reach the stipulated value of 0.1 mol%A in the bottom product.
7.24(A stripping column with a given number of trays)³The vapour phase alkylation of
phenol is carried out by a selective zeolite catalyst to yield a mixture of 35 mole
% p-cresol and the rest phenol.The mixture which is at its bubble point is to be
separated at 1 atm pressure in a stripping column having nine ideal trays and a partial
reboiler at a rate of 50 kmol/h to yield 95%p-cresol as the bottom product.The
relative volatility of phenol in the mixture is 1.76.Calculate(a)the composition of
the top product and (b)the boil-up rate,V/W,where V is the vapour rate and W is
the rate removal of the bottom product.
7.25(Performance of a column with an additional number of trays)³ A column having
16 trays of 25%overall efficiency separates a mixture of 60 mole%benzene and
40 mole%toluene available as a saturated vapour.The overhead product is 85
mole% benzene and the bottom product is 20 mole%benzene.It is possible to add a
section having eight trays of the same efficiency to the column.If all process
conditions remain unchanged,calculate the percentage saving in steam fed to thereboiler
that can be achieved by this increase in the number of trays.On which tray of the
modified column should the feed be introduced?Equilibrium data for the system is
given under Example 7.13.
7.26(Given the number of trays and efficiency,to determine the product composition)³A
distillation column has five plates that are 60%efficient.The heat input to the stillpot is
416 Chapter 7 Distillation

100,800 kcal/h and the condenser load is 280,000 kcal/h.The reflux is at 37℃
below the boiling point.A feed,an equimolar mixture of benzene and toluene,enters the
column at a rate of 50 kmol/h.Also the feed is 55%vapour.Latent heat of
vaporization of the liquid can be taken as 7000 kmol/kmol irrespective of the
composition.The specific heat of liquid is 38 Btu/(lb)(mol)(°F).Find the
compositions of the top and the bottom products.
7.27(McCabe-Thiele construction—feed is not supplied at the optimum location)³A
distillation column receives an equimolar saturated liquid mixture of benzene and
toluene (α=2.51).The top product has 95 mol%benzene,the bottom product
contains 95 mol%toluene,and the reflux ratio is 2.0.(a)Determine the feed tray and
the number of ideal trays if the feed is supplied to the optimum location.(b)How
many more trays would be required for this separation if the feed is supplied at the
ninth ideal tray from the top?(c)Determine the number of real trays if the Murphree
efficiency is 60%and the feed enters the optimum position in the column.
7.28( McCabe-Thiele method,number of trays given,Murphree efficiency given)² A
distillation column which separates pinene and limonene consists of a
reboiler, 15 theoretical plates and a total condenser.The feed is at its bubble point
and has 72%pinene in it.The overhead product contains 95 mole%pinene and
the bottom product has 94%limonene.Determine(a)the reflux ratio to be
maintained,(b)the location of the feed plate,(c)the number of ideal stages required for
the above separation for total reflux.Given:a =1.71.
7.29(A column receiving two feeds)³A distillation column for separation of methanol from
water receives two feeds—100 kmol/h saturated liquid having 30 mol%methanol,and
100 kmol/h 20%vaporized feed having 60 mol%methanol.The top product should have
96 mol%methanol,and the bottom must not contain more than 3 mol%of it.If an
external reflux ratio of 1.45 is used,calculate the amounts of the top and bottom
products, and determine the number of ideal trays required for the separation.The
vapour-liquid equilibrium data are given in Example 7.15.
7.30(Withdrawal of a side stream from a distillation column)² A saturated liquid feed
having 45 mole%methanol is distilled at a rate of 200 kmol/h in a column to yield
a top product,96%methanol,a bottom product,97%water,and a liquid side
stream, 20 kmol/h,having 70 mole%methanol,from the appropriate tray.Determine the
number of ideal trays required.From which tray should the side stream be withdrawn?
A reflux ratio of 1.5 may be used.
7.31(A column with an arrangement for heat supply to a particular tray)³ A distillation
column separates an equimolar mixture of methanol and water at its bubble point to
a top product having 95%methanol and a bottom product with 95%water.
(a) How many trays should be used to achieve this separation if the column is
operated at total reflux?
(b) Determine the number of theoretical trays required and the location of the feed
tray if a reflux ratio of 1.5 is used.
(c) It is planned to instal a heading coil on the third tray from the top so as to
vaporize 10%of the liquid it receives.What will be the number of trays for this
arrangement?
 Problemg 417

7.32(A column receiving two feeds;feeds supplied to the wrong plates)³ A column
receives two feeds—20 kmol/h,40 mole%benzene,and 40 kmol/h,60 mole%benzene,
both liquid at the respective bubble points.The top product rate is 30 kmol/h with 94%
benzene,and the reflux ratio is 1.5.After an annual shutdown,the feed pipe connections
got interchanged inadvertently.Can you predict the top product composition at this
condition?The reflux ratio remains unchanged.
7.33(Side stream withdrawal from a column—algebraic calculations)³ A continuous
distillation column receives a saturated liquid feed (zp=0.45).It produces a distillate
of xp=0.98 and a bottom product of xw=0.015.A side stream amounting to 25%of
the downflowing liquid(xs =0.75)is withdrawn as a saturated liquid from the
appropriate tray.The rectifying section operating line for the part of the column above
the point of side stream withdrawal is y=0.821x+0.175.Determine the equations of
the operating lines for the middle and the last sections of the column.What fraction
of the feed is drawn as the bottom product?
7.34(Binary batch distillation)' A charge of 15 kmolof an equimolar mixture of methanol
and water is batch-distilled to recover 85%of the alcohol.Calculate the amount of
distillate and its composition.Equilibrium data are available under Example 7.15.
7.35 (Multicomponent batch distillation)² A mixture containing 2 kmol each of n-hexane,
n-heptane and n-octane is batch-distilled at 1 atm pressure to remove 80%of hexane.
Taking K-values from Figure 7.8,calculate the amount and composition of the
distillate. What fraction of heptane remains in the still?
7.36 (Batch distillation with constant reflux)3 A batch distillation column having a stillpot
and one ideal tray separates a mixture of benzene and toluene.At the beginning there
is 10 kmol of liquid in the still with 40 mole%benzene.The rate of vapour generation
is 15 kmol/h and a reflux ratio of 3.0 is used.Determine the concentration of the
overhead vapour and the instantaneous rate of removal of benzene.The relative
volatility of benzene is 2.51.
7.37 (Batch distillation with variable reflux)³Fifty kilomols of aqueous methanol
(60 mole%methanol)is charged into a batch still having a reboiler and five ideal
trays. The reflux ratio is continuously increased so that the distillate always contains 90
mol% methanol.If distillation is stopped after the reflux ratio required to maintain the
stipulated top product concentration exceeds 8.0,calculate the fractional recovery
of methanol.
7.38(Batch distillation)³ Twenty kilomoles of a mixture of A and B(xp=0.45)is charged
in the stillpot of a batch distillation unit.A constant vaporization rate of 5.0 kmol/h
is maintained and there is a total condenser.(a)What is the concentration of the
distillate after one hour?(b)At the end of one hour,it is planned to start
withdrawal of the condensate from the receiver at a rate equal to that of the rate of
vaporization.Thus the amount of condensate in the receiver remains constant (it is
also assumed to be well- mixed all the time).Calculate the concentration of the
distillate in the receiver at the end of two hours of operation.The equilibrium
vaporization constants at the operating condition are:K₄=2.6,and Kg=0.9.
418 Chapter 7 Distillation

7.39(Batch distillation in a unit having a partial condenser)² The vapour from a batch
still flows to a partial condenser in which 50 mole%of the vapour is condensed.The
condensate is fed back to the still and the uncondensed part flows to a second total
condenser and gets accumulated in a receiver vessel (Figure 7.36).The still is
charged with 10 kmol of a mixture of A and B and batch distillation
continues.What is the composition of the accumulated distillate after 5 kmols of the
charge is distilled out? The relative voltality is aAg=2.8.

Figure 7.36 A batch still with a partial condenser.

7.40(Continuous distillation using open steam)²An aqueous solution of ethanol with

25 mole%of the alcohol is to be distilled in a tray column at a rate of 200 kmol/h to
get a distillate with 80 mol%ethanol.The feed is at its bubble point.If 95%recovery of
the alcohol in the distillate is required,and saturated open steam at 1 atm is fed to the
bottom of the column,calculate the number of ideal trays required for the
separation.A reflux ratio of 2.2 is suggested.Constant molar overflow may be
assumed.(The VLE data is given under Example 7.24.)
7.41(Use of the Ponchon-Savarit method)³ A dilute aqueous solution of ethanol is to be
concentrated from 20 mass%to 85 mass%alcohol in a tray tower at 1 atm
pressure. The feed rate is 8000 kg/h at its bubble point.The bottom product must not
contain more than 3.5 mass%ethanol.Determine(a)the minimum reflux ratio,(b)the
number of ideal trays,and(c)the reboiler and condenser heat duties.The enthalpy-
concentration and the equilibrium data are given under Example 7.24.
7.42(Use of the Ponchon-Savarit method)³ An aqueous solution of ammonia is
continuously generated in the absorption column for its recovery from the
ammonia reactor bleed stream.Ammonia is separated from this aqueous solution by
distillation at around 20 atm pressure.A distillation unit is to be designed for treating
5000 kg/h of a solution containing 25 mass%ammonia.The top product should
have 97 mass% ammonia and the bottom must not have more than 1.5%of it.A
reflux ratio of 1.6 may be used.
If the feed is at its bubble point,determine(a)the number of ideal trays,
(b)the location of the feed tray,and (c)the number of ideal trays if constant molar
overflow is assumed.
 Problems 419

x or y 0.10530.2094 0.312 0.414 0.514 0.614 0.712 0.809 0.905

0
HL,kcal/kmol -500 -970 -1310 -1540 -1650 -1580 -1400 -960 -
0
520
Hy,kcal/kmol 8430 7955 7660 749 721 692 6620 6300 5980 547
5 0 0 0
x Or 0.92 0.942 0.981 1.00
3 0.962
HL,kcal/ -430 -210 -110
kmol Hw - 0.0
kcal/kmol 5350 3 5050 4870 4250

[Reference states:pure liquids at their boiling points at 20 atm pressure]

7.43(Calculation of the packed height)²A saturated aqueous feed(20 mole%ethanol;
50 kmol/h)is to be distilled in a packed tower filled with 1-inch metal Pall ring.The top
product should have 80 mole%ethanol and the bottom not more than 2 mole%of it.A
reflux ratio of R=1.7 may be used.(a)If a vapour flow rate of 70%of flooding velocity
is maintained,determine the tower diameter.(b)Given the following values of heights of
individual transfer units—Hc =0.4 m and Hn=0.25 for the enriching section;
H₁c=0.28 m and Hμ=0.11 for the enriching section—calculate the packed
height required.

7.44(Packed height and HETP)²An aqueous solution of methanol(30 mol%methanol;

2000 kg/h)is to be separated in a 0.7 m diameter packed tower to yield a distillate
having 97%methanol and a bottom product having 4%methanol.The following values
of the volumetric mass transfer coefficients are supplied.

Rectifying section Stripping section

kxā =800 Ka =170) k;a =1250 k,a =255 kmol/(m³)(h)(△x or △y)

A reflux ratio of 1.4 times the minimum may be used.Calculate the height of the packed
section.Also determine the HEPT of the packing.
7.45(Relation between the reflux ratio and the boil-up ratio)¹If the relative volatility
remains constant,show that the reflux ratio R and the boil-up ratio R,,are related
as follows (Stichlmair and Fair,1998)for distillation of a binary mixture.

7.46(The minimum reflux ratio if the relative volatility is constant)'If the relative
volatility is constant and the feed is a saturated liquid,show that the minimum reflux
ratio is given by the following expression.

7.47(A column receiving cold reflux)²A saturated liquid feed containing 50 mol%A and
50 mol%B enters a distillation column at a rate of 100 kmol/h.The top product
must have 95 mol%A,and 4%of A should leave at the bottom.An external reflux
ratio of R =2 is maintained.However,the reflux is subcooled having an enthalpy of
4,000 kJ/ kmol of reflux.Given the following relations for enthalpies (kJ/kmol)of
saturated liquid and vapour,calculate(a)the equations of the top and the bottom
operating lines,and (b) the boil-up ratio.
420 Chapter 7 Distillation

Saturated liquid:HL=9000-3000x
Saturated vapour: Ht=40,000-3000y
7.48(A column receiving open steam)³ An equimolar mixture of methanol and water is
to be separated at a rate of 200 kmol/h in a tray tower to yield a top product having 96
mol% methanol.At least 97%of the total methanol is to be recovered.A small reboiler
that can generate 150 kmol/h vapour hour is available and will be used.Any additional
heat supply necessary will be met by injecting live steam at the bottom If a reflux ratio
of 2.0 is used, determine the amount of live steam to be supplied per hour and the
number of ideal trays required.The column operates at essentially atmospheric
pressure.
7.49(A leaking batch still)² Forty kilomols of a mixture of methanol and water (40 mol
% methanol)was charged in a still for batch distillation to yield 15 kmol of distillate
over a period of 1 hour.Immediately after distillation started,the drainage valve at the
bottom of the still was found leaking.The liquid that had leaked out over the period of
1 hour is found to be 5 kmol.Both the rate of distillation and the leakage at the valve
occurred at uniform rates.If the relative volatility of methanol is approximately
taken as 3.0, calculate the distillate composition and the amount of methanol that had
leaked out.
7.50(The minimum reflux ratio for multistage batch distillation)² An equimolar mixture
of A and B having 50 mol%A is to be batch-distilled in a multistage column
maintaining a constant reflux ratio.It is desired that the initial distillate should have
90 mol%of A. If the relative volatility of A with respect to B is 3.0,what is the
minimum reflux ratio required?
7.51(A packed column operated at total reflux)²A packed distillation column for
separation of benzene and toluene is operated at total reflux.The benzene concentration
in the distillate is 97 mol%and that in the bottoms is 2 mol%.If the relative volatility
of benzene in the mixture is α=2.51,calculate the number of overall gas-phase
transfer
units.
7.52(A mullistage batch distillation unit having a large number of trays)³ It is an
interesting exercise to theoretically calculate the separation capability of a multistage
batch column having an infinite number of trays (see Bauerle and Sandall,AIChE J.,June
1987,1034-1036).An equimolar mixture of A and B(a₄g=3.5)is to be batch
distilled in a column having a very large number of trays at a constant reflux ratio of
2.5.If one- third of the liquid is distilled out,calculate the composition of the
accumulated distillate.
7.53(Number of trays given,get the reflux ratio)³ An equimolar mixture of iso-pentane
and benzene is to be separated into a top product having 96 mole%iso-pentane and a
bottom product with 95%benzene.The feed rate is 100 kmol/h,saturated vapour.A
column of suitable diameter having twenty trays of 40%efficiency and a partial
reboiler is available.If saturated liquid reflux is fed back to the column,what reflux
ratio should be used to get the desired separation in the column.The average relative
volatility is 2.5. (The problem can be solved algebraically as well as by tray-by-tray
calculation.)
7.54(Stripping of an aqueous solution using open steam)² Ethanol is to be steam-stripped
from a dilute aqueous waste stream in a tray tower using open steam.The feed that
has 2.5 mass%ethanol in it is heated to its bubble point before it enters into the
column.The
 References 421

steam rate is 0.25 mole per mole of the feed.At this low concentration,the
equilibrium relation is approximately linear,y=8.5x.Determine the number of ideal
trays required if 95%of the ethanol is to be removed.
7.55(A column with side streams)³ A distillation column should separate 200 kmol/h of a
saturated liquid feed containing 45 mole%methanol and 55 mole%.The top product
should have 97 mole%methanol and the bottom,96 mole%water.The reflux is saturated
liquid and a reflux ratio of 2.0 is suggested.A vapour side stream containing 80 mole
% methanol is to be withdrawn at a rate of 50 kmol/h from the appropriate tray
and condensed in a heat exchanger.Half of it should be taken as an intermediate product
and the rest returned into the column as an additional reflux
stream.Determine(a)the number of ideal stages required,(b)the feed tray,(c)the tray from
which the side stream should be withdrawn,and(d)the tray that should receive the
additional reflux.

REFERENCES

Billet,R.,Distillation Engineering,Chemical Publishing,1979.

Billet,R.,Packed Towers in Processing and Environmental Engineering,VCH,1995.
Divekar,U.M.,Batch Distillation,Taylor and Francis,1995.
Eubank,P.T.et al.,‘Simplify flash calculations',Chem.Eng.,Nov.2000,125-130.
Fair,J.R.,'Distillation,whither,not whether',Chem.Eng.Res.&Des.,66(July 1988)363-370.
Forbes,R.J.,Short History of the Art of Distillation,E.J.Brill,Leiden,1948.
Hala,M.et al.,Computer-aided Data Book of Vapor-Liquid Equilibria,Kodansa,Tokyo,1975.
Jafarey,A.,J.M.Douglas,and TJ.McAvoy,'Shortcut techniques for distillation column design
and control column design',Ind Eng.Chem.Proc.Des.Dev,18(1979)197-202.
Kister,H.Z.,Distillation Operation,McGraw-Hill,New York,1989.
Kister,H.Z.,Distillation Design,McGraw-Hill,New York,1992.
Kunesh,J.G.et al.,'Distillation:still towering over other options',Chem.Eng.Progr.,Oct.1995,
43-54.
Lewis,W.K.,'The efficiency and design of rectifying columns for binary mixtures,’Ind.Eng.
Chem.,14(1922)492.
Porter,K.E.,'Why research is needed in distillation',Trans.Inst.Chem.Engrs.,73 (Part A),May
1995,357-362.
Ryan,J.M.,'Replotting the McCabe-Thiele diagram',Chem.Eng.,May 2001,109-113.
Smoker,E.H.,‘Analytic determination of plates in fractionating columns',Trans.AIChE,
34(1938)165-172.
Sorel,E.,La Rectification de l'Alcohol,Gauthiers Villars,Paris,1893.
Stichlmair,J.G.,and J.R.Fair,Distillation—Principles and Practice,Wiley-VCH,New York,
1998.
Yuan,K.S.,and B.C.-Y.Lu,‘Vapour-liquid equilibria,’J.Chem.Eng.Data,8(Oct.1963)549.
 8 Liquid-Liquid Extraction

Liquid-liquid extraction(sometimes abbreviated LLX)is a mass transfer operation in which a

solution(called the feed which is a mixture of a solute and a carrier liquid)is brought into intimate
contact with a second immiscible or slightly miscible liquid (called the solvent)in order to achieve
transfer of the solute(s)from the feed to the solvent.The two liquid phases that have different
densities are then separated.The solute-rich phase (this is the solvent stream,now enriched with
the solute)is called the extract;the residual feed stream that may have a little of the solute left
in it is called the raffinate.If the carrier in the feed and the solvent are partly miscible,the
raffinate will also have a little solvent dissolved in it,and the extract phase will contain a little
dissolved carrier.The solute is separated from the extract phase in an acceptably pure form,and
the solvent dissolved in the raffinate is recovered.An extraction process generally involves
four major steps.

(a) Bringing the feed and the solvent into intimate contact by dispersing one phase into
the other as droplets.
(b) Separation of the extract and the raffinate phases that have different densities.
(c) Removal and recovery of the solute from the extract phase in a relatively pure form
(by distillation,evaporation,crystallization,etc.).
(d) Removal and recovery of the solvent from each phase,usually by distillation.
Separation of a liquid mixture or solution by distillation is operationally simpler
than extraction.For example,a binary liquid mixture having components of different volatilities
can, in principle,be separated into two relatively pure products(a'distillate'and a 'residue')in a
single column.But separation of the same mixture by extraction requires at least one distillation
column in addition to the extractor.Very often more than one distillation column is used for the
recovery of the solvent from the raffinate (called raffinate clean-up)and for separation of the
carrier liquid from the extract phase(Figure 8.1).Phase separation of the extract and the
raffinate may not be rapid if the difference in their densities is small and the interfacial
tension is low.Loss of solvent may also occur in some cases.In its totality,solvent
extraction is a more elaborate technique than distillation.In a typical liquid-liquid
extraction process,only about 15%of the capital cost goes towards the extractor and the
remaining 85%goes towards the distillation
422
 4Solute,C+(B)
A Few Examples of Solvent Extraction 423

Extract
B+C(A) Note:Species in the brackets
Feed are present in low concentration.
evaporation.
A+C or re-extraction
Distillation
crystallization

Recycled Solvent B+(A,C

solvent* Solvent B+(A,C)
*The recycled solvent may have a little dissolved carrier in it.
Extraction
Column**The 'makeup'solvent is added to compensate for the loss of solvent in the operation
Solvent |Carrier,A+(B,C)
B+(A,C)l

Makeup solvent**
Raffinate ,clean-up"
A+(B,C) bydistillation
Raffinat strippin
e g

Schematic of an extraction unit with product recovery and rafinate clean-up arrangements;A:carrier,B:solvent,
Figure
8.1

columns and other equipment for solvent recovery and product purification.Also,only about
5% of the operating cost of the unit is required for the extractor and the remaining 95%goes
towards solvent recovery.Despite these limitations,there are situations when the technique of
distillation either fails or becomes uneconomic.A few such cases,where solvent extraction is
an attractive separation technique,are described below.

(a) The components to be separated have close boiling points.For example,aromatics are
extracted from paraffinic feedstocks in the refineries by using a solvent like sulphur
dioxide,n-methyl pyrolidone,sulpholane,etc.The number of distillation trays becomes
prohibitively large if the relative volatility is close to unity(say less than 1.2),and solvent
extraction,therefore,may be an attractive alternative for such a mixture.
(b) Separation of heat-sensitive materials such as antibiotics,vitamins,etc.Penicillin is
recovered from the fermentation broth by using a suitable solvent such as butyl
acetate. (c)Recovery of non-volatile solutes,usually from aqueous solutions,in hydro-
metallurgy. (d) Recovery of a solute from a very dilute solution—for
example,bioseparation(proteins,
antibiotics,high-value bioproducts).
(e) Removal of organics from aqueous streams—for example,removal of phenol from
aqueous wastes.

8.1 A FEW EXAMPLES OF SOLVENT EXTRACTION

Liquid-liquid extraction is also called'solvent extraction'.A number of common industrial

extraction processes are listed in Table 8.1(also see Cusack and Glatz,1996).A few
such representative processes are briefly described below.
 42
4

Cha
Table 8.1 Some commercially important extraction processes Exra

Extraction process Feed Solven

1.Separation of BTX(benzene,toluene and Petroleum fractions containing aromatics Sulpholane(tetrahydrothiophene,1-1-

xylenes)from petroleum fractions.(BTX dioxide) urfural,N-
is used as a feed-stock for the methylpyrrolidone,diethylene glycol
preparation o petrochemicals) etraethylene glycol

2. Lube oil extraction Hydrocarbons including n-paraffins,iso- _iquid SO₂,phenol,furfural,liquid

paraffins,naphthenes, aromatics and mixed aliphatic- propane, N-methyl-pyrrolidone
aromatic ring structures
3.Separation of aromatic hydrocarbons Petroleum fractions containing aromatics Tetraethylene glycol-wate
from
petroleum fractions
4.Extraction of caprolactum from "lactum oil 'Lactum oil',aqueous (NH₄)₂SO₄-liquor Benzene,toluene,trichloroethylene,etc
containing caprolactum(such liquids are obtained
in the process of caprolactum manufacture

5.Extraction of phenolics from coal tar Light liquor containing phenolics (obtained in a sobutyl acetate
and liquors coa carbonization plant
6.Extraction of phenol from aqueous wastes Aqueous waste streams,coal carbonization Butyl acetate,di-isopropyl ether,MIBK
plants phenolic resin plants
7.Extraction of citral (a flavouring substance Lemon grass and orange oi An alcohol and a lower
used in food and some other industries) hydrocarbon(solvent pair;for
example,methanol and pentane
8.Refining of oils and fats (mono-and Oil and fat product A polar solvent like acetone or a lower
alcoho
diglycerides removed from tri-
glycerides) 9. Extraction of coppe Dilute Cu-ion bearing acidic leach liquo Hydroxylamine,proprietary solvents like LIX-
63 IX-64N,LIX-65N,LIX-70,etc
10.Extraction of penicillin Penicillin fermentation broth n-Amylacetate (most common),n-butyl
acetate
11.Removal of H₂S Liquefied natural gas (LNG Monoethanolamine (MEA),methanol-
diethanolamine amine (MDEA)
 A Few Examples of Solvent Extraction 425

8.1.1 Extraction of Aromatics

Solvent extraction is an important separation technique in petroleum refineries,particularly for
lube oil production.The viscosity index(V.I.)is an important parameter for a lubricating oil.
Many undesirable compounds,especially aromatics that reduce the V.I.,have to be removed from
the lube oil feed stock to ensure the required viscosity index.Aromatics (benzene,toluene and
xylenes,BTX)must also be removed from kerosene and jet fuels.This can be done conveniently
by using a solvent selective for aromatics,sulphur,nitrogen,and oxygenated compounds.
Important solvents are furfural,sulpholane(tetrahydrothiophene-1,1-dioxide),N-methyl
pyrrolidone(NMP),diethylene glycol,tetraethylene glycol,methyl-ethyl-ketone(MEK),and
methyl-isobutyl-ketone(MIBK)which selectively remove aromatics and weakly polar
compounds(Lucan,2000).Phenol and sulphur dioxide are no longer used because of their
toxicity and other problems.The process involves extraction followed by distillation-stripping of
both the raffinate(that contains the purified lube and some solvent)and the extract
(containing the aromatics and the solvent).A very simple flow diagram of the sulpholane
process is shown in Figure 8.2(a).A rotating disk contactor (RDC,see Section 8.5.4)is
commonly used for thisUnwashed
purpose.Theraffinateseparated aromatics are further fractionated in pure
Raffinate (paraffins
form for use as feedstocks for the petrochemical industry.
(wJ
W

Water
Extract
(aromatics)
Oil feed recovery
column
Extractor
column Extractive distill
Extrac colum
t
Water n
colum
Recycle sulpholane
n Water
Aromati
cs wash

Sulpholan Wate
r
e
Backwash w

Figure 8.2(a) Separation of aromatics from a feedstock—the sulpholane process.

8.1.2 Recovery and Concentration of Antibiotics by Solvent Extraction

Penicillin,a major antibiotic,is produced by fermentation.The concentration of the substance
in the fermentation broth is small (typically 20-35 gram penicillin per litre broth).Recovery and
concentration of penicillin from the broth is done by extraction(Hatton,1985)using a solvent
such as amyl acetate,butyl acetate,or methyl-isobutyl-ketone (MIBK).At a pH of about
2, penicillin remains in the acid form and has a low solubility in water.But at this pH,it is
favourably
426 Chapter 8 Liquid-Liquid Extraction

transported to an organic solvent (mentioned earlier)from the aqueous fermentation broth because
of a high distribution coefficient.However,a reversal of the distribution coefficient occurs at a
pH above 7.This pH-dependent distribution of penicillin in the water-ester pair is made use
of to recover,purify and simultaneously concentrate the antibiotic from the broth.The
extraction process,which is carried out at about 4℃,is schematically shown in Figure
8.2(b).

Spent solvent,for recycle

Spent broth Buffer solution

(raffinate) (pH~7.5)
Figure 8.2(b) Recovery and concentration of penicillin by extraction.

The pH of the fermentation broth is adjusted to about 2 by dosing sulphuric acid.It is then
brought into intimate contact with the solvent in a centrifugal extractor (Pod I).A Podbielniak
extractor (often abbreviated Pod')is commonly used and a solvent-to-broth ratio of 0.1 to
0.2 is maintained.More than 90%recovery of penicillin occurs and its concentration in the
solvent or ester-phase becomes a few times more than that in the feed broth.The penicillin-rich
extract (the ester-phase)is now contacted with a basic buffer solution of pH 7.5 in a second
extractor (Pod II)when most of the antibiotics get transferred into the aqueous phase in the
salt form (generally it is potassium penicillin).The concentration in the extract further
increases a few times in this extractor that uses an organic-to-aqueous phase ratio of 5 to
10.The raffinate from the second extractor (the ester-phase)is recycled to Pod I as the
solvent.Penicillin is crystallized from the aqueous extract by adjusting the pH once again.

8.1.3 Extraction of Caprolactum

Caprolactum is produced and used in large quantities for the manufacture of nylon-6,a bulk
polymer.It is synthesized from cyclohexane(cyclohexane →cyclohexanol →cyclohexanone
→cyclohexanone oxime →caprolactum).The last step of the process involves reaction of the
oxime with sulphuric acid when caprolactum and ammonium sulphate are formed.The aqueous
reaction mixture separates into an organic-rich phase('lactum oil'containing 65-70%
caprolactum)and a water-rich phase having ammonium sulphate and 2-3%caprolactum.The
two phases are fed at appropriate locations of a rotating disk contactor [Figure
8.2(c)].Toluene, benzene and trichloroethylene are good solvents(the last two are carcinogens
and are not used any more).Caprolactum goes to the extract,and ammonium sulphate
remains in the raffinate. The two streams are further treated to get caprolactum in a pure form
and to recover the solvent and ammonium sulphate.
 Extract
Water
A Few Examples of Solvent Extraction 427

‘Lactum oil’
(NH₄)₂SO₄aq.
phase,2-3% Lactum Oil Ammonium
Toluene
Extractor Sulphate solvent
caprolactum Recovery (Solvent)
Reaction product Extracto
r
Extracto
r
settling tank Raffinate
Aqueous waste
to discharge

Caprolactum to recovery
(NH₄)₂SO₄ to recovery
Feed from the reactor

Figure 8.2(c) Recovery of caprolactum by solvent extraction.

8.1.4 A Few Other Applications

Solvent extraction has many other uses in food,pharmaceutical,metallurgical,environmental,
and organic and inorganic chemical industries.It is used for purification of wet-process
phosphoric acid to prepare the food-grade material.Recovery of acetic acid from a dilute aqueous
solution has been practised since long because separation by distillation is very energy-intensive.
Ethyl acetate and di-iso-propyl ether are the preferred solvents.Extraction of protein from ground
fish or refining of fats by using propane as the purifying solvent (Solexol process)are typical
applications in the food industry.Natural vitamins A and D are extracted from fish liver oil using
liquid propane.Solvent extraction has proved to be effective in wastewater treatment.A typical
application is separation and recovery of toxic organics like phenol.With the rapid growth in
biotechnology,separation of high value bioproducts from dilute aqueous solutions (often called
bioseparation)has assumed great importance.Solvent extraction is an effective and widely used
technique for this purpose.One novel application is separation and concentration of proteins and
other biomolecules by 'aqueous two-phase extraction'(Rao et al.,1998).The carrier and the
solvent phases are aqueous solutions of two mutually incompatible polymers.The most common
two polymers used for this purpose are polyethylene glycol (PEG)and dextran.Two major
disadvantages of the technique occur due to small density difference and low interfacial tension
of such two 'immiscible'aqueous phases.
Solvent extraction is an important technique of recovery of some metals.Extraction of
copper from the ore leach liquor is a very important process.It can recover copper from very
dilute solutions.A chelating extractant derived from hydroxyoximes or quinolinol in kerosene
solution is largely used.Applications to nickel and cobalt extraction are also well known.Solvent
extraction is an important separation step in 'nuclear fuel reprocessing'.Spent fuel from a nuclear
reactor contains 238U,235U,239Pu,239Th,and a few other fission products.Reprocessing consists
of a number of steps for the separation of plutonium and residual uranium from the rest with
a view to reusing them by mixing with fresh nuclear fuel.Alternatively,these materials may be
disposed of safely.
428 Chapter 8 Liquid-Liquid Extraction

The spent fuel is first dissolved in nitric acid,and the hexavalent basic nitrates of
uranium and plutonium—UO₂(NO₃)₂and PuO₂(NO₃)₂-are extracted from the aqueous
solution using a solvent like tri-n-butyl phosphate mixed with kerosene.The metals are
then recovered from the extract and recycled.Separation and concentration of uranium from
the ore leach liquor are also done by solvent extraction.The mixer-settler type extractors are
commonly used in metal extraction.

8.2 LIQUID-LIQUID EQUILIBRIA(LLE)

A liquid-liquid extraction system contains at least three components—the solute(C),the carrier

liquid in the feed(A),and the extracting solvent (B).For example,in the process of extraction
of penicillin from the fermentation broth described in Section 8.1,penicillin is the solute(C),
water is the carrier(A),and butyl acetate is the solvent(B).Quite often the total number of
components is more than three;the carrier itself may have more than one liquid in it,there
may be more than one solute in the feed,or the solvent may be a mixed solvent.The equilibrium
data for a liquid-liquid system are of vital importance in the selection and design of an
extraction equipment.

8.2.1 Classification of Ternary Systems

Here we shall confine our discussion only to ternary systems comprising a carrier (A),a solvent
(B),and a solute(C).Three binary mixtures can be formed out of these components:A-B,
B-C and C-A.The mutual miscibility behaviour of the components in each of these binaries
determines the nature of the equilibrium diagram for the ternary system.Most of the
ternary systems fall in one of the following categories.

(a) The carrier(A)and the solvent(B)are practically immiscible.The equilibrium in such

a system may be represented in the form of a‘x-y'plot as in the case of distribution
of a solute between a carrier gas and a solvent.If the solute concentration is
small,a Henry's law-type linear distribution law applies.
(b) The solute is miscible with the carrier and with the solvent in all proportions,but
the carrier and the solvent are only partially miscible(A-C and B-C are miscible
pairs;the pair A-B is partially miscible).Such a system is called a Type-I ternary
system.About 75%of ternary liquid systems fall in this category.
(c) The solute is completely miscible with the carrier;but both the solute and the carrier
have limited miscibility with the solvent(the binary A-C is miscible in all
proportions;the pairs B-C and A-B are only partially miscible).A ternary mixture of
this type is called a Type II system.

8.2.2 Experimental Determination of Liquid-liquid Equilibrium Data

As in the case of determination of gas-liquid or vapour-liquid equilibria,liquid-liquid
equilibrium data are obtained by measuring the concentrations of the three components in
the two liquid phases in equilibrium at a given temperature.The following steps are
followed:(a)Suitable
 Liquid-Liquid Equilibria (LLE) 429

quantities of purified A,B,and C are taken in an equilibrium cell maintained at a constant

temperature.The content is mixed vigorously for a sufficient time to ensure attainment of
equilibrium.(b)The content is allowed to separate into two phases.(c)Samples are drawn from
the two phases and analyzed for the concentrations(expressed as mass fractions or mole
fractions)of A,B,and C.A set of such experiments conducted with varying amounts of the three
components at a constant temperature yields the data for the construction of a liquid-liquid
equilibrium diagram.The liquid phase rich in the solvent (B)is called the extract,and the other
phase which is rich in the carrier'is called the raffinate.

8.2.3 Graphical Representation of Liquid-liquid Equilibrium Data

For any of the two liquid phases in equilibrium in a ternary system,there are three concentration
terms of the three components.If concentrations are expressed in mole fraction or in mass
fraction,the sum of the three concentrations is unity.It is not possible to describe a phase
or the equilibrium of two phases in contact in terms of the three concentrations using the
normal rectangular coordinate system.But this can be done conveniently on an 'equilateral
triangular graph'.Also there are two other techniques of representation of ternary equilibrium
data using the rectangular coordinate system:(a)a 'right-angled triangular diagram'in which
only two concentrations are plotted,and (b)using rectangular coordinates and ploting the
mass fractions (or mole fractions)of the solute and of the solvent in the two phases on
‘solvent-free basis'.

The equilateral triangular diagram

The basis of the technique of presentation of equilibrium data on an equilateral triangular graph
paper is that the sum of the distances of a point within an equilateral triangle from the three
sides is equal to the height of the triangle.On the equilateral triangle ABC in Figure 8.3(a),the
vertices A,B and C represent the 'pure components'A,B and C respectively;the sides AB,BC
and CA

%B
Figure 8.3(a) Liquid-iquid equilbrium data presented in the equilateral triangular coordinates.
430 Chapter 8 Liquid-Liquid Extraction

represent mixtures of A and B,B and C,and C and A respectively.A point within the △ABC
represents a mixture of the components A,B and C.Consider the point M,for example.The
sum of its distances from the three sides is MN₁+MN₂+MN₃=CT,which is equal to the
altitude of the triangle.From Figure 8.3(a)it is found that the point M lies on the dotted line
representing 60%C(MN₁=0.6CT,CT being the altitude).Also,the point M lies on the dotted
lines representing 16%A and 24%B respectively.So a mixture of A,B and C having
16%A,24%B,and 60%C is represented by the point M on the triangular diagram.The LLE
diagram of a ternary system is depicted in Figure 8.3(b).Here the solute C is miscible with the
carrier A and with the solvent B in all proportions,but the carrier and the solvent are only
partially miscible (Type I system).The curve RPS is the equilibrium diagram in the equilateral
triangular coordinate system. It is obtained by plotting the data points representing the two
liquid phases in equilibrium.The point R on the line AB represents the solubility of the
solvent B in the carrier A;the point S represents that of the carrier A in the solvent B if
there is no solute.

Figure 8.3(b) Liquid-liquid equilibrium data presented in the equilateral triangular coordinates.

The pair of points G,and H,on the curve represents two liquid phases in equilibrium;Gi
is rich in the carrier(raffinate phase)and H,is rich in the solvent (extract phase).The line
G₁H₁ is called a tie line.Also shown are two other tie lines G₂H₂and G₃H₃.Since such a line
connects two points representing two phases in equilibrium,it is called a tie line(see Section
7.1.2).There is an infinite number of such tie lines corresponding to an equilibrium
diagram.Usually,these are not parallel.The length of a tie line decreases as we move away from
the side AB,and eventually the last tie line reduces to a point P.The point P,that demarcates
the raffinate and the extract sides of the equilibrium curve,is called the plait point.The type of
equilibrium curve RPS is called binodal because it has two arms RP and PS,representing the
raffinate and the extract sides. The equilibrium curve also demarcates the miscible
and immiscible regions on the graph.A liquid mixture having an 'overall
composition'corresponding to a point K below the equilibrium
 Liquid-Liquid Equilibria (LLE) 431

curve RPS is a two-phase mixture.Such a mixture,when left undisturbed,separates into

two phases at equilibrium.The compositions of these two phases are given by the terminals
(G₂and H₂)of the tie line passing through the point K;their amounts are given by the 'Lever
Arm Rule' [see Eq.(7.4)].
The equilibrium curve is different for a Type II system;Figure 8.3(c)shows a representative
equilibrium diagram.The raffinate and the extract arms of the equilibrium diagram do not
meet. So there is no plait point.A few tie lines are shown in the figure.

Figure 8.3(c) Liquid-liquid equilibrium for a type ll system(A-Band B-Cpartially miscible).

The right-angled triangular diagram

The rectangular coordinate system is used to prepare such a plot.Mass fractions of the solute
in the two phases(the raffinate and the extract phases)at equilibrium are plotted against the
corresponding mass fractions of the solvent [Figure 8.4(a)].Concentrations of the extract phase
(usually in mass fraction)are denoted by y₄,yg,and yc;those of the raffinate are x₄,xg,and
xc. The raffinate arm PQ is obtained by ploting the set of points(xg,xc);the extract arm
PR is

Raffinate arm,xg Vs xc

(a) (b)

Figure 8.4 (a)Equilibrium plot on the right triangular coordinate,and (b)the x-yplot.
432 Chapter 8 Liquid-Liquid Extraction

obtained by plotting the set of points(yp,yc).The point P is the plait point.The point D₁on
the raffinate arm and D₂on the extract arm represent compositions at equilibrium.If they are
joined, we get the tie line D₁D₂.The equilibrium diagram can also be drawn on the xc-
yc plane [Figure 8.4(b)].The tie line D₁D₂corresponds to the point D on that plane.

Equilibrium plot on solvent-free basis

In this presentation of LLE data,the mass ratios of the solute(X and Y)in the two phases are
plotted versus the corresponding mass ratios (z or Z)of the solvent,all on 'solvent-free basis'.
The quantities (X,Y,and z or Z)are defined below.

the raffinate
f

the extract
f

Here x is the mass fraction of a component in the raffinate,and y is that in the extract.A typical
equilibrium plot on“solvent-free basis”is shown in Figure 8.5.The X-z and Y-Z plots of LLE
are similar to the enthalpy-concentration diagrams (x-Htand y-Hv)used in distillation calculations.
Such plots(X-z and Y-Z)are called Maloney-Schubert diagram or Janecke diagram.

EXAMPLE 8.1(Janecke diagram) Draw the Janecke diagram for a liquid-liquid system
using the following equilibrium data.Show the tie lines on the diagram.

Raffinate phase Extract phase

XA XB Xc YA YB Yc
0.939 0.0601 0.0 0.06 0.94 0.0
0.7327 0.0654 0.0219 0.0520 0.918 0.03
0.4402 0.0732 0.4866 0.036 0.88 0.084
0.246 0.090 0.664 0.0185 0.851 0.1305
0.103 0.1047 0.7923 0.0069 0.8276 0.1655
0.0 0.1103 0.8897 0.0 0.8246 0.1754

Solution
The X-z and Y-Z data are calculated from the above table.

0.0 0.0234 0.525 0.730 0.885 1.0

(for the raffinate phase)

0.064 0.067 0.079 0.099 0.117 0.124

0.0 0.366 0.70 0.876 0.960 1.0

(for the extract phase)

15.67 11.2 7.33 5.71 4.8 3 4.7

The X-z and Y-Z plots and the tie lines are shown in the Janecke diagram,Figure 8.5.
 Liquid-Liquid Equilibria(LLE) 433

z,Z 9-

X,Y
Figure 8.5 Janecke plot of liquid-liquid equilibrium data.(A few tie lines are also shown.)

8.2.4 Effect of Temperature on Liquid-Liquid Equilibria

The effect of temperature on liquid-liquid equilibria shown in Figure 8.6 is pretty strong.
Miscibility of a liquid pair generally increases with temperature.With increasing temperature,the
miscibility of the B-C pair(the solvent and the solute)in a Type II system increases more quickly
than that of the A-B pair.At the critical solution temperature of the B-C pair,a Type II system

A B

A (ii)T=34.5℃

(a) (b)

Figure 8.6 Effect of temperature on liquid-liquid equilibria:(a)effect of temperature on solubilty for the system n-hexane
(A)- methyl-cyclohexane(C)-aniline(B),and (b)temperature effect illustrated by a three-dimensional sketch.
434 Chapter 8 Liquid-Liquid Extraction

turns into a Type I system.This behaviour is displayed by the n-hexane(A)-

methyl- cyclohexane(C)-aniline(B)system with increasing temperature [Figure 8.6(a)].The
two-phase region of the equilibrium diagram for a Type II system still contracts with increasing
temperature and eventually vanishes at a temperature called its critical solution temperature',tes
[Figure 8.6(b)]. The critical solution temperature is the minimum temperature at which the
components A,B and C of a Type I system becomes miscible in all proportions.

8.3 SOLVENT SELECTION

The right solvent is the key to successful separation by solvent extraction(Cusack et al.,1991;
Cusack and Glatz,1996).Solvents used are mostly organic.The important criteria for
solvent selection are given below.The recent computational strategies of molecular interaction for
solvent selection in diverse applications have been reviewed by Gani et al.(2006).

(a)Selectivity: ‘Selectivity'or preferential uptake of the solute by the solvent over the
carrier is the single most important factor in choosing a solvent for an extraction
job.Selectivity or 'separation factor'is defined as

(8.1)

Selectivity of the solute varies with the compositions of the two phases in equilibrium and
depends on temperature.It is unity at the plait point because the compositions of the two
phases become the same.A theoretical approach to selection of a solvent for a particular type
or class of solute was proposed by Robbins(see Cusack et al.,1991).The basis of the
approach is the following simple equality of the activities of the solute in the two phases at
equilibrium.

xc(Yc)g=yc(Yc)e
→ (8.2)

where(Yc)e and(Yc)r are the activity coefficients of the solute in the extract and the raffinate
phases respectively,and K is the 'distribution coefficient'or 'partition coefficient'of the solute
for the carrier-solvent pair.It appears from Eq.(8.2)that if the activity coefficient of the solute
is small in the extract phase,the distribution coefficient is large,and the solvent has a better
selectivity for the particular solute.Analyzing the equilibrium data of a large number of systems
(more than 900),Robbins(1980)prepared a qualitative summary(Table 8.2)of the solvent-
solute interaction in terms of its effect on the activity coefficient.The functional groups of solute
are numbered and named in the left two columns of Table 8.2.The numbers given in the top
row also represent solvents having the corresponding functional groups.The rest of the table
is a matrix having +,-and O as the elements.A‘+'sign at a location indicates that
compounds belonging to the particular group of solvents in the column tend to raise the
activity coefficient of the solute belonging to the group in the row.For example,a solute
having a phenolic group (group 1 of the solute class)exhibits a high activity in a solvent
(like a paraffin)belonging to group 11 or 12(the 1,11 and 1,12 positions of table have
a‘+'sign).But in a solvent of group 5,the activity coefficient of the same solute is lower(the
1,5 position has a‘-’sign).Thus for extraction of phenol,a ketone is a good solvent because the
activity of phenol in a ketone is low and the distribution coefficient is predicted to be
large.Table 8.2 classifies solvents primarily on the basis of hydrogen bonding and electron
donor-acceptor interaction with solutes.
 SolventSelection 435

Table 8.2 Solute-solvent group interactions-preliminary guide to solvent selection*

Solute Solvent class

class Group 1 2 3 4 5 6 7 8 9 10 11 12
1. Phenol 0 0 0 0
一 一 一 一 一 一 一 一
2. Acid,thiol 0 0 一 0 一 一 0 0 0 0 + +

3. Alcohol,water 一
一 0 + + 0 一 一 + + + +

Active-H on multihalo paraffin 0 0 + 0 0 +

一 一 一 一 一 一
H-accepto
5. Ketone,amide with no H 一
+ 一 0 + 十 + + + + +
on N sulphone,phosphine 一
oxide
6. Tertiary amine 一 0 一 + 0 + + 0 + 0 0
7. Secondary amine 一
0 一 一 + + 0 0 0 0 0 +

8. Primary 0 一 一 + + 0 0 + + + +
amine,ammonia
amide with 2H on N
9. Ether,oxide,sulphoxide 一
0 + 一 + 0 0 + 0 + 0 +

10. Ester,aldehyde,carbonate 一
0 + 一 + + 0 + + 0 + +
phosphate,nitrate,nitrite
nitrile,intramolecular
bonding (for example,o-
nitro phenol
11. Aromatic,olefin,halogen + + + 0 + 0 0 + 0 + 0 0
aromatic multi-halo-paraffin
without active H,mono-halo-
paraffin
Non-H-bonding
12. Paraffin,carbon disulphide + + + + + 0 + + + + 0 0

Key: Deviation from normality for mixtures (+)=positive;(-)=negative;(0)=neutral

*Source:Robbins,L.A,Chem.Eng.Prog,76,October 1980,pp.58-61.

(b)Carrier-solvent immiscibility: If the mutual solubility of the carrier and the solvent is
low,they can be satisfactorily separated in the settler.Only a small quantity of the solvent will
be retained in the raffinate and a small quantity of the carrier will remain dissolved in the
solvent. So the cost of further separation of the phases by distillation or otherwise will be
small.
(c)Interfacial tension: Interfacial tension between the carrier and the solvent has two
opposing effects.A low interfacial tension favours fine dispersion of one liquid in the other,thereby
increasing the specific interfacial area of mass transfer.The power consumption for dispersing
one liquid into the other is also lower.On the other hand,coalescence of droplets leading to
the separation of the raffinate and the extract phases does not occur readily if the interfacial
tension
is low.It is desirable to strike a balance between these opposing effects while selecting a solvent.

(d)Density: The driving force for phase separation in a settler is the difference in
the densities of the two phases.The density of the lighter phase should generally be at least
5%less than that of the heavier phase in order to ensure smooth phase separation.
436 Chapter 8 Liquid-Liquid Extraction

(e)Viscosity: The solvent viscosity should be low.This reduces power consumption

for mixing the phases.
(f)Other factors: The solvent should preferably be less expensive,non-toxic,and non-
corrosive.It should have a low flamability and volatility.Another very important phenomenon
is accumulation of impurities in the solvent.If the solvent is of low volatility,it leaves the
solvent clean-up tower at the bottom(Figure 8.1)and is recycled.There is a strong
probability of accumulation of impurities and surface active agents.This causes lowering
of interfacial tension and surface resistance to mass transfer between the two phases.The
performance of an extractor may be greatly reduced by such phenomena.It has been estimated
(see Chem.Engg. Progress,June 2002,p.74)that the presence of impurities can reduce the
capacity of a column by 20%or more and its efficiency by as much as 60%.
Hardly any solvent will satisfactorily meet all the above criteria.Choosing a solvent is
again a matter of striking a balance between the properties and cost of the solvent on the one
hand, and the equipment and operating costs and ease of operation on the other.

8.4 DESIGN CALCULATIONS FOR STAGE-WISE EXTRACTION

While dealing with the problem of separation of a liquid mixture,a decision has to be taken first
about the separation process(such as distillation,extraction,crystallization,etc.)to be adopted.
If liquid-liquid extraction appears to be the choice,the next job is to select the solvent to be used.
The design of extractors is far less standardized than that of absorption or distillation columns.
Pilot plant tests may have to be done if reliable design data collected from operating units
handling a similar mixture are not available (Cusack and Glatz,1998).
Like other mass transfer operations,solvent extraction can be carried out in a staged or
in a continuous contact equipment (see Section 8.6).The important stage-wise pieces of
contact equipment are(i)mixer-settler,(ii)sieve tray column,and (iii)Schiebel
column.Continuous contact takes place in an equipment like(i)the rotating disk contactor
(RDC),(ii)Graesser raining bucket contactor,(ii)Podbielniak extractor,(iv)the packed
column,and(v)the spray column,etc.In this section,we will discuss the methods of
determination of the number of ideal stages required for solvent extraction in a stage-wise
contact equipment.The methods to be described here are based on graphical construction of
ideal stages for partially miscible ternary systems.Determination of the number of ideal stages
for extraction systems in which the solvent and the carrier (the A-B pair)are practically
immiscible can be done by following the procedures already described in Chapter 4.

8.4.1 Single-Stage Operation

A single-stage equilibrium contact device is shown in Figure 8.7(a).The feed enters the
mixer at a rate F having a solute concentration xp(the solute concentration in the raffinate is
denoted by x and that in the extract by y,both in mass%).The solvent is supplied at a rate
of S;it has a solute concentration ys.The liquid-liquid dispersion attains equilibrium and
leaves the mixer at a rate M with an overall solute concentration xw.The
raffinate(flow rate =R,solute

The solute is separated from the extract (solvent)phase (as shown in Figure 8.1)and the solvent is
recycled. So the feed solvent is likely to have a little solute left in it.
 Design Calculations for Stage-Wise Extraction 437

Figure 8.7(a)Schematic of a single-stage extraction unit.

concentration =xg)and the extract (flow rate =E,solute concentration =ye)phases leave the
settler after phase separation.The following material balance equations may be written.
Total material balance:
F+S=M=E+R (8.3)
Solute balance: Fxp+Sys=Mxu =Eye+Rxg (8.4)

→ (8.5)

Combining the above two equations,we may

write
Fxr+Sys=(F+S)xm

→ (8.6)

The ternary equilibrium data are plotted on a suit-

able diagram.Let us select the equilateral
triangu- lar diagram [Figure 8.7(b)].The
compositions of the feed and the solvent
streams are located at
points F and S on the diagram'.By virtue of the
Lever Arm Rule (Section 7.4),we may conclude
that the mixture of mass M and solute concentra- Figure 8.7(b) Single-stage liquid extraction
tion x can be represented by a point M on the line
calculation using the equilibrium plot on the right
joining F and S.From Eqs.(8.3)and(8.4),we
triangular coordinate.
may also write

(8.7)

The above equation indicates that the point M also lies on the line joining the points E and R.
Since the mixer acts as a 'theoretical'or 'equilibrium stage',the phases E and R are at equilibrium
and must lie on the terminals of the tie line through the point M on the equilateral
triangular diagram.Thus the solute concentrations in the extract and the raffinate phases (ye
and xg)can

+By convention the symbols F and S represent the flow rates and locations of the two points representing
their compositions.Similar convention has been used in Section 7.2.
438 Chapter 8 Liquid-Liquid Extraction

be obtained by drawing the tie line through the point M.The steps of the graphical procedure
are given below.

(a) Draw the ternary equilibrium curve on the equilateral triangular diagram(or any
other suitable diagram).Locate the points F and S.
(b) Calculate xm from the material balance equation [Eq.(8.5)]and locate the point M
on the line FS.
(c) Draw the tie line ER through the point M.The terminals of the tie line give the extract
and raffinate concentrations,ye and xg.The amount of the extract and raffinate phases
(E and R)and the percentage of the solute separated from the feed can now be calculated
from Eqs.(8.3)and(8.4)or Eq.(8.7).

If a required percentage separation of the solute is specified,the necessary solvent

rate can be calculated.However,this will involve a trial-and-error procedure.This is
illustrated in Example 8.2 using the right triangular coordinate.

EXAMPLE 8.2(Single-stage extraction) One thousand kilograms of an aqueous

solution containing 50%acetone is contacted with 800 kg of chlorobenzene containing
0.5 mass% acetone in a mixer-settler unit,followed by separation of the extract and the
raffinate phases. (a)Determine the composition of the extract and the raffinate phases and the
fraction of acetone extracted.(b)Also calculate the amount of solvent required if 90%of the
acetone is to be removed.Equilibrium and tie line data are given below.
Aqueous phase(Raffinate) Organic phase (Extract)
Water Chlorobenzene Acetone Water Chlorobenzene Acetone
XA XB Xc yA YB Yc
0.9989 0.0011 0.0 0.0018 0.9982 0.0
0.8979 0.0021 0.1 0.0049 0.8872 0.1079
0.7969 0.0031 0.2 0.0079 0.7698 0.2223
0.6942 0.0058 0.3 0.0172 0.608 0.3748
0.5864 0.0136 0.4 0.0305 0.4751 0.4944
0.4628 0.0372 0.5 0.0724 0.3357 0.5919
0.2741 0.1259 0.6 0.2285 0.1508 0.6107
0.2566 0.1376 0.6058 0.2566 0.1376 0.6058

Solution
Given:mass of the feed,F=1000 kg;mass fraction acetone(C)in the feed,xcr =0.5;and
the mass fraction of chlorobenzene in the feed,xg.p =0.
(a) Solvent: mass,S=800 kg; yc,s =0.005; yBs =0.995
From Eqs.(8.3)and(8.5),

M=F+S=1800;
The equilibrium data are plotted using the right triangular coordinates [Figure 8.8(a)].The points
F and S are plotted on the diagram;the point M is located on the line FS(for xm,c
=0.28).The tie line RE through M is determined by trial taking help of the xc-yc curve [Figure
8.8(b)]drawn
 Design Calculations for Stage-Wise Extraction 439

alongside on the same scale.It is to be noted that a point on the xc-yc curve gives the
equilibrium concentrations of the solute(C)in the two phases.The point P on the xc-yc diagram
corresponds to the tie line RE.
From Figure 8.8(a)or 8.8(b),the solute concentrations in the raffinate(R)and the
extract (E)phases are:
xcR=0.236 and YcE=0.302
From Eqs.(8.3)and(8.7),

E+R=1800 and → E =
1200 kg R=
600 kg

Mass of acetone leaving with the raffinate =(R)(xc,r)=(1200)(0.302)= 362.4 kg

1.0

0.8

0.6

xc Yc F
Y
0.4
P
M E
R
0.2

0.0 S
0.4 0.6
0 0 0 0 0 0 0
Xg
x
(a) c

Figure 8.8
Single-stage extraction calculation illustrated:(a)Right triangular coordinate,and (b)x-ydiagram.

Mass of acetone in the feed =(1000)(0.5)=500

kg Acetone entering with the solvent =(800)(0.005)=4
Net amount kg
of acetone transported to the extract stream =362.4-4 =358.4 kg

i.e.

(b) If 90%of the acetone is removed, 71.7%

acetone remaining in the aqueous phase =(500)(0.1)=50 kg

It is to be noted that at this low concentration of the solute,the mutual solubility of water
and chlorobenzene is negligible.Therefore,the raffinate may be assumed to be virtually free from
chlorobenzene.Then the concentration of acetone in the raffinate is 50/550 =0.0909.
At xcr=0.0909,we have ycE=0.105(from the equilibrium curve).
Also,the mass of the raffinate,R =550 kg
440 Chapter 8 Liquid-Liquid Extraction

If S is the mass of the solvent required,we can write the following material balance for
the solute.
(1000)(0.5)+(S)(0.005)=(S+450)(0.105)+(550)(0.0909)→S= 4027
kg

8.4.2 Determination of the Tie Line Through a Point on the

Equilibrium Line

Only a few experimental tie line data for a ternary system are generally available.There are two
‘interpolation'techniques of drawing a tie line through any point on the equilibrium curve.Both
the techniques use the available tie line data and a 'conjugate line'(Sherwood and Pigford,1952;
Seader and Henley,1998).One technique is illustrated in Figure 8.9.A horizontal line is drawn
through the end G of the tie line GH.A vertical line is drawn through the point H.The two
lines meet at K.The locus of the point K is called the conjugate line'.Now let us use this
conjugate line to draw a tie line through any point Gi on the equilibrium curve.A horizontal line
is drawn from G₁that meets the conjugate line at K₁.A vertical line through K₁meets the
equilibrium curve at H₁.Then G₁H₁is the tie line through the point Gi.

Figure 8.9 Construction of a conjugate line using the tie-linedata.

8.4.3 Multistage Cross-current Extraction

A multistage cross-current cascade is schematically shown in Figure 8.10.The solvent is fed
to the stages separately and the amounts need not be equal.The feed is supplied to the stage at
one

Mixed extract

Figure 8.10 Schematic of a cross-current extraction cascade.

 Design Calculations for Stage-Wise Extraction 441

end of the cascade (let us call it stage 1).It moves from one stage to the next in succession with
gradually decreasing solute concentration.If the solvent and the carrier liquid have
negligible miscibility,extraction calculations can be done following the procedure described in
Section 4.6.4. Here we shall deal with ternary systems in which the carrier and the solute have
limited solubility.
The graphical method of calculation is convenient.Any of the three types of equilibrium
diagrams (drawn using equilateral triangular,right triangular or 'solvent-free'coordinates)may
be used.But the calculation procedures are similar.
Let there be N number of stages in the cross-current extraction cascade.The flow rates and
concentrations of all the input and output streams are shown in Figure 8.10.We may write
the
following mass balance for the nth stage.
equations Total mass balance
R-1+S=M₁=En+R (8.8)
Mass balance of the solute C (8.9)
Rn-IXn-1+SnYs=MXn =E₁₂Yn+RnXn
The principle of multistage extraction calculation is similar to that of a single-stage extraction
unit.From Eq.(8.8),we see that if the flow rates and concentrations of the streams Rp-I and
S,are known,the point M,can be located on the line joining Rμ-i and S,.Again,if the tie line
through the point Mn is drawn,its terminals give the points Rn and E..A step-by-step
procedure is given below.

(a) Stage 1 receives the fresh feed which does not generally contain any
solvent.Putting n =1,in Eq.(8.8),we get the material balance equation for stage 1.

F+S₁=M₁=E₁+R₁
(8.10)
The point F is located on the x-y plane.The point S,is also located.The point
M₁is located on the line joining F and Si by using the Lever Arm Rule or by
calculating the value of xmi from Eq.(8.9).The tie line through the point M₁is
drawn and the points E₁and R₁are located at its terminals.
(b) For stage 2,the solvent rate is S₂and the rate of input of feed is R₁(which is
nothing but the 'first-stage raffinate').The point Sz is located on the graph;the other
point R₁ is known.These two points are joined and the mixture of the phases Mz is
located on the line joining these points R,and Sz.Again the terminals of the tie line
through Mzgive the points E₂and R₂.
(c) The procedure is repeated for the remaining stages.In the above analysis,we have
tacitly assumed that the rates of solvent input to the stages and its concentrations are
known. The flow rates and concentrations of the raffinates'and 'extracts'from all
the stages can be found out by following the above steps.In practical
problems,the solute concentrations,if any,in the feed solvent streams to the
different stages remain the same.The procedure is illustrated in Example 8.3.

There may be other versions of the design problem.For example:the feed rate and
composition,the solvent composition and the maximum allowable concentration of the solute in
the final raffinate are given;the same amount of solvent is fed to the stages;it is required
to determine the solvent rate if the extraction is to be done in a specified number of
stages.This and other versions of the design problem may be solved using the principles
discussed above. But trial-and-error calculations may sometimes be necessary depending upon
the nature of the problem.
442 Chapter 8 Liquid-Liquid Extraction

EXAMPLE 8.3 (Cross-current extraction calculation) One thousand kilograms of

an aqueous
solution containing 35 mass%trimethyl amine (TMA)and 65%water is to be extracted using
benzene as the solvent.A three-stage cross-current extraction scheme is suggested.The
amounts of solvent (98%benzene,2%TMA)to be used in successive stages are 815 kg,950
kg and 2625 kg.Determine the fraction of the solute removed if the stages are ideal.The
compositions of the raffinate and the extract (two phases)as well as the tie-line data are
given below(water: A;benzene:B;TMA:C).
Water-rich phase Xg 0.004 0.006 0.01 0.02 0.03 0.036 0.07 0.13
xc 0.05 0.10 0.15 0.20 0.35 0.30 0.35 0.40
Benzene-rich phase YB 0.95 0.90 0.84 0.78 9.71 0.63 0.50 0.26
yc 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
Tie-line data: xc 0.04 0.083 0.13 0.215 0.395
yc 0.035 0.068 0.09 0.145 0.31

Solution
The problem is solved using the right triangular coordinate.
Feed,F=1000 kg.Feed composition:35%TMA(xc,f=0.35);65%water(x₄,p =0.65).
The equilibrium data are plotted and the tie lines are drawn(dotted lines)in Figure 8.11.

xc Yc

Xg

Figure 8.11 Graphical solution for a three-stage cross-current extraction cascade.

Stage 1: The solvent rate,S₁=815 kg;ys.s=0.98,ycs =0.02(2%TMA,rest

M₁=1000+815 benzene). kg;xcMi=[(1000)(0.35)+(815)(0.02)]/1815
=1815 =0.202
The points F(xg,p=0,xcr=0.35),S(yBs=0.98,yc,s =0.02)are located on the diagram.The
point M₁is located on the line FS(xcMi=0.202).The tie line R₁Ei is drawn;the extremities
of the tie line give the compositions of the raffinate and extract phases leaving stage 1 in
equilibrium.
 Design Calculations for Stage-Wise Extraction 443

From the figure, Xc,R1=0.24; yc,Ei=0.166

Total material balance:Eq.(8.3), M₁=R₁+E₁=1815 (i)
Solute balance: (M₁)(xc,Mi)=(R₁)(xcRi)+(E₁)(yc,Ri)
→ (1815)(0.202)=(R₁)(0.24)+(E₁)(0.166) (ii)
Solving the material balance equations (i)and (ii),R₁= 882 kg 933
E₁=
kg
Stage 2: The raffinate from stage 1(R₁)is the feed to stage 2.Solvent added,S₂=950
kg; yc,s₂=0.02.
M₂=R₁+S₂=882+950=1832 kg;solute balance:M₂xc,M₂=(R₁)(xc,ri)+(S₂)(yc,s₂)
Putting the values of different quantities,xc.Mz =0.126.
The composition of the solvent to the second stage being the same as that to the first,it
is represented by the same point S.The line RS is joined and the point M₂(xc.Mz=0.126)is
located on this line as shown in Figure 8.11.The tie line R₂E₂is drawn through the point
M₂.
The compositions of the raffinate and the extract phases from stage 2 are obtained from
the figure as:xcR₂=0.15 and yc,E₂=0.105
Material balance equations similar to Eqs.(i)and (i)are 977.7
written.Solving
kg these equations,we get

R₂= 854.3 E₂=

Stage 3: Similarly,the third stage receives R₂=854.3 kg 'feed'and S₃=2625 kg of the

solvent. Proceeding in the same way we can locate the point M₃(xcM₃=0.052)on the line R₂S
and draw the tie line through M₃to meet the equilibrium curve at the points
R₃(xcg₃=0.0596)and E₃(yc,E₃=0.0506).The amounts of the phases can be obtained from
material balance as before: 2938.5 kg

R₃= 540.8 and E₃=

Total amount of TMA leaving the stages
=(E₁)(yc,E₁)+(E₂)(yc,E₂)+(E₃)(yc,E₃)
=(933)(0.166)+(977.7)(0.105)+(2938.5)(0.0506)=406.2 kg

Total amount of TMA entering the three stages with the solvent
=(S₁+S₂+S₃)(yc,s)=(815+950 +2625)(0.02)=87.8 kg
Net amount of TMA removed =406.2-87.8 =318.4 kg
Total amount of solute in the feed =(1000)(0.35)=350 kg
Fraction of TMA removed =(318.4/350)(100)= 91%

8.4.4 Countercurrent Extraction-Determination of the Number of

ldeal Stages

A countercurrent extraction cascade,along with the flow rates and concentrations of the
input and output streams at the stages,is shown in Figure 8.12.The concentrations and flow
rates
444 Chapter 8 Liquid-Liquid Extraction

of the feed and the solvent are usually given.If the solvent rate is not specified,it can be
taken as a suitable multiple of the 'minimum solvent rate'.We have to determine the number
of ideal contact stages required if the maximum permissible concentration of the solute in the
raffinate is given.We may write the following material balance equations.
Total material balance over the entire unit (over envelope I):F+S =E₁+Rn =M (8.11)

Solute balance over envelope I:Fxp+Sys =E₁yi+Ryxv =Mxm (8.12)

Total material balance over envelope II:Rp-1+S=En+RN (8.13)
Solute balance over envelope II:Rn-Xn-I+Sys =EnSn+Rw×v (8.14)

The equilibrium curve is drawn using a suitable coordinate system.From the known
compositions of the feed,the solvent and the raffinate,the points F,S and Rw,can be located on
the diagram. The point M representing the mixture of F and S is also located on the line
FS.Equation (8.11) says that the point M lies also on the line joining the points Rv and
E₁(the point E₁represents the extract phase leaving stage 1;see Figure 8.12).Therefore,the line
RyM when extended meets the equilibrium curve at the point Ei.

Figure 8.12 Schematic of a countercurrent extraction cascade.

Now we rewrite Eq.(8.11)in the following form:

E₁-F=S-R=△ (8.15)
Also from Eqs.(8.13)and (8.15),

E-R =S-R=△ (8.16)

Here △may be considered to be a fictitious stream obtained by 'removing'a mass F of the
feed from the first stage extract E,,or by removing'a mass Ry of the 'last stage raffinate'from
the solvent S.It represents a 'difference point'(similar to that identified in Section 7.8)lying on
the line FE,extended and also on RS extended.In other words,it is the po int of intersection of
FE₁and RwS.Also,it follows from Eq.(8.16)that if the line Rn-1E,is extended,it has to
pass through the difference point △.These results can be directly used to determine the number of
ideal contact stages required to achieve the given degree of separation.
Since the stages are ideal,the streams E,and R,leaving the nth stage are at
equilibrium.Thus the tie line through the point E,meets the equilibrium curve at
R.Equation(8.16)says that for n=2,the line joining R,and △meets the equilibrium curve at
Ez.The tie line through E₂meets the equilibrium curve at the point R₂.The procedure is
repeated till the point Ry representing the raffinate is reached.The number of tie lines drawn
in the process to reach the point Ry is the number of ideal stages.The procedure is illustrated
in Example 8.4.
 Design Calculations for Stage-Wise Extraction 445

EXAMPLE 8.4(Mullistage countercurrent extraction) It is planned to extract diphenyl

hexane(DPH)from a solution in docosane(A)using'pure'furfural(B)as the solvent.The
feed enters the extractor cascade at a rate of 2000 kg/h with 45%DPH(C)that has to be
reduced to 4%in the final raffinate.The solvent rate is 2500 kg/ h.Determine the number
of theoretical stages required.Extraction is to be carried out at 45°℃.Several compositions on
the extract and the raffinate arms and the tie-line data in mass%of the components at 45°C
are given below.
Equilibrium data
A: 96.0 84.0 67.0 52.5 32.6 21.3 13.2 7.7 4.4 2.6 1.5 1.0 0.7
B: 4.0 5.0 7.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 99.3
C: 0 11.0 26.0 37.5 47.4 48.7 46.8 42.3 35.6 27.4 18.5 9.0 0.0

Tie-linedata
Raffinate (Docosane)phase,mass% Extract (Furfural)phase,mass%
A B C A B C
85.2 4.8 10. 1.1 89.1 9.
69.0 6.5 0
2.2 73.6 8
43.9 13.3 24.
6.8 52.3 24.
5 2
42.6 40.
9

Solution
Given:F=2000; xcF=0.45; xcn =0.04; S=2500; xcs =0.0

By Eq.(8.5).

The raffinate(i.e.the stream R)has 4%DPH in it.So mass fraction of DPH in it

is xc =0.04.
The equilibrium data are plotted using the right triangular coordinate in Figure 8.13(a);the
tie lines are shown by light dotted lines.The points F(0,0.45),S(1.0,0),M(on the line FS at
XcM=0.2),Rw(at xc=0.04 on the equilibrium curve)are located.Ry and M are joined and the
line is extended to meet the equilibrium curve at Ei.The lines FEl and RwS,when extended,meet
at the 'difference point',△.
The stages being ideal,the tie line through E₁meets the equilibrium curve at the point Rj,
the raffinate phase leaving the first stage.Also,putting n=2,it is e vident from Eq.
(8.16)that E₂lies on the point of intersection of the line R₁△ and the equilibrium curve.In
fact,R,Ez is the 'operating line'for the second stage of the cascade.The tie line through the
point E₂meets the equilibrium curve at R₂.Proceeding in the same way,we can draw successive
stages till the point Rv is reached.
From Figure 8.13(a),the number of ideal stages required for the separation is 4.
An alternative technique can be more conveniently used for graphical construction of stages.
A line emanating from the difference point,△,intersects the extract arm of the LLE curve at a
point E+i [corresponding solute concentration is yc =(yc)n+l]and the raffinate arm at a point
R [where xc=(xc),].A few such lines(drawn as broken lines)are shown in Figure 8.13(b).
The locus'of the point [(xc)n,(yc)n+il is the operating line on the xc-yc plane
[see
446 Chapter 8 Liquid-Liquid Extraction

Mass fraction of solute

(C)

Mass fraction solvent (B)

Figure 8.13(a) Graphical construction of ideal stages for countercurrent extraction using the right-angled
triangular coordinate system

xc,Yc

xg,Yp

Figure 8.13(b) Graphical constructlion for obtaining points on the operating line.

Figure 8.13(c)].The set of(xc,yc)values derived from Figure 8.13(b)and used to draw the
operating line on Figure 8.13(c)is given below.
tc 0.04 0.1 0.14 0.17 0.22 0.26 0.30 0.33 0.38 0.415
Yc 0.03 0.051 0.018 0.09 0.125 0.15 0.178 0.20 0.252 0.280

The equilibrium line is drawn in Figure 8.13(c)using the given 'tie line'data.The
operating line is also drawn by plotting the above xc-yc data.Stages are now constructed by
drawing stages
 Design Calculations for Stage-Wise Extraction 447

Yc
xc
Figure 8.13(c) Construction of stages on the Xc-ycplane.

between the equilibrium line and the operating line.The number of ideal stages is 4.8 [compared
to 4 obtained from Figure 8.13(a);the difference probably occurs because of the error in
drawing the tie lines].
This technique of construction is simpler and gives a more accurate estimate of the
number of stages and is recommended for use.

8.4.5 Stage-wise Extraction with Reflux

The solute concentration in the extract leaving a countercurrent cascade can at best be
nearly at equilibrium with the feed stream.It is possible to have a richer extract by use of reflux
at the product end of the cascade.This works like adding reflux to the rectifying section of a
distillation column.An arrangement of countercurrent multistage extraction with reflux is
schematically shown in Figure 8.14.

Figure 8.14 Countercurrent multistage extraction with reflux.

8.4.6 The Minimum Solvent Rate

This is an important quantity often determined in connection with the design of an
extraction equipment.An infinite number of contact stages (or an infinite height of a
continuous contact
448 Chapter 8 Liquid-Liquid Extraction

device such as a packed tower)is required to perform a given separation if the minimum
solvent rate is used.If the △ point for an infinite number of stages is known,the minimum
solvent rate, Sm(the suffix m indicates 'minimum'),can be calculated by using the Lever Arm
Rule.

(8.17)

To determine the minimum solvent rate S,the equilibrium curve is drawn on a suitable
coordinate (for example,the right triangular coordinate)and the points F,S and Rv are located
from the given compositions of the feed,the solvent and the raffinate.The points Rw and S are
joined and produced.A tie line through the point F and a few others below it are drawn.All
these tie lines are extended to meet the line RwS produced at a number of △ points.The meeting
point closest to Sis△(see Figure 8.15)if the tie lines are inclined towards the point S for the
particular liquid-liquid system.There may be systems for which the tie lines slope away from
the point s.In such a case,the extended tie lines intersect the line SRw produced on the left
side of the diagram yielding a set of △ points.The minimum solvent rate corresponds to the △
point farthest from S if it lies on the left or nearest to S if it lies on the right.It may be noted that
in many cases, the tie line passing through the feed point F corresponds to the minimum solvent
rate.This means that the pinch point lies on the feed end of the cascade.Determination of the
minimum solvent rate is illustrated in Example 8.5.
Once the minimum solvent rate is found,the actual solvent rate is chosen on the basis of
economic considerations.A higher solvent rate will no doubt reduce the fixed costs because
less number of stages are required,but the operating cost will be higher primarily
because of (i)handling a larger quantity of liquids,(ii)larger equipment
size,and(iii)higher cost of separation of the solvent.

EXAMPLE 8.5 (Minimum solvent rate calculation) Acetic acid (C)is to be extracted from a
45%aqueous solution using isopropyl ether(B)as the solvent at 20℃.The feed rate is
1500 kg/h and the raffinate must not contain more than 2.5%acid.If the solvent supplied
to the extractor has 0.5%acetic acid in it,calculate the minimum solvent rate.The
liquid-liquid equilibrium data at 20℃ are given below.
Water layer (raffinate),mass% Ether layer (extract),mass%
A B C A B C
0.981 0,012
0.006 0.005 0.993 0.001
0.971 0.015 9 0.007 0.989 8
0.955 0.016 0.014 0.008 0.984 0.003
0.917 0.019 1 0.01 0.971 7
0.844 0.023 0.028 0.007
0.019 0.933
0.711 0.034 9 9
0.039 0.847
0.589 0.044 0.064 0.019
0.069 0.715
0.451 0.106 2 3
0.108 0.581
0.371 0.165 0.133 0.048
0.255 0.151 0.487
2
0.367 0.11
0.443 4
0.464
0.216
0.311
0.362

Solution
The equilibrium data are plotted on the right triangular coordinate to get the equilibrium
curve (Figure 8.15).A set of tie lines are also drawn(these are the dotted lines in Figure
8.15).The
 Design Calculations for Stage-Wise Extraction 449

xc,Yc

Xg,Yg

Figure 8.15 Graphical determination of the minimum solvent rate (△m is the difference point corresponding to the
minimum solvent rate).

point F(feed F=1500 kg/h;xgr=0,xcr=0.45)and the point S(solvent;ybs =0.995,

yc,s =0.005)are located on the diagram.The raffinate has 2.5 mass%acid in it.The point Rv,
representing the raffinate,is located on the equilibrium curve corresponding to xcRn =0.025.
The points Rv and S are joined and the line RyS is extended.
A set of tie lines are drawn including one which,when extended,passes through the
feed point F.The tie lines are found to slope towards the point S,and meet the extension of
the line RwS at a number of △ points.The △ point (△m)nearest to S corresponds to the
minimum solvent rate,S.Here it happens for the tie line TL.We use Eq.(8.17)and material
balances to calculate Sm
The length segments R△m(=4.13 units)and S△m(=1.17 units)are measured from the
diagram.
Then Sm/Rw=Rw△m/S△m=4.13/1.17 =3.53 (i)
But Rw is not known,and Sm cannot be obtained from the above equation alone.It is
necessary to obtain the concentration of the extract stream E,corresponding to the minimum
solvent rate. The line F△ intersects the extract arm of the equilibrium curve at Ei and the
concentration of the solute in it is found to be y₁=0.232.Now we can write down two more
equations—the total material balance and the solute balance.

Total material balance: F+Sm=Rn+E₁ → 1500+Sm=Rn+E₁ (ii)

Solute balance: F(0.45)+Sm(0.005)=Rx(0.025)+E₁(0.232) (ii)

Solving the above Eqs.(i),(i)and (ii)we get,Sm=[1942.4 kg =minimum solvent rate.

450 Chapter 8 Liquid-Liquid Extraction

8.5 LIQUID-LIQUID EXTRACTION EQUIPMENT

The liquid-liquid extraction operation involves intimate con tact between two immiscible
or partially miscible liquid phases compared to a gas or vapour and a liquid phase in gas
absorption and distillation.A few major differences between these two important fluid-fluid
contacting phenomena are discussed here.

(a) Dispersing one liquid in another one is more difficult than dispersing a gas in a
liquid. When a gas bubbles through a liquid on a tray,the large difference in the densities
of the phases and the small viscosity of the gas cause a high bubble rise velocity.This
creates turbulence,rapid bubble breakage and coalescence and a large interfacial area of
contact. But the shear stress required for the breakage of a drop is much higher than
that for a bubble.Since the rise velocity of a drop in a liquid is rather small
(because of small buoyancy),the required shear stress is not always generated by the
motion of a drop alone.
(b) Unlike the gas-liquid system,a small density difference in a liquid-liquid system
(besides a low interfacial tension)causes difficulty in separating a liquid-liquid dispersion
into two clear liquid phases.
(c)A substantially higher mechanical energy input per unit volume of the medium is required
for creating a liquid-liquid dispersion compared to that of a gas-liquid dispersion in
a stirred vessel.

For the reasons mentioned above,the solvent extractors mostly have design and
construction features much different from those of absorption and distillation columns.A
classification of the
more common extractors is given in Figure 8.16 (Reissinger and Schroter,1978;Lo et
al.,1983). Their Extractors
Commercial construction and operation are briefly described below.Table 8.3 shows some
important characteristics of common extractors.

Phase contact by centrifugal force

Classification
Centrifugal by ope ofagitation
extractors
Podbielniak and a few others (for example,Robatel,Delaval)
Unagitated columns Pulsed columns

Reciprocating plate columns Mechanically agitated columns

Perforated plate,oi Sieve plate

Spray column Pulsed

Packed column Perforated plate column
Packed trayRotary
or SieveSieve tray
agitated contactors
Sciebel column
Oldshue-Rushton column Rotating disk contactor
Kuhni column

Figure 8.16 Classification of commercial extractors.

 Liquid-Liquid Extraction Equipment 451

Table 8.3 Characteristics of the common extractors (Wankat,1988)

Extractor class Fxtractor type lmportant characteristics

Mixer-settlers Agitated vesse High stage efficiency,handles wide phase ratios

Static mixers and liquids with high viscosity,flexibility,reliable
scale-up,not suitable for large number of theoretical stages
Unagitated columns Plate,packed and Low capital cost,low operating/maintenance cost,simple
spray columns construction nandles corrosive materials

Pulsed columns Perforated plate Low HETS,high mass transfer coefficient,no internal moving
parts
Packed columns
Rotary agitated RDC,Oldshue-Rushton Moderate to high capacity,reasonable HETS
columns
Scheibel,Kuhni extracto accommodates many theoretical stages,moderate cost,low
cost of operation and maintenance

Reciprocating plate Karr columr High loading,low HETS,high versatility and

flexibility,simple construction,handles liquids with
suspended solids
Centnifugal Podbielniak Short contact time,suitable for unstable materials,small size (limited
space requirement),handles easily emulsifiable and small △p
systems

8.5.1 The Mixer-settler

This is the simplest and oldest type of extraction equipment.A stage of a mixer-settler
cascade [Figure 8.7(a)]consists of a'mixer'and a 'settler'.

Mixer
A common mixer is a vertical vessel in which one liquid phase is finely dispersed into the other
by an agitator.The vessel is generally provided with four baffles to prevent the formation of
vortex and also to create intense turbulence.The two liquid streams enter the mixer near the
bottom.Sufficient time of contact is allowed for mass transfer from one phase to the other.This
is the 'holding time'.The dispersion leaves the mixer at an upper level.A liquid-liquid mixing
vessel is broadly similar to the one shown in Figure 5.15 except that it should be provided
with two liquid inlets and one outlet for the dispersion.
A variety of impeller designs are available,for example,propeller,turbine,paddle,etc.A few
common impeller types are shown in Figure 8.17.An impeller is usually positioned halfway the
liquid depth.Power consumption or the rate of mechanical energy input depends upon a number
of factors—the dimensions of the tank,the volume of dispersion,the impeller size and the
design, the physical properties of the liquids(density,viscosity,interfacial tension),the ratio
of the masses of the liquids in the tank('phase ratio’),the degree of dispersion
required,etc.Another important factor is,which phase is dispersed in the two-phase
dispersion.If we start with pure A(the carrier)and go on adding B(the solvent)to it,we see
that up to a certain mass per cent of A,it(i.e.the phase A)remains the continuous phase and B
remains in it in the form of droplets. But after a threshold phase ratio,phase inversion occurs
when B becomes the continuous phase while A remains dispersed in it.The power
consumption,hydrodynamics and mass transfer characteristics of a liquid-liquid dispersion
greatly change when the inversion point is crossed.
452 Chapter 8 Liquid-Liquid Extraction

(a) (b) (c) (d) (e)

Figure 8.17 Afew common impellertypes:(a)marine-type propeller,(b)centrifugal turbine,(c)pitched-blade turbine,(d)flat-

blade paddle,and (e)flat-blade turbine (Treybal,Mass Transfer Operations,1980).

As an alternative to mechanical agitation,dispersion of the phases in the mixing vessel may

be achieved by pump circulation,inline non-mechanical mixing by using a jet or nozzle,a static
mixer or even by air agitation.It is understandable that an intense agitation or mixing will produce
very small droplets and will provide a high rate of mass transfer because of enhanced interfacial
area and mass transfer coefficient.Even a stage-efficiency of nearly 100%may be achieved.But
this benefit is partially overshadowed by the accompanying problem of separation of the
dispersion in distinct phases in the settler.So,a balance between the two—namely creating a very
fine dispersion to achieve a high stage-efficiency and the time and efficiency of settling-has to
be reached.Drop-size in dispersions typically ranges between 0.1 and 1 mm.

Settler
A dispersion leaves the mixer almost as an emulsion.This emulsion separates into two phases
in the settler by coalescence of the fine droplets.A higher interfacial tension between the liquids
enhances the coalescence rate;a lower value tends to produce a relatively stable
emulsion that is difficult to separate into two phases.This factor also governs the selection of
a solvent in liquid extraction.Phase separation becomes faster if the drop-size is larger,both the
interfacial tension and the density difference between the liquids are higher,and the
viscosity of the continuous phase is low.It may be noted that the drops are not of uniform
size.There is always a'distribution'of drop-size and'drop-size'generally means the average
size of the drops.
In order to improve the separation efficiency and to reduce the holding time and the
volume of the setler,settling aids may be used.Tower packings,wire-mesh packings or
oblique plate nests are effective settling aids.The surface of the settling aid is better wetted
by the droplets or the dispersed phase.So,the impinging drops stick to the settling aid and then
coalesce to form bigger drops that separate out of the dispersion.
A settling tank is a horizontal vessel provided with horizontal baffles (Figure 8.18).Typically,
it has a length up to four times the diameter.For a system having △p≥0.1 g/cm³,a settler can
separate about 300 gal/h of dispersion for 1 ft²of phase disengagement area (it is taken as
LD,, L=vessel length,D,=diameter).
It will be pertinent to identify the advantages and disadvantages of the mixer-settler
device. The advantages are:(a)high-stage efficiency (90%or more);(b)operational flexibility—a
mixer- settler can handle difficult-to-disperse systems,like those having a large interfacial tension
and/or
 Liquid-Liquid Extraction Equipment 453

Figure 8.18 Horzontal gravity-setting vessel for phase separation of iquid-liquid dispersion (Treybal,1963).

large density difference;it can also operate with varying flow rates and phase
ratios; (c)scale-up design of mixer-settlers can be done more reliably from laboratory test
data;(d)it can handle high viscous liquids and also liquids having suspended solids.The
disadvantages are: (a)considerable pump and piping cost (for this reason,the use of mixer-
settlers is often limited to separation jobs requiring less than five theoretical stages);(b)a
larger floor area is required;
(c)more solvent cost,because a large volume of solvent is always retained in the settling
vessels. Mixer-settlers are widely used in wet metallurgical processes.

Tower extractor
The tower extractor,developed by Lurgi Co.,accommodates the mixers and setlers into a
compact continuously operated unit as shown in Figure 8.19.The mixers of the cascade are
placed outside the tower which has compartments for separating the phases.A drop
coalescence zone is provided between a mixer and the corresponding settler.

Figure 8.19 Lurgi tower extractor (Humphrey et al,1984).

454 Chapter 8 Liquid-Liquid Extraction

8.5.2 Centrifugal Extractors

Centrifugal extractors are based on the use of centrifugal force'to cause countercurrent radial
flow of the two liquid phases.Two common extractors of this kind are the Podbielniak
extractor' and the Quadronic extractor'.The first one is the oldest centrifugal extractor put to
commercial use.
The Podbielniak extractor(Figure 8.20)consists of a cylindrical drum rotating around a
horizontal shaft.A number of concentric perforated cylindrical shells are fixed to the drum.The
shaft is hollow except at the solid middle section.Both the heavy and the light phases enter
through the shaft but from opposite directions.The heavy liquid is let out near the centre of the
drum.The light liquid is channelled to the inner periphery of the rotating drum.Because of the
density difference of the liquids,the heavy phase flows radially outwards and displaces the
light liquid phase that flows radially inwards (i.e.in the opposite direction).The heavy
liquid that reaches the periphery returns through the channels and leaves the unit through an
annular region around the shaft.The light liquid collects near the centre and also leaves
through an annular passage around the shaft.The Podbielniak extractor is functionally similar to
a sieve tray column in which the trays,as if,form concentric perforated shells and
countercurrent radial flow of the phases occurs.

Light-liquid

Light liquid
Heavy liquid

Distribution of the phases in a Podbielniak

contactor

Figure 8.20 The Podbielniak extractor:(1)rotor and shaft assembly,(2)base,(3)bearings,(4)multi-V-belt drive,

5)concentically assembled perforated elements,(6)liquid distibution tubes,(7)tubular passage for cleaning and
flushing, and(8)inlet and outlet ports.

The rotating drum,fixed to the trunnions carried on ball bearings,is provided with a drive
pulley and is covered by an outer casing.Proper sealing arrangements are made at the contact
between stationary and rotating parts.Drum diameters typically range from 1.5 to 3 ft,and the
length may vary from 0.5 to 1 ft.The rotational speed generally varies from 2000 to 5000 rpm,
and the contact time between the phases is only a few seconds.The extractor typically provides
about 3 to 5 theoretical stages of contact and is suitable when the liquid density difference
is △p≥0.05 g/cm³.The advantages of the Podbielniak extractor are:(a)very short contact
time
 Liquid-Liquid Extraction Equipment 455

between the phases(this makes the equipment suitable for unstable and sensitive materials
like pharmaceuticals),(b)low space requirement,and (c)can handle liquids having a small
difference in densities.The disadvantages are:(a)high capital cost,and (b)high maintenance
cost.

8.5.3 Unagitated Extraction Columns

An extractor belonging to this category has a cylindrical shell with internals.The heavy liquid
enters at the top and the light at the bottom through a distributor.One of the liquids remains
dispersed in the other.Countercurrent flow of the liquids is driven by gravity and
bouyancy forces.Drop breakage and coalescence occur all along the column and new
interfacial area is created or the interfacial area is 'renewed'.The drop breakage and
coalescence phenomena are enhanced in column extractors in which there is mechanical energy
input by the motion of the internals(for example,a rotor)in the column.
Because the drops move under the effect of buoyancy only,the maximum allowable flow
rates of the phases in a given column get limited by flooding of the tower.The mechanism of
flooding is the same as that in a gas-liquid contactor.However,a small difference in the densities
of the phases makes the flooding phenomenon more sensitive towards changes in flow rates.
Axial mixing of the phases occurs to some extent in the column.This reduces the theoretical
rate of mass transfer in a countercurrent equipment.This phenomenon will be discussed
later.

Spray towers
The spray tower is the simplest type of column extractor.It consists of a vertical cylinder with
no internals,except spray nozzles at the top for the heavy liquid [Figure 8.21(a)].Droplets of
the dispersed phase form at the nozzles and move downwards through the light
continuous phase.The 'throughputs’(i.e.the flow rates of the two phases through the
column)greatly
Light liquiddepend
out upon Lightthe density Lightdifference
liquid in liquid out and viscosities of the
phases.Alternatively,the
Heavy liquid in heavy liquid
Interface
Heavy liquid in
Interface Heavy liquid in
Coalesced
Interface
dispersed
phase
Perforated
plate Redistributor

Downcomer
Light liquid in

Light liquid in Heavy liquid out

Light liquid in

Heavy liquid out Heavy liquid out

(a) (b) (c)

Figure 8.21 Unagitated column extractors:(a)spray column,(b)packed column,and (c)perforated-plate (sieve-plate)column.

456 Chapter 8 Liquid-Liquid Extraction

may be continuous and the light solvent may be distributed at the bottom through a perforated
pipe to form droplets that will rise upwards.In this case,the drops finally separate out from the
dispersion and coalesce into a clear liquid phase at the top above the level of inlet of the heavy
phase from the bottom.Considerable 'axial mixing'(also called backmixing)occurs in
the continuous phase,lowering the available driving force for mass transfer.The small rate of
drop breakage and coalescence in the dispersion is also responsible for the low mass transfer
rate.As a result,the spray tower does not normally give more than one to two theoretical
stages.
Because of the simple construction and operation,spray columns are used for simpler
operations like nutralization,washing,etc.But these are pretty common in 'direct contact'
heating or cooling of liquids.

Packed extraction columns

These are more efficient than the spray tower because the packing in the tower reduces
backmixing and enhances drop breakage and coalescence(with frequent distortion)of the
drops, thus providing a higher rate of mass transfer.The tower construction [Figure 8.21(b)]is
similar to the packed gas absorber;it is provided with the packing support,the liquid
distributor and redistributor,nozzles,etc.Similar packing materials are
used(rings,saddles,modern high performance packings and structured
packings).However,sufficient space must be provided above and below the liquid inlet
nozzles for phase separation of the liquids.The separation efficiency of a packed column is
strongly influenced by the wettability of the packing.If the packing is wetted by the dispersed
phase,there will be more coalescence of the drops and hence the separation efficiency will
be reduced.The 'height of a theoretical stage'(HETS)typically ranges between 0.6 and 1.6
m.

Sieve-tray columns
The construction of a sieve-tray extraction column is similar to the one for gas absorption or
distillation.The heavier phase flows across a perforated plate through which the lighter liquid
rises as drops [Figure 8.21(c)].The drops coalesce to form a phase-separated layer that remains
in-between the dispersion and the immediate upper tray.This clear lighter phase then enters
the upper tray as the dispersed drops.The heavier phase flowing down to the next lower tray
is relieved of the lighter dispersed phase in the downcomer (this is comparable to the
vapour- liquid disengagement in the downcomer in a distillation or gas absorption tower).The
size of the perforations of a sieve tray may be %inch to %inch.The tray spacing is
considerably larger than that used in gas-liquid contacting.Weirs are not needed for a sieve
tray extraction column.

Pulsed columns
A periodic pulse to the accumulated heavier liquid at the bottom of a packed or a sieve tray
is known to increase the mass transfer rate.A reciprocating unit imparts pulses (typically 1.5
to 4 hertz)to the lighter phases entering at the bottom.These are called pulsed extraction
columns' and were quite popular at one time.Columns up to 1 m diameter are reportedly used in
the nuclear industry(Ruthven,1997).
Spray,packed and sieve-tray columns are non-proprietary columns(i.e.not covered
by patents).But the class of column extractors with mechanical energy input are
proprietary (patented)columns.The more important ones are described in the following
section.
 Liquid-Liquid Extraction Equipment 457

8.5.4 Rotary Agitated Extraction Columns

An extractor of this kind consists of a tall column having a long rotating shaft fitted with a set
of impellers.The column is divided into a number of compartments by a set of fixed partition
plates (annular,in most cases).These extractors provide a pretty large number of theoretical
plates in a single unit (as many as 30 in some designs),and have a low HETS.A few such
devices (Figure 8.22)are described below.

Scheibel column
This is the oldest column extractor with mechanical agitation.There are at least three
designs. The one shown schematically in Figure 8.22(a)(i)consists of a vertical shell
divided into a number of compartments by annular partition disks.A central agitator shaft has
a set of double- bladed paddle or turbine impellers,one for each compartment.Dispersion is
created by the agitator.In an older version,a wire mesh packing filled a part of a
compartment.The packing helps in drop coalescence but makes the column prone to fouling.

Oldshue-Rushton column
It is an offshoot of the Scheibel column in which the wire-mesh packing is
avoided.Annular partition disks (also called compartment baffles)are used as before but these
are now perforated and have smaller inner diameter [Figure 8.22(a)(ii)].Vertical baffles are
placed along the column wall.Each compartment is agitated.This column was developed in
the 1950s.Pretty large diameter units are now used.

(i) (

Figure 8.22(a) Schematics of agitated extraction columns:(i)Schiebel column,and (i)Oldshue-Rushton column.

458 Chapter 8 Liquid-Liquid Extraction

Kuhni extractor
This is also similar to the Scheibel column,but does not contain any packing.A baffled turbine
impeller agitates the contents in each compartment.Stators of the shape of perforated
plates

phase out
(
(ii)

(iii) (iv)
Figure 8.22(b) (i)Kuhni extractor,(ii)Karr column,(ii)rotating disk contactor (RDC),and (iv)asymmetric rotating
disk contactor(ARDC)[Seader and Henley,1998].
 Selection of Extractors 459

separate the compartments.The column offers up to ten theoretical stages per

metre.A schematic of this extractor is shown in Figure 8.22(b)(i).
Karr column
The Karr column [Figure 8.22(b)(ii)]is a descendant of the pulsed sieve-tray column.It has
a reciprocating shaft with perforated plates mounted on it.The plates typically have 50-
60%free area.The extractor is suitable for systems having intermediate to low interfacial
tension.

Rotating disk contactor(RDO)

This extractor,developed in the 1950s by the Shell Company in the Netherlands,has been widely
used in the chemical and petroleum industries.Nowadays,this is the best known agitated column
extractor.Horizontal disks mounted on a central shaft in a vertical cylinder act as the
agitating elements [Figure 8.22(b)(iii)].A set of annular disks,having inner diameter slightly
bigger than the rotating disks,is also mounted on the shaft.The rotor disks break the drops by
shear force. The column has considerable flexibility of operation.It can be run at up to
50%of the rated capacity.It can also handle liquids having suspended solids.But it is not
suitable for highly viscous liquids.Typical throughputs range between 1500 and 6000
gal/h,but capacities higher than these can also be built.
Considerable backmixing occurs in the RDC.A maximum of 0.5 to 1 theoretical stages
can be achieved per metre of height.It is very convenient to handle large throughputs.RDC
units up to several metres in diameter are in use.A recent modification of RDC is the
asymmetric rotating disk contactor (ARDC)shown in Figure 8.22(b)(iv).In this equipment
the shaft with its agitating disks is placed asymmetrically (i.e.away from the centre-line)in
the column.
The details of extraction equipment are available in Lo et al.(1983).A good brief
overview of extraction equipment is also available in Ruthven(1997).

8.6 SELECTION OF EXTRACTORS

The more important factors that govern the selection of an extractor are:(a)fluid properties,
(b)throughputs and phase ratio,(c)settling characteristics of the liquid-liquid dispersion,
(d)residence time in the extractor,(e)the number of theoretical stages required,(f)presence
of suspended solids,(g)available space(floor area and height),and above all (h)the cost and
maintenance of the equipment.A simple chart for preliminary selection of an extractor
(Reissinger and Schroter,1978)is shown in Figure 8.23.More detailed guidelines for extractor
selection are given by Lo et al.(1983).
A few extractors based on novel ideas have been developed in the recent years.One is
the membrane extractor in which mass transfer between the two liquid phases occurs
through a porous 'hollow-fibre'membrane that keeps them separated(see Chapter
14).Application of an electric field has proved to be effective in producing very small droplets of
a polar liquid like water or an aqueous solution to create a better dispersion.A lot of work has
been done on it as well as on mass transfer and drop coalescence in an electric field (Godfrey
and Slater,1994),although the commercial applications have been only a few as yet.
 Process
460 Chapter 8 Liquid-Liquid Extraction
YES
Minimum residence time required Centrifugal contactor
NO
Emulsifying tendency Centrifugal contactor
NO YES Reciprocating plate column
Limited headroom,or
flow rate over 400 gal/min,or
long residence time required
NO YES
Mixer-settler Mixer-settler
Small number of stages required
NO
Mechanically agitated column
YES
Column without mechanical agitation (Sieve tray,packed bed)

Figure 8.23 Simple guidelines forextractorselection.

8.7 HYDRODYNAMICS AND MASS TRANSFER IN A STIRRED

LIQUID-LIQUID DISPERSION

Despite a large number of bench scale and pilot plant experimental studies (Godfrey and
Slater, 1994),there is a dearth of generalized correlations for the design of commercial scale
extraction equipment.Also the available correlations are hardly suitable beyond the systems and
range of parameters for which these have been developed.Here we cite a few correlations
available for mixer-type extractor calculation.These are generally applicable for mixing with
four to six flat- blade turbine type impeller.

Drop-size,minimum impeller speed and power requirement

The drops in a liquid-liquid dispersion have a wide range of size distribution and several statistical
distribution functions have been used to describe drop-size distribution(Godfrey and Slater,
1994).The physical process involves breakage and coalescence of drops in an agitated liquid
mixture.Several mean values of drop-size have also been defined,the most widely used one is
the volume-to-surface diameter dʒ2,called the Sauter mean diameter.

(8.18)

The more important properties and parameters that determine the drop-size and its distribution,
 Hydrodynamics and Mass Transfer in a Stirred Liquid-Liquid Dispersion 461

impeller power requirement,rate and efficiency of mass transfer are:tank diameter (D,),impeller
type and diameter(D),volume fraction of the dispersed phase(φ),the impeller rpm(N;),the
densities,viscosities of the two liquid phases and of the mixture(Pe,Pa,Pm;Le,Ha,Hm),and the
interfacial tension(G).The interfacial area of liquid-liquid contact per unit volume of the
dispersion(a)can be expressed in terms of the Sauter mean drop diameter as

(8.19)

Sauter mean drop-size

Here are two correlations for the Sauter mean drop-size in a stirred dispersion.
Gnansundram et al.(1979)correlation:

We<10,000 (8.20a)

=0.39(We)⁰.6 , We>10,000 (8.20b)

Calabrese et al.(1984)correlation:

(8.21a)

(8.21b)

Minimum impeller speed

Depending upon the liquid properties and the fractional dispersed phase holdup,a minimum
impeller speed Nim is required to maintain a stable dispersion.The following correlation
(Skelland and Ramsey,1987)is useful to calculate this speed.

(8.22)

Power consumption

The power input to the impeller under a given set of conditions can be expressed in terms of a
dimensionless group called the power number (Po)as a function of the impeller Reynolds
number (Re;).If the impeller(turbine type)Reynolds number in a baffled vessel is above
10,000,the power number asymptotically attains a value of 5.7 (Godfrey and Slater,1994).This
relation is useful to estimate the impeller power requirement in many situations.
Po =5.7 for Re;>10,000 (8.23)
The dimensionless groups used in LLX and their physical significances are described below.

(8.24a)
462 Chapter 8 Liquid-Liquid Extraction

(8.24b)

(8.24c)

(8.24d)

(8.24e)

(8.24f)

(8.24g)

(8.24h)

The density and viscosity of the two-phase dispersion are expressed as (Godfrey and Slater,
1994)

Pm=9Pa+(1-φ)pe and
(8.25)

respectively.

EXAMPLE 8.6 (Mixer-type extractor calculation:minimum impeller speed,power and

interfacial area) Acetic acid is to be extracted from a dilute aqueous solution having
3%acid with di- iso-propyl ether as the solvent in a mixer-settler device.The impeller is of four
flat-bladed turbine type,and the mixing vessel has four vertical baffles.The aqueous feed is
the dispersed phase.
The following data and information are given:feed rate =1200 kg (3%acid);solvent rate
=4500 kg ether,practically free from the acid;pe=730 kg/m³;pa=1010
kg/m³;interfacial tension,σ=13.5 dyne/cm;μe=2.5 cP;μa =0.9 cP.
Calculate (a)the height and diameter of the tank(take H/D,=1.1),(b)the minimum impeller
speed to maintain a stable dispersion,(c)the impeller power input if the impeller speed
is maintained 20%above the minimum value,and (d)the Sauter drop diameter ds,and the
specific interfacial area.

Solution
We perform calculations on the basis of the following configuration of the mixert:impeller-flat-
blade turbine(4 blades);height/diameter ratio,H/D,=1.1;number of vertical baffles
=4;baffle width,w =D/12.

+The common practice of mixer vessel design is:H/D,=1;D/D,=V;number of baffles =4 to 6;baffle

width, w=D/12 to D/10;baffle height =at least 2D),symmetrically placed;gap between a baffle and
the tank
bottom≈D/2;gap between the edge of a baffle and the vessel wall (called 'offset')=w/6.
 Hydrodynamics and Mass Transfer in a Stirred Liquid-Liquid Dispersion 463

(a)Volumes of the phases:dispersed,Va=1200/1010=1.188 m²;ether,Ve=4500/730=6.164 m³.

Total volume of liquid in the vessel =1.188+6.164 =7.352 m³;φ=1.188/7.352 =0.1616.
Keep 20%of the vessel volume free →Vessel volume =7.352/0.8 =9.19 m³

Take H=1.1D,→volume =(π/4)(D,)²(1.1D,)=9.19 m³→D,=2.2 m ];H= 2.42 m

(b) Density of the dispersion,

Pm=PaQ+P₆(1-9)=(1010)(0.1616)+(730)(1-0.1616)=775.2 kg/m³
Viscosity of the dispersion [Eq.(8.25)],

Interfacial tension,σ =13.5 dyne/cm =0.0135 N/m

Take impeller diameter,D;=0.5D, → D;=(0.5)(2.2)=1.1 m

Minimum impeller speed for maintaining the dispersion is given by Eq.(8.22),i.e.

(c) Use an impeller speed 20%excess of the minimum speed,i.e.

N₁=(0.844)(1.2)=1.013 rps =60.8 rpm

Since the impeller Reynolds number is larger than 10,000,we use the asymptotic
relation, Eq.(8.23).

→ Power input,P =7.4 kW(9.92 hp)

Power density =(7.4 kW)/(7.352 m³dispersion)=1kW/m³

(d) Use the Gnansundram et al.(1979)correlation,Eq.(8.20).
464 Chapter 8 Liquid-Liquid Extraction

→ d₃₂=(4.68×10⁴)(1.1)m =0.5mm
Let us also calculate the Sauter mean drop diameter using the Calabrese et al.correlation,
Eq.(8.21).

d₃₂=7.15×10-⁵m=0.0715 mm
The second correlation gives a much smaller value of the Sauter mean drop diameter.

Correlations for mass transfer coefficients

The dispersed phase mass transfer coefficient can be approximately calculated from the
following relation (Treybal,1963)assuming the drops to be rigid.A drop can generally be
considered 'rigid' if it is smaller than about 1mm and the interfacial tension is more than 15
dyne/cm.

(8.26)

where(Sha)is the dispersed phase Sherwood number,ka is the dispersed phase mass
transfer coefficient,and Da is the diffusivity of the solute in the dispersed liquid.More
correlations for the dispersed phase mass transfer coefficient in an agitated liquid-liquid
dispersion have been suggested by Skelland and Xien(1990).
The continuous phase mass transfer coefficient can be calculated from the Skelland
and Moeti(1990)correlation.

(8.27)

If the distribution of the solute in the two phases follows a linear relation,x=m'y*,the
overall mass transfer coefficient based on the dispersed force concentration difference is
given by

(8.28)
 Hydrodynamics and Mass Transfer in a Stirred Liquid-Liquid Dispersion 465

The phenomenon of mass transfer between a drop

(or a bubble)and a surrounding liquid depends upon
a
number of physical factors,the two important factors
being internal circulation and Marangoni effect.Rela-
tive motion between a drop(or a bubble)and the
con- tinuous phase creates shear stress at the
fluid-fluid interface which,in turn,gives rise to a
circulating motion within the drop.This is called
internal circula- tion(Figure 8.24).This
Figure 8.24 Intemal circulation in a moving drop.
phenomenon,which becomes more prominent in a
large drop,greatly increases the drop-side mass
transfer coefficient.However,the
interfacial shear may not be sufficient to create internal circulation in a small drop.A
small drop behaves more like a 'rigid sphere'and mass transfer within it occurs essentially by
molecular diffusion.
Interfacial tension between two fluids is influenced by the presence of a dissolved solute.
The solute concentration gradient near the interface that occurs during mass transfer creates
a gradient of interfacial tension along the surface of a drop or bubble.This causes interfacial
motion and even interfacial turbulence,influencing the rate of mass transfer as well as drop
coalescence. The phenomenon is called Marangoni effect which has been discussed at length in
the available literature (see,for example,Godfrey and Slater,1994;Thorton,1992).

Mass transfer in a batch agitated vessel

Let us consider a batch agitated vessel having a mass Ma of the dispersed and M.of the
continuous phase (assumed immiscible).The initial mass fraction of the solute in the dispersed
phase is x₁and the solvent is 'pure'.Transfer of the solute occurs from the dispersed to
the continuous phase.The equilibrium relation is lin ear,x=m'y*,where y*=mass fraction
solute in the continuous phase in equilibrium with a mass fraction of x in the dispersed
phase.It is further assumed that the solute concentration is low and the amounts of the
individual phases remain practically constant.If the overall volumetric mass transfer
coefficient is known,it is possible to calculate the mass transfer efficiency of the vessel.
The solute concentrations in the phases (x and y)at any time are related by the mass
balance equation.

M₄x₁=M₄x+Mcy → (8.29)
The flux of the solute(kg/m²s)is given by
N²=KoaPa(x-x*); where x*=m'y=m'(x₁-x)(Mg/M-) (8.30)
The instantaneous rate of transport of the solute from the dispersed phase is

(8.31)
→

where V=Va+V₆=volume of dispersion,and φ=V₁/V

466 Chapter 8 Liquid-Liquid Extraction

Here Va and Ve are the volumes of the dispersed and the continuous phases
respectively; V is the total volume of the dispersion;and φ is the volume fraction of the
dispersed phase.
The time required for a change of the solute concentration from x₁to xz in the
dispersed phase can be obtained by integrating Eq.(8.31).

(8.32)

EXAMPLE 8.7(Calculation of the mass transfer coeficient and the batch contact time) Consider
Example 8.6.If the distribution coefficient is m'=3.77,calculate(a)the dispersed and the
continuous phase mass transfer coefficients,and(b)the contact time required to attain
95% of the ultimate concentration of the solute in the dispersed phase.

Solution
(a) We shall first obtain the diffusivities of acetic acid in water and in the
ether. Diffusivity in water(dispersed phase),

D₄=1.2×10-⁹m²/s(literature value)
Let us use the Wilke-Chang equation,Eq.(2.66),to estimate the diffusivity of acetic
acid in the solvent.
The following values are used:molar volume of the solute,v =0.0641 m³/kmol;mol.wt.
of the solvent =102;viscosity of the solvent,μ=2.5×10³kg/m.s,T=298 K;association
factor =1.0 for the ether.
Putting the values in the Wilke-Chang equation,diffusivity of the solute in the continuous
phase,

D=7.34×10-10m²s
Average drop-size,ds₂=5×10-⁴m(see Example 8.6)
Dispersed phase mass transfer coefficient from Eq.(8.26):

The following values of the different dimensionless groups are calculated for estimation of the
continuous phase mass transfer coefficient from Eq.(8.27).Take impeller speed,N;=1.013
rps; other parameters as in Example 8.6.
Sc=4.66×10³; (Fr)=0.11; Eo =0.183; (Re)=3.58×10
(Sh)=(1.237×10-⁵(4.66×10³)¹³(0.115)⁵¹12(0.183)⁵4(0.1616)-2

kc= 1.35×10-2 m
 Extraction Equipment Design 467

Overall coefficient,dispersed phase basis

→ 577×10-5m/s

(b) At equilibrium,the material balance equation,Eq.(8.29),becomes

M₁X₁=M₄Xeq+M-Yeg Where xeq =m'yeg
Given:Ma=1200 kg;Mc=4500 kg(both are assumed to remain constant since the
concentrations are low);x₁=0.03;m¹=3.77.From Eq.(8.29)at equilibrium,
→ (1200)(0.03)=(1200)(xeg)+(4500)(xeg/3.77) → xeq =0.01504
Final concentration of the solute in the dispersed phase

x₂=Xg+(x₁-Xeg)(1-0.95)=0.01504 +(0.03-0.01504)(1-0.95)=0.01579
Putting the values of the different quantities (V=7.352 m³,a =1940 m²/m³)in Eq.(8.32),

t = 8s

It appears that the mass transfer process in an agitated contactor is very fast.However,the actual
time required for achieving a given fractional transport of the solute will definitely be larger than
the theoretically calculated value because of many reasons including interfacial resistance to
mass transfer.

8.8 EXTRACTION EQUIPMENT DESIGN

The design of an extractor primarily involves the determination of its physical dimensions
(diameter and height)as well as the dimensions and size of the internals (e.g.agitator size and
rpm,packing size,size and rpm of the rotor,etc.depending upon the type of the extractor).The
height of a continuous contact equipment like a packed or spray tower is expressed as the
product of NTU and HTU.That of a perforated tray column,an RDC,a Scheibel extractor or
one of this type is expressed as the product of HETS+(height equivalent to a theoretical
stage) or HETP and the number of theoretical stages.
It is not difficult to determine the number of theoretical stages required to achieve a specified
degree of separation of a liquid mixture by solvent extraction.The examples solved in this chapter
illustrate the procedures.However,there is no well-defined procedure in open literature for
the determination of the height of a theoretical stage.A large number of correlations have
been

+The term HETS (rather than HETP)is more frequently used to indicate the mass transfer efficiency of
an extractor unit,although both have the same meaning.
468 Chapter 8 Liquid-Liquid Extraction

suggested covering different aspects of drop-size distribution,drop breakage and coalescence,

impeller power consumption,mass transfer coefficient,effect of axial dispersion,etc.(Treybal,
1963;Laddha and Degaleesan,1978;Lo et al.,1983;Thornton,1992;Godfrey and Slater,1994).
These correlations and theoretical analyses help a lot for better understanding of the phenomenon
of liquid extraction but are only of limited utility so far as the design of a real-life equipment
is concerned.Workable design of extraction equipment is still largely based on pilot plant tests
and use of tested scale-up rules (Schweitzer,1997).Pilot tests are carried out in columns of a
few inches diameter.A useful guide to evaluation of the performance and efficiency of
extraction columns has been suggested recently by Glatz and Parker (2004).
Unagitated columns like the spray tower,packed tower or the sieve tray column
accommodate only a few theoretical stages.Spray towers are suitable for applications such
as washing or neutralization of a liquid stream.Considerable 'backmixing'occurs in a spray
tower.The diameter of an extractor is determined from flooding considerations.Both random
and structured packings are used in a packed extraction tower as for gas absorption or
distillation.The continuous phase should preferably wet the packing.The HETS varies from 2
to 7 ft for a random packing,and 1 to 5 ft for structured packing s.Ranges of
diameter,throughputs and HETS of a few commercial extractors are given in Table 8.4.

Table 8.4 Maximum throughput and size of diferent extractors (Reissingerand Schroter,1978)+

Type Maximum Maximum Maximum HETS

load,m³/m².h column dia,m throughput.m³/h m

Scheibel extractor <10 1.5 25 0.1-0.25

RDC 40 8.0 2000 0.3-0.70
ARDC 20 4.0 250
Lurgi tower 30 8.0 1500
Kuhni extracto 50 3.0 350 0.1-0.25
Karr extractor 80-100 1.5 <180 0.15-0.3
The above data apply for the following ranges of the physical properties of the liquids:interfacial tension:30-40 dyne/cm
viscosity:near that of water;phase input ratio:1:1,vv;density dfference:0.06 g/cm³ .

NOTATIONS

A,B,C :carrier,solvent,and solute respectively.

a :specific interfacial area of contact,m²/m³
d₃₂ :‘volume surface mean'or‘Sauter mean'drop diameter,m
D,D; :diameter(t =tank,i =impeller),m
F,E,R,S :quantity (or flow rate)of feed,extract,raffinate and solvent respectively,kg or kg/h
HETS :height equivalent to a theoretical stage
ke,ka :individual mass transfer coefficient (c =continuous,d =dispersed),m/s
Koa :overall mass transfer coefficient,dispersed phase basis,m/s
m' :solute partition coefficient given by x =m'y*
 Short and Multiple Choice Questions 469

Ma,Mc,M:amount of dispersed phase,continuous phase,or mixture of two phases,kg or kg/h

N; :impeller speed,rpm or rps
P :power input,kW/m³
Sm :minimum solvent rate,kg/h
x,y :mass fractions of a component in the raffinate phase and the extract phase
respectively
X,Y :mass fractions of the solute on solvent-free basis,see Section 8.2.3
z,Z :mass fractions of the solvent on 'solvent-free'basis,see Section 8.2.3
βcA :separation factor of C,Eq.(8.1)
μa,μe,μm :viscosity of the dispersed and continuous phases,and of the mixture respectively,
kg/m.s
Pa,Pe,Pm:density of the dispersed and continuous phases and of the mixture respectively,
kg/m³
φ :fractional holdup of the dispersed phase,Va/V=dispersed phase volume/dispersion
volume
△ :a fictitious stream and its mass,Eq.(8.15)

SHORT AND MULTIPLE CHOICE QUESTIONS

1.Consider distribution of the solute C in two partially miscible solvents A(carrier)and

B(solvent).What is the selectivity of separation at the plait point?
(i)1.0 (ii)very large (iii)zero
2.One hundred kilograms of a 50%solution of C in A(carrier)is equilibriated with 70 kg
of solvent B containing 2%of C.At equilibrium,the raffinate phase has a mass of
80 kg and has 52%A and 8%B in it.What is the selectivity or separation factor of
C? (i)0.15 (ii)3.0 (ii)10.2
3.Which of the following is a realistic value of the stage efficiency of a mixer of
good design?
(i)100% (ii)10% (iii)85%
4.Three solvents have been identified for the extraction of a solute from an aqueous
solution.The interfacial tension values in N/m corresponding to the three solvents are:
(i)σ₁=0.003 (ii)σ₂=0.01 (iii)o₃=0.05
Which solvent appears to be suitable?
5.If the interfacial tension of a carrier-solvent pair is very small,which of the
following problems may appear?
(i) Dispersion of the solvent in the carrier becomes more power-
consuming. (ii)Phase separation of the liquid-liquid dispersion becomes
difficult.
(ii) Interfacial mass transfer resistance becomes large.
470 Chapter 8 Liquid-Liquid Extraction

6. Which of the following changes causes a Type-II liquid-liquid system to become a Type-I
System?
(i) An increase in temperature
(ii) An increase in pressure
(ii) Temperature increased to the critical solution temperature of the solvent-solute pair.
7.While finding out the minimum solvent rate Sm for a countercurrent extraction cascade
without reflux it was found that the line RvS and the tie line through the feed point
F were parallel (so that the point △,lies at infinity).If it is so,which of the
following
relations is correct?
(i)Sm=RN (ii)(xc)r=(yc)E₁ (ii)xp/xy=ys/y₁ (iv)xs-y₁=xp-xv
(v)F=E₁
8. The coefficient of distribution of the solute C between two mutually immiscible liquids
A(carrier)and B(solvent)is K=yc/xc=0.75.Draw the equilibrium curve using the
right triangular coordinates.
9. For the above case,what is the slope of the tie line if the mass fraction of the solute in
the solvent phase is yc =0.1?
(i)0 (ii)0.0984 (iii)0.037
10. An ideal countercurrent mixer-settler cascade containing six stages removes 95%of the
solute from the feed.One of the mixers has developed a mechanical problem and
is bypassed.For the same percentage removal of the solute from the feed,the solvent
rate should be
(i)increased (ii)decreased (ii)may be kept unchanged.
11.Equilibrium data for the water(A)-acetone(C)-chloroform(B)system are given in
Problem 8.2.How much chloroform should be added to 1 kg of an aqueous
solution containing 20%acetone so that after equilibriation,the acetone concentration in
the non- aqueous phase becomes 10%?
(i)0.829 (ii)0.95 (iii)1.17]
12.If extraction of the solute C in the ternary system A-B-C is conducted at a considerably
elevated temperature,the rate of mass transfer will definitely increase.The power
consumption is also less because the viscosities of the liquids decrease at an increased
temperature.In this context,is it advisable to carry out extraction at an elevated
temperature?Discuss.
13. The following mass and solute concentrations are given for an ideal single-stage
extraction system:F=500 kg;xp=0.4;S=400 kg;xs=0.The amount and
concentration of the extract are E=550 kg,and ye=0.33.What is the distribution
coefficient K of the solute at the condition of the mixer-settler?
(i)0.523 (ii)2.15 (iii)6.23
14.What kind of solvent is suitable for the following separations?Answer using Table
8.2. Extraction of:
(i) pyridine/ethyl alcohol/propionic acid from an aqueous solution
(ii) BTX from reformer products
 Short and Multiple Choice Questions 471

(iii) o-nitrophenol from a dilute aqueous solution

(iv) phosphoric acid from the crude acid obtained by the 'wet process'.
15.For what kind of liquid-liquid system is the use of extract reflux more convenient?
(i)Type I system (ii)Type Ⅱ (iii)Both of these
16. What should generally be the minimum fractional density difference between the
carrier (A)and the solvent(B)so that phase separation may not be very difficult?
(i)20% (i(ii)5% (iii)1%
17.Can two tie lines intersect within the two-phase region of an LLE diagram?
Explain qualitatively.
18. The solvent(B)in liquid extraction has the following as its analogue in
distillation. (i)Enthalpy
(ii) The more volatile component
(iii) The reflux stream
19.In liquid-liquid equilibrium studies,a system is called Type-II if
(i) the A-C pair is immiscible
(ii) the B-C and A-B pairs are partly miscible
(iii)the B-C pair is completely miscible.
20.What would be the effects of the following factors on flooding of an RDC?
(i) The increased flow rate of the lighter continuous phase
(ii) The larger density difference of the phases
(ii) The larger interfacial tension between the phases
(iv)The higher rotor speed
21.Which of the following factors favour formation of a stable and more
effective dispersion?
(i) Low interfacial tension
(ii) Large density difference of the phases
(ii)Low viscosity of the dispersed phase
(iv) Higher impeller rpm
22. What is Marangoni effect?Does its effectiveness depend upon the direction of mass
transfer?
23. Develop Eq.(8.19).
24. In which of the following cases is the separation of the solute(C)from the carrier
(A) using solvent (B)impossible?
(i)A,B,and C are completely miscible
(ii)A-C and B-C pairs are completely miscible
(ii)A-B is partly miscible
25. In a liquid-liquid dispersion,the volume fraction of the continuous phase is
0.7.The Sauter mean drop diameter is 500 μm.What is the specific interfacial area
of contact in m²/m³?
(i)3600 (ii)1250 (iii)10
472 Chapter 8 Liquid-Liquid Extraction

26. The diameter of an extractor column for pilot test is generally taken in the
range: (i)1-6 mm (ii)3-15 cm (iii)0.3-1.0 m
27. Which of the following is a likely value of the HETS of an RDC?
(i)2 m (ii)0.4 m (iii)0.1 m
28. Give a few examples of applications/potential applications of solvent extraction
for wastewater treatment.
29. An unstable product is to be recovered by extraction,and the contact time in
the extractor should not be more than 30 s.The interfacial tension for the system is
low. What kind of extractor appears to be suitable?
(i)Karr extractor (ii)Scheibel column (iii)Podbielniak extractor

PROBLEMS
8.1(Extraction in an immiscible system)¹ A stream of wastewater containing 2%benzoic
acid is to be extracted with benzene at a rate of 2000 kg/h in order to remove 98%of
the solute.If water and benzene are assumed to be mutually immiscible and the
distribution coefficient is K=w/w,=1.707 at the given temperature (where w,and w,
are the mass fractions of the solute in water and benzene phases respectively),calculate
the following:
(a) The minimum rate of benzene required for countercurrent separation of the
mixture.
(b) The number of stages required if 1.3 times the minimum solvent is used.
(c) The fraction of the solute removed if the same amount of solvent is used for
the separation using a four-stage countercurrent cascade.
(d) The amount of solvent required if the separation of 98%is done in a five-
stage countercurrent unit.
(e) The total amount of solvent required for the separation in a four-stage cross-
current device if the same amount of solvent is fed to each stage.
8.2 (Single stage extraction)³ Five hundred kilograms of an aqucous feed containing
50 mass%acetone is contacted with a solvent containing 98%chloroform and
2% acetone.The mass ratio of the feed to the solvent is 1.1.Calculate the mass
and composition of the extract and also the fraction of acetone in the feed
extracted.The operation is carried out at 25°C and the equilibrium and tie line data
are given below (Wankat,1988).
Aqueous phase(mass fraction) Chloroform phase(mass fraction)
Water Chloroform Acetone Water Chloroform Acetone
XA Xg Xc YA YB Yc
0.8297 0.0123 0.158 0.013 0.70 0.287
0.7311 0.0129 0.256 0.022 0.557 0.421
0.6229 0.0171 0.36 0.044 0.429 0.527
0.456 0.051 0.493 0.103 0.284 0.613
0.345 0.098 0.557 0.186 0.20 0.61
 Problems 473

8.3 (Cross-curremt extraction,partially miscible system,equal amount of solvent to each

stage)²Acetone is to be extracted from an aqueous solution(500 kg/h,50 mass
% acetone)using TCA(trichloroethane,it is carcinogenic!)in a three-stage cross-
current cascade.Two hundred kilograms of solvent (98%TCA,2%acetone)is
added to each stage.Given the following LLE data,calculate the flow rate of the
raffinate and the
fraction of feed acetone removed in each stage.
Extract arm(mass fraction) Raffinate arm(mass fraction
Yc VA YB Xc XA XB
0.60 0.13 0.27 0.55 0.35 0.10
0.50 0.04 0.46 0.50 0.43 0.07
0.40 0.03 0.57 0.40 0.57 0.03
0.30 0.02 0.68 0.30 0.68 0.02
0.20 0.015 0.785 0.20 0.79 0.01
0.10 0.01 0.89 0.10 0.895 0.005

Tie-linedata
Extract (mass fraction acetone) Raffinate(mass fraction acetone)
0.18
0.12
0.40 0.29
0.56 0.44

8.4(Cross-curremt extraction,partially miscible system,equal amount of solvent to each

stage)³As an alternative strategy of removing acetone from the feed in Problem
8.3 supplied at the rate of 1000 kg/h,it was decided to use a four-stage cross-
current cascade with different amounts of the solvent (TCA)—250,300,350 and 400
kg—in the successive stages.Since the first stage received the fresh feed,less
solvent was supplied to it.Calculate the total amount of the solute removed from
the feed.The equilibrium data given in Problem 8.3 are applicable.Assume that there is
no acetone in the solvent supplied.(Courtesy:Dr.Basab Chaudhuri)
8.5(Optimum solvent rate for an N-stage cross-current extractor)³Consider an N-stage
cross-current extraction unit shown in Figure 8.10.A solution of C in the carrier liquid
A(Xo kg solute per kg A)is to be treated at a rate ofF kg/h.Pure solvent B is supplied
to the stages at a rate S,kg/h to the nth stage.Extract from the nth stage leaves at
a concentration of Y,kg C per kg B.The equilibrium relation is linear
[Y;=ψ(X;)=αX;]. The carrier liquid (A)and the solvent(B)are virtually immiscible and
the stages are ideal. If c₁(Rs per kg)is the price of the recovered solute and cz is
the processing cost (Rs per kg solvent),it is required to determine the optimum rate
of solvent flow to the nth stage and the maximum profit.For the sake of
simplicity,work it out for a four-stage cascade.(Note that here X and Y have meanings
as defined in this particular problem and should not be confused with the
meanings of these notations used for partially miscible systems.)
8.6(Countercurrent extraction,minimum solvent rate,number of stages)²An aqueous
solution of acetic acid(35%acid,rest water)is to be extracted with pure'di-iso-
propyl ether in a countercurrent cascade at a rate of 2000 kg/h.A solvent rate of
2970 kg/h
474 Chapter 8 Liquid-Liquid Extraction

is suggested.The raffinate stream must not contain more than 10%of acid in it.The
ternary phase equilibrium data are available under Example 8.5.Determine the number
of ideal stages required.Also determine the minimum solvent rate for the job.
8.7(Number of stages;minimum solvent rate)³ An aqueous solution of acetic acid (35%
acid;1000 kg/h)is to be extracted with pure'MIBK(B)at 25°C supplied at a rate
of 1300 kg/h.The raffinate may contain 3%acid(C).Determine the number of ideal
stages and also the minimum solvent rate required to perform the separation in a
countercurrent cascade.The LLE data at 25°℃ are given below.
Raffinate(Aqueous phase Extract (MIBK phase)
XA XB Xc YA YB yc
0.9845 0.0155 0.0 0.0212 0.9788 0.0
0.9545 0.017 0.0285 0.028 0.9533 0.0187
0.858 0.025 0.117 0.054 0.857 0.089
0.757 0.038 0.205 0.092 0.735 0.173
0.678 0.06 0.262 0.145 0.609 0.246
0.550 0.122 0.328 0.220 0.472 0.308
0.429 0.225 0.346 0.310 0.354 0.336
8.8 (Multistage countercurrent extraction)³ A feed of one thousand kilograms aqueous
solution of pyridine per hour(50%by mass)is to be extracted with pure benzene to
reduce the solute content in the raffinate to 2%.Determine the number of ideal stages
required if the solvent rate is 1.3 times the minimum.
Equilibrium datu
Water layer
Benzene layer
Pyridine,mas Benzene,mass% Pyridine,mass% Benzene,mass%
s% 1.17
0.0 3.28 94.54
3.55
0.0 9.75 87.46
7.39
0.0 18.35 79.49
13.46
0.15 71.31
22.78 26.99
0.25 31.42 66.46
32.15
0.44 34.32 64.48
42.47
2.38 36.85 59.35
48.87
3.99 39.45 56.43
49.82
4.28 39.27 55.72
56.05
19.56 48.39 40.05
8.9(Janecke diagram)³ The mutual solubility and the tie-line data for the MEK(A)-
ethylene glycol(C)-water(B)system at 30°℃ are given below:
Extract (MEK phase) Raffinate(water)
YA VB Yc XA XB Xc
0.884 0.111 0.005 0.208 0.697 0.095
0.871 0.112 0.017 0.21 0.656 0.134
0.849 0.113 0.038 0.221 0.583 0.196
0.827 0.116 0.057 0.236 0.524 0.240
0.806 0.118 0.076 0.261 0.461 0.278
0.50 0.205 0.295 Plait point
 References 475

(a)Prepare the maloney-Schubert (or Janecke)diagram for the above system.Show the
tie lines.(b)A solution of ethylene glycol in water (30%glycol,70%water)is extracted
with MEK at arate of 500 kg/h.The MEK flow rate is also 500 kg/h.Determine the flow
rates and compositions of the raffinate and the extract phases using the Janecke
diagram.
8.10(Time of contact in a stirred liquid-liquid extractor)³For the stirred liquid-liquid
contacting described in Example 8.7,calculate the time required for achieving
99%of the equilibrium transfer of acetic acid from the dispersed aqueous
phase.All other parameters remain the same.
8.11(Minimum impeller speed and power in an agitated extractor)³Benzoic acid is to be
extracted from an aqueous solution using toluene as the solvent.A batch extractor
is charged with 1000 kg of the feed containing 3.5%benzoic acid and 2500 kg
toluene. The mixing vessel has a four-blade turbine impeller and four vertical
baffles.Assuming the phases to be virtually immiscible,calculate (a)the minimum
impeller speed to have a stable dispersion,(b)the impeller power if its speed is
25%above the minimum, (c)the Sauter mean drop size,and (d)the contact time
required to attain 98%of the equilibrium concentration in the continuous phase.
The following data and information are given:pa=998 kg/m³;pe =870 kg/m³;
μa=0.9cP;μ=0.6cP;σ=25 dyne/cm;distribution coefficient,m'=10.1 m³raffinate/m³
extract.The organic phase is continuous.
8.12(Murphree efficiency of a stirred extractor)³A continuously operated agitated mixing
vessel of total liquid volume V,receives a feed(dispersed phase)at a rate of Qa
m³/s. If the overall volumetric mass transfer coefficient based on the dispersed
phase concentration is Koaa,show that the Murphree dispersed phase efficiency of the
mixer is given by

C₄=dispersed phase concentration.

REFERENCES

Cusack,R.W.,P.Fremeaux,and DJ.Glatz,‘A fresh look at liquid-liquid extraction',Chem.

Eng.,Feb.1991,66-76;March 1991,132-138;April 1991,112-120.
Cusack,R.W.,and DJ.Glatz,'Apply liquid-liquid extraction to today's
problems',Chem.Eng., July 1996,91-100.
Cusack,R.W.,'Designing a separation process',Chem.Eng.,May 1998,128-136.
Cusack,R.W.,'Pilot plants confirm process validity',Chem Eng.,June 1998,102-109.
Gani,R.et al.,‘A modern approach to solvent selection',Chem.Eng.,March 2006,30-42.
А16C hanter 8 Liauid=L.iauid Extraction

Glatz, D. J., and W. Parker, ‘Enriching liquid-liquid extracton’, Chem. Eng. Progr., Nov 2004,
44-48.
Godfгеу, ].С., and М.J. Slater, Liquid-liquid Exiraction Equipment, John Wiley, New York,
1994.
Hauon, Т.A., Liquid-hquid extraction of antibiotics’, in Comprehensive Biotechnology, Vol.
2, М. Моо-Young (Ed.), Pergamon Press, 1985.
Наиег, Е., and R. Marг, Liquid extraction in biotechnology’, Chem. Enв . Tech., 63(1994)
809-816.
Humphrey, J.L., ).А. Rocha, and J.R. Fair, ‘The essentials of extraction’, Chem Eng., Sept.
1984, 76-95.
Laddha, G.S., and T.E. Degaleesan, Transport Phenomena in Liquid Extraciion, Tata McGraw-
Hilі, New Delhi, 1978.

Lо, Т.С., М.Н.I. Baird, and C. Hansen (Eds.), Handbook of Solvent Extraction, John Wiley,
New ТогК . ТОЯЗ,
Lucan, A.D. (Ed.), Моdern Petroleum Technology, John Wiley, New York, 2000.
Rao, К.S.M.S., M.R. Guin, and P. Todd, ‘Recent developments in aqueous two-phase
extraction in bioprocessing’, Sep. Pur. Methods, 27(1998) 1-49.
Reissinger, K.Н., and J. Schroter, ’Selection critena for lquid-lquid extraction’, Chem
Eпв-, 6(1978) 109-118.
Ruthven, R.D., Encyclopedia of Separation Technology, John Wiley, New York, 1997.
Schweitzer, P.A., Handbook of Separation Techniques for Chemical Engineers, McGraw-Hill,
New York, 1997.
Seader, J.D., and E.J. Henley, Separation Process Principles, John Wiley, New York, 1998.
Sherwood, T.K., and R.L. Pigford, Absorpiion and Extraction, McGraw-Hill, New York,
1952, 402—419.
Skelland, A.H.P., and Hu Xien, ’Dispersed-phase mass transfer in agitated liquid-liquid systems’,
lnd. Eng. Chem. Res., 29(1990) 415-420.

Skelland, А.Н.Р., аnd L.Т. Moeti, ‘Mechanism of continuous-phase mass transfer in agitated
liquid-liquid systems’, Ind. Eng. Cnem. Res., 29(1990) 2258-2267.
Thornton,l.D., Science and Praciice of Liquid-liquid Extraction, Claredon Press, Oxford, 1992.
Todd, D.В., *lmproving performance of centrifugal extractors’, Chem. Eng., July 1972,
152-158.
Treybal, R.E., Liquid Extraction, 2nd ed., McGraw-Hil, New York, 1963.
Wankat, PC., Equilbrium Siaged Separations, Elsevier, New York, 1988.
 Solid-Liquid Extraction

Solid-liquid extraction is the process of separation of soluble constituents of a solid material

using a suitable solvent.Usually the soluble material is the target product,and the 'inert'solid
residue is a by-product or just a solid waste(for example,in extraction of oil from oil
seeds,the oil is the product,and the solid residue or cake is a by-product).In some cases,the
undesirable soluble materials are removed from the solid by using a solvent and the extracted
solid is the product (for example,extraction of de-fatted soy flour using aqueous ethanol as the
solvent for removing sugars and some non-protein solids;the solid residue called‘soy
protein concentrate'is the product;the solutes extracted may be recovered as by-
products).The overall process of liquid- solid extraction basically involves four steps:
(i)intimate contact between the solid feed with the solvent;(ii)separation of the solution(or
extract)from the exhausted solid;(iii)separation of the solvent (and the entrained solid,if
any)from the extract followed by purification of the product; (iv)recovery of the solvent from
the moist solid(by squeezing/pressing and drying to get a dry cake).Solid-liquid extraction is
also called'leaching',although here we shall use the term leaching in a slightly restrictive
sense.This operation is different from'dissolution'in the sense that in dissolution almost the
entire solid gets into solution leaving very little or no 'inerts'behind. But in solid-liquid
extraction or in 'leaching',a substantial part of the solid does not dissolve and the soluble
matters diffuse out through the solid during solid-liquid contact.

There are many examples of solid-liquid extraction in chemical and allied industries.Veg-
etable oils are frequently extracted from oil seeds by a suitable solvent.Sometimes a part of the
oil is removed from the seeds by pressing,and the residual oil in the 'cake'is recovered by
extraction.Hexane is the most popular solvent for oil extraction because (i)it can be easily
removed from the extract by 'flashing',(ii)it is non-toxic,(iii)it is reasonably cheap,and
(iv)it is miscible with vegetable oils in all proportions.Use of chlorinated solvents (e.g.trichlo-
roethylene)has been discontinued mainly because these are toxic and carcinogenic.The solvent
hexane is separated from the extract and the oil is subjected to the refining process.The
process of 'solvent extraction'of oil seeds is schematically shown in Figure 9.1.Solid-liquid
extraction is widely used in the food industries and a detailed account of it has been given by
Schwartzberg (1980).
477
 Hulls
Seed
Decortication/dehulling
478 Chapter 9 Solid-Liquid Extraction Kernel Steaming(optional)
to Cleaning
5-8%moisture
and drying to 5-8%moisture
(removal of the hard shell, necessary for low-oil, hard kernels
if any,and the skin)
Direct
extraction Solvent
Oil meal
(30-35%) Extraction Cake Pressing (A screw is common)
solvent (continuous belt,horizontal Pelletization/ flaking
basket,Hildebrand or Bollman extractor is commonly used)

Desolventizer
Flashing Oil Steam stripping Oil for refining
Oil and Solvent
Meal
Steam Solvent Solvent
Meal (for
animal feed)
Solvent recycled

Figure 9.1 Solvent extraction of oilseeds.

9.1 CLASSIFICATION OF SOLID-LIQUID EXTRACTION

SYSTEMS

Solid-liquid extraction may involve different physico-chemical mechanisms depending upon the
characteristics of the solid (particle size,porosity or compactness,reactivity,solute content,etc.)
and of the solvent.If the particle size of the solid is not small,there may be substantial diffusional
resistance to transport of the solute within the solid.Whenever possible,the solid is broken down
or disintegrated into particles or flakes (in the case of oil seeds,for example)to enhance the rate
of extraction.Sometimes an acidic,alkaline or a complexing solution may be used for
solubilization of the target substances.Rickles(1965)classified commercial solid -liquid
extraction systems into the following categories.

Diffusional extraction
Almost the entire mass transfer resistance lies in the solid phase in such a case and hence the
name diffusional extraction.An example of a system of this category is extraction of sugar from
sugar beet.Sugar beets are cut into small pieces called ‘cossettes'which are treated with warm
water (70-75°C).Diffusion within the solid occurs through denatured cell walls and through
the intersticial liquid.The solvent (water)also diffuses in the opposite direction,thus diluting
the solute within the cells.The rate and time of extraction depend mainly upon the thickness of
the pieces,the 'effective diffusivity'of the solute in the solid,and the concentration of sugar in
the extracting liquor.Many other solid-liquid extraction systems in which the extraction rate
is controlled by solid-phase diffusion of the solute,are encountered in food processing
industries (Schwartzberg,1980).
 Classification of Solid-Liquid Extraction Systems 479

Washing extraction
If the solid particle size is pretty small,the solid-phase diffusional resistance becomes negligibly
small.In such a case,extraction virtually becomes a process of washing the solid with the solvent.
An example is extraction of oil from 'flakes'of oil seeds.Flakes are pretty thin(fraction of a
millimetre).Further,during the flaking process much of the cells are ruptured and the diffusional
resistance for transport of the solute within the solid becomes small.In washing extraction,a
substantial amount of solvent is retained in the slurry after washing.The solute concentration in
the liquid retained in the slurry is nearly the same as that in the bulk liquid.
Leaching
This involves dissolution of one or more substances from solid particles accompanied
by chemical reaction(s).An acid,alkali or the solution of a complexing chemical is commonly
used for solubilizing the target materials.Leaching of ores (oxides,carbonates,sulphides,etc.)is a
major step in hydrometallurgy.Leaching of copper minerals by sulphuric acid or an
ammoniacal solution,leaching of gold from its ores by sodium cyanide solution are typical
examples (use of cyanides is less common nowadays because it is a severe pollutant).Low-grade
ores are sometimes leached under drastic conditions.For example,a recently developed
method of leaching low- grade nickel ore,called nickel laterite,uses sulphuric acid at 250°
℃ and 650 psi pressure to dissolve the nickel (Hairston,1999);cobalt is the by-product.An
extraction vessel with acid resistant bricks or with titanium cladding may be used under
such an extreme condition.
‘Bioleaching'is a novel technique (Ciminelli et al.,2001)of dissolving ores,particularly the
low-grade ones,carried out at near ambient condition without the use of chemical agents.
Bacterial species like Thiobacillus Ferrooxidans and thermiphilic species such as
Sulphobacillum, Acidianus,and Sulpholobus convert ores,particularly sulphide ores,to
soluble sulphates.The process,though slow,is non-polluting since no sulphur dioxide is emitted
unlike the conventional roasting process.Bioleaching is in commercial use for extraction of
copper(about one-fifth of global extraction of copper is done by
bioleaching),gold,zinc,nickel,etc.

Chemical extraction
This is functionally similar to the leaching operation but usually refers to recovering solutes
from solids of organic nature.Recovery of gelatin from animal bones using an alkaline solution
is an example of chemical extraction.
A few more commercially important solid-liquid extraction systems of the above categories
are described in Table 9.1.

Table 9.1 Commercialy importantiquid-solid extraction systems (Rickles,1965;Schwatzberg,1980)

Solute(s Feed solid Solvent/Product

(a)Diffusional extractio
Soluble coffee Coffee beans Water
Fish oils Fish meal,whole fish Alcohols,hexane,etc.to produce fish
proteir concentrate

(Contd.)
 Classification of Solid-Liquid Extraction Systems 479
Sugal Sugar beets Water,to produce suga
Water Fruits Sugar solution—for'osmotic dehydration'of fruits

(Contd.)
480 Chapter 9 Solid-Liquid Extraction

Table 9.1 Commercially important liquid-solid extraction systems (Rickles,1965;Schwartzberg,1980)[Contd.]

Solute(s Feed solid Solvent/Product

(b)Washing extraction
Vegetable oils Oilseeds Hexane,hydrocarbons
Flavours/Odours Flowers Ethanol
Sugar Sugarcane Water
Vanilla Vanilla beans Ethanol(35%)-Water(65%
(c)Leaching
Phosphorc acid Phosphate rock Sulphuric acid
Sodium aluminate Bauxite Caustic solution
Gold Gold ore Sodium cyanide
Copper Copper ore Sulphuric acid,complexing reagents
(d)Chemical extraction
Gelatin Bones and skins Aqueous solution (pH 3 to 4)
Lignins Wood chips NaOH solution,sulphide or sulphite
odine Seaweeds Sulphuric acid
Pectin Apple pumace (pulp Dilute acid

9.2 THE RATE OF SOLID-LIQUID EXTRACTION

The rate of extraction or 'leaching'of a solute from a solid substance depends upon a
number of factors.A few important factors are described below.

9.2.1 Physical Characteristics of the Solid

The solute may remain distributed in the solid in different ways.The type of the solid matrix
also varies—for example,it may be porous or nonporous,it may consist of plant or animal
tissues. If the solute is distributed within an insoluble matrix of the inert'solid,it gradually
dissolves and diffuses out leaving a porous structure.In some cases,the solid may be available
as a slurry or a paste.If the solute has an affinity for the insoluble solid,it may remain partly
adsorbed to it. Thus,the rate of extraction depends upon the nature and characteristics of
the solid.
Admittedly,the rate of extraction becomes faster if the particle size of the solid is small or
if the solid is porous.Since rigid solids like metal ores and most compact solids dissolve
slowly, such materials are crushed and ground (about 60 to 100 mesh)before contacting with the
solvent. Reactive solvents (for example,an acidic solvent)are sometimes used.The
undissolved residue (often called inerts)may have a porous structure.But separation of the
inerts'from the slurry may not always be easy(for example,separation of the residue after
acidulation of phosphate ore in the process of manufacture of phosphoric acid).Materials of
plant or animal origin are not generally smashed or disintegrated because the cell walls
may be broken and thereby insoluble and undesired solid may come out.Separation of such
insoluble colloidal solids may pose a problem.This is why sugar beets are sliced to thin
pieces(but never smashed)and extraction of sugar is done with hot water.Transport of
sugar occurs by 'osmotic passage' through the cell walls.In any case,the feed solid has to be
prepared'in a suitable form or shape for quick extraction of most of the solute present in it.
 Solid-Liquid Contacting Strategy 481

9.2.2 Solvent

A solvent in which the solute has a high solubility is definitely preferred.But it should not dissolve
the undesired solids.Further,the solvent should have a low viscosity,a low boiling point,and
should be non-toxic and reasonably cheap.It is easier to remove a low-boiling solvent from
the product liquor by 'flash vaporization'

9.2.3 Temperature
Diffusivity of the solute in the solid as well as its miscibility with the solvent increases
with temperature.Also,the viscosity of the solvent becomes less at an elevated temperature and
it can penetrate into the interstices of the solid more easily.So the extraction rate
increases with temperature.Heat sensitivity of the solute,volatility of the solvent and possible
thermal effects on the inert or residual solid (for example,solubility,degradation,change in
consistency,etc.) limit the temperature of extraction.

9.2.4 Agitation

Intense agitation increases the solid-liquid mass transfer coefficient and thereby increases the
rate of extraction but may disintegrate the solid as well,causing a settling
problem.However,if the solid phase offers the controlling resistance,the effect of agitation on
the rate of extraction is not pronounced.

9.3 SOLID-LIQUID CONTACTING STRATEGY

The techniques of solid-liquid contacting may be broadly of two types:(i)fixed bed

contact,and (ii)dispersed contact in an agitated tank or vessel.

9.3.1 Fixed Bed Contacting(Percolation)

The simplest equipment for fixed bed contacting is an open or closed vessel with a perforated
support plate(also called false bottom)placed a little above the bottom.The solid rests on the
support plate(Figure 9.2).The size of the perforations should be such that the extracting liquid
can leave through it without much hindrance but the solid cannot.The liquid is fed at the top
of the bed.Fixed bed contacting may be of two types:(i)spray percolation,and (ii)full
immersion.
In spray percolation [Figure 9.2(a)],the liquid is distributed at the top and trickles
down through the bed of solid.Extraction in a fixed bed is not generally a once-through
process.The liquid leaving the bed is recirculated till a certain concentration is reached or
till the solute concentration in the bed reduces to the desired extent.Repeated extraction
with two or more fresh batches of solvent may be necessary in some cases.A common
problem of fixed bed extraction by spray percolation is channeling of the solvent as it
flows through the bed.As a result,there may be a number of pockets in the bed that do not
come in good contact with the solvent and extraction remains incomplete.
In full immersion [Figure 9.2(b)],the solid is kept dipped in the liquid for a
predetermined time after which it is drained and taken for recovery of the
solute.Alternatively,the solvent enters
482 Chapter 9 Solid-Liquid Extraction

the packed bed of the solid continuously at the bottom and leaves at the top,keeping the bed
fully immersed.Recycling of the solution may be done if necessary.

Figure 9.2 Schematics offixed bed solid-liquid extraction.

9.3.2 Dispersed Contacting

In a disperse contact device,the solid and the extracting solvent are agitated in a vessel of suitable
shape,size and design.Different types of agitators have been in use depending upon the
characteristics of the solid.Solid-liquid contacting is followed by separation of the 'inerts'from
the solution and recovery of the product from the solution as usual.

9.4 SOLID-LIQUID CONTACTING EQUIPMENT

Solid-liquid contacting may be done in a batch or a continuous equipment.The more

common types of equipment are described below.

9.4.1 Batch Equipment

Percolation leaching(fixed bed contacting),which is a batch process,has already been briefly
described in Section 9.3.1.A mechanically agitated tank for leaching is shown in Figure 9.3(a).
A number of such tanks may be arranged in series to form a batch contact battery for oil
extraction from seeds.After extraction is complete,the miscella(containing the oil,the solvent,
and a little suspended solid)is removed.The residual solvent in the exhausted meal may be
removed bypassing steam through it.Air agitation of the content of a leaching tank is sometimes
done.An air-agitated batch extractor,called the Pachuca extractor,is shown in Figure 9.3(b).
This type is popular for metallurgical leaching.It is a vertical tank having an acid-resistant lining
with a central draft tube through which air is bubbled.The rising bubbles lift the solid as well
as the liquid,causing circulation of both.At the end of the batch time,the flow of air is stopped
and the content is taken out and separated.
 Solid-Liquid Contacting Equipment 483

(a) (b)

Figure 9.3 (a)A batch extraction vessel,and (b)the Pachuca extractor.

A multi-batch extraction unit uses a battery of batch contact vessels(Figure 9.4).Each

vessel is charged with solids.Fresh solvent enters the vessel containing solids having the lowest
solute concentration.It flows successively to vessels containing solids of higher solute content.
At one end of the battery the relatively strong extract contacts a fresh batch of solid and the rich
liquid from the vessel is taken for further processing.The exhausted solid leaves the battery at
the other end.Typical movement of the solids is shown in the figure.

Figure 9.4 Muli-batch contact for solid-liquid extraction.

9.4.2 Continuous Contact Equipment

Several types of continuous contact extractors have been in use,particularly for vegetable oil
extraction and in food processing industries (Rickles,1965).The characteristics of
continuous extractors have been described in detail by Schwartzberg(1980).Continuous
extractors are generally operated in the countercurrent mode.For the same degree of
extraction,a stronger extract solution can be obtained in the countercurrent operation.The more
common continuous extractors are described below.
484 Chapter 9 Solid-Liquid Extraction

The vertical basket or the Bollman extractor

This type of extractor,widely used for the
extraction of vegetable oils from seeds,
consists of a number of baskets fixed to an
endless chain having a descending and an
ascending leg(Figure 9.5)enclosed in a
vapour-tight chamber.Each basket has a wire-
mesh bottom.Two chambers at the bottom of
the vessel separated by a partition plate hold the
extract streams.Liquids percolating along the
two legs flow down to these two chambers.
The solid (crushed or flaked seeds)is fed from
a vapour-tight hopper into the basket at the top
of the descending leg,and partially enriched
solvent (half miscella)is sprayed on the solid.
The liquid percolates through the slowly
moving baskets and collects at one of the
bottom compartments of the unit.Fresh
solvent is sprayed on the top basket in the
ascending leg and percolates through the rising
baskets and collects in the other chamber at the
bottom in the form of 'half-miscella',which is
sprayed at the top basket of the ascending leg
as stated before.Percolation of the liquid
occurs countercurrent to the solid movement
in the ascending leg,but cocurrent in the
descending leg.The baskets are
generally 0.5-0.7 m Figure 9.5 The Bollman extractor.
deep(Schwartzberg,1980).An extractor of this
type may be 40-60 feet high, can handle as
much as 50 ton/h seeds with the chain driven
by a 1-2 hp motor.Because there is no
agitation,the rich solvent leaving the
extractor remains reasonably clear.Channelling
of the liquid in the baskets may occur.

The Hildebrand extractor

This is a vertical,total immersion extractor.It
consists of a U-shaped screw conveyer fitted
with three screws—one each in the vertical
legs and one in the horizontal section of the
barrel (Figure 9.6).The helical profiles of the
screws are perforated to allow flow of the
solvent.The solid is fed at the top of one of Figure 9.6 The Hildebrand extractor.
the legs and is propelled through the
barrel.The
 Solid-Liquid Contacting Equipment 485

solvent is fed at the top of the other vertical leg and flows
countercurrent to the solid through the perforations of
the screws.This is an example of a continuous counter-
current extraction device.The rich miscella is with-
drawn through a strainer for further treatment and sol-
vent separation.The major disadvantages of the device
are:(i)a little overflow of the feed with the outgoing
liquid, (ii)excessive disintegration of the solid if the
feed is in the form of flakes,and (iii)occasional choking
with fines.

The Bonotto extractor

A vertical Bonotto-type extractor is shown in Figure 9.7.
It consists of a vertical column divided into a number of
compartments by horizontal plates.Each plate has a slot
that is oriented in the opposite side of the slot in
an adjacent plate.The slots are like the downcomers
in a distillation column.There is a scrapper on each
plate. The scrappers are fixed to a shaft running
axially through the column.
The solid enters the column at the top through
a screw feeder.It moves from one plate to the next
lower plate by the action of the scrapper.The solvent
flows up through the column and the rich extract leaves
at the top. A section of the column at the top is enlarged
Figure 9.7 The Bonotto extractor.
in diameter to reduce carryover of the solid.The
exhausted solid is taken out through another screw
conveyer at the
bottom.The operation is somewhat similar to gas-liquid contacting in a tray tower.

Horizontal basket extractor

The type of horizontal basket extractor shown in Figure 9.8(Schwartzberg,1980)is widely used
for oil extraction from seeds.It consists of a train of horizontal baskets fitted to a drive chain

Figure 9.8 Continuous horizontal basketextractor.

486 Chapter 9 Solid-Liquid Extraction

enclosed in a big chamber.Each basket has a wire-mesh or perforated bottom.Below the train
of moving baskets there are a few compartments on the floor of the enclosing chamber.There
are arrangements for feeding the solid and spraying solvent on the baskets.When an
empty basket reaches the feed point,it gets loaded with the solid from the feed hopper.As the
loaded basket advances,it is sprayed with the full miscella from a bottom compartment.Before a
basket makes a complete turn,the nearly exhausted solid is sprayed with fresh solvent.The
liquid percolates through the solid in each basket,leaves through the perforated or wire-mesh
bottom and collects below.Liquid from a chamber is pumped to the previous spray.This creates
a partial ‘countercurrent effect'.The rich extract from the collection chamber next to the solid
feeding point is taken out for further processing(i.e.solvent separation and product
recovery).The exhausted solid leaves.The device is enclosed in a vapour-tight housing to avoid
leakage of the solvent vapour.

Continuous belt extractor

A typical unit shown in Figure 9.9 is used for extraction of sugar from sugarcane or
beet.The solid is fed at one end of a perforated endless moving belt
(Schwartzberg,1980).Fresh solvent is fed at the solid discharge end.The liquid drains into a
catch basin and is pumped to the top of the adjacent section of the bed as shown in the
figure.

Figure 9.9 Continuous beltextractor.

Rotocel extractor
A rotocel extractor has a rotating basket construction (Figure 9.10).It consists of a number of
cells(usually 15 to 18)fixed to a central rotor.Each cell or basket is fitted with a hinged
perforated or screen bottom so that the solvent can percolate through the flakes of seeds or
any other solid feed.The extracting liquid is sprayed on the top of a cell.The fresh solid
enters the device at one end and the spent solid enters at the other.Below the rotating cells is a
circular tank divided into a number of compartments,each of which receives the extract from
one or more cells.The liquid or miscella from a compartment is pumped and sprayed on the
next basket in the countercurrent direction.The exhausted solid containing some entrained
solvent is removed by opening the hinged bottom.This emptied compartment continues to
rotate and then receives an amount of fresh feed,thus completing a cycle.
 Solid-Liquid Extraction Equilibrium 487
Rotocel extractors have the advantages that the solid is not subject to attrition and counter-
current extraction is achieved.Besides extraction of oils from flaked seeds,these are used
for removing solubles from plant materials(like leaves,bark,etc.)and also for leaching of
sugar beets.The construction of smaller units may be a little different from the one shown in
Figure 9.10.

Figure 9.10 The rotocel extractor.

A few other types of solid-liquid extractors(Kennedy,Olier,Crown extractors,etc.)and

their applications have been described by Schwartzberg(1980).

9.5 SOLID-LIQUID EXTRACTION EQUILIBRIUM

Consider an 'inert'(or 'carrier')solid A containing a soluble substance C distributed in it.A

mass of the solid is kept in contact with the solvent B for a sufficient time.The
following physicochemical phenomena may occur.

(a) If the solid is in the form of fine particles or flakes,the solid-phase diffusional
resistance is small.Given sufficient time,the system will reach ‘equilibrium'.Here
equilibrium means that the concentration of the solute in the clear bulk solution will be
equal to that in the liquid retained in the slurry.The amount of liquid or solution
retained in the slurry depends upon the characteristics of the solid and the density
and viscosity of the solution.
(b) If the solid is in the form of lumps or slices,the concentration of the bulk solution
and that of the intersticial or retained solution will again be equal at
'equilibrium'.However, it may take a substantially longer time to attain equilibrium.
(c) If the solute reacts with a reagent present in the solution,leaching occurs till either
the solute or the reagent is exhausted.
488 Chapter 9 Solid-Liquid Extraction

Solid-liquid extraction 'equilibrium data'for design calculations are reported in terms of the
concentration of the solute in the clear liquid (called overflow)and the fraction of the liquid in
the slurry(called underflow)and its concentration.Such data can be obtained by simple
laboratory experiments (George,1959).An amount of the solid is mixed with different
amounts of the solvent and kept mixed for a period of time.The slurry is then separated from the
mixture (by filtration or settling).The solute concentrations in the overflow and the
underflow are determined by analyzing samples of both the streams.We denote the mass
fraction of a species in the overflow by y and that in the slurry by x.The subscript denotes the
species.For example, xg is the mass fraction of the solvent in the underflow.If no subscript is
used,x or y refers to the mass fraction of the solute in the underflow and the overflow
respectively.There are two common techniques of representation of solid-liquid extraction
equilibrium data.

9.5.1 The Triangular Diagram

As in the case of presentation of liquid-liquid equilibrium data,the three vertices of a right-angled

triangle stand for 100%A,100%B and 100%C respectively.Mass fractions of the solute in
the corresponding streams (xc and yc)are plotted against the solvent concentrations (xg and
yg). The concentrations of the two streams at equilibrium are located at the ends of a 'tie
line' (see Figure 9.11 under Example 9.1).

9.5.2 The Ponchon-Savarit Diagram

In the Ponchon-Savarit type diagram,the mass ratio Z of the inert or carrier A to that of B
and C together is plotted against the mass fraction of the solute on A-free basis in both
underflow and overflow(i.e.Z versus Xc and Yc).

Underflow
(9.1)

Overflow:
(9.2)

The kind of 'equilibrium'we describe here is not the same as thermodynamic equilibrium
in case of other mass transfer operations.The composition of the sludge depends upon
the settling time.If more time is allowed,the mass fraction of solid in the sludge will definitely
be larger and that in the overflow will be smaller.The fraction of liquid retained in the sludge
also depends upon the viscosity and density of the solution.With increasing density and
viscosity of the solution,the fraction of liquid in the sludge will be more.Thus the
'equilibrium data'will depend upon the condition of the system —the particle size of the solid,the
settling time allowed, and the density,viscosity and concentration of the
solution.However,unless the inerts adsorb the solute,the concentrations of the overflow liquid
and that retained in the sludge (on solid-free basis)are likely to be the same (i.e.Xc =Yc).
A tie line on the right triangular equilibrium plot joins the compositions of the two phases in
‘equilibrium'.If the liquid concentrations in the two phases on solid-free basis are equal,the tie
lines on the X-Y-Z plane are vertical lines.The construction of solid-liquid'equilibrium
diagrams'is illustrated in Example 9.1.
 Solid-Liquid Extraction Equilibrium 489

EXAMPLE 9.1 (Solid-liquid extraction equilibrium data) A set of experimental test data on
solid-liquid extraction 'equilibrium'for the system oil seed meal(A)-hexane(B)-oil(C)is
reported below.Mixtures of the 'components'at various overall composition are stirred in a
laboratory vessel and then allowed to settle.Samples of the overflow (oil +solvent hexane +
traces of the inert meal)and the underflow (inert meal +entrained solution)were drawn and
analyzed.The following data were collected.

Overflow(100 kg),solution Underflow(1 kg),slurry

00
W₄ (kg) Wg(kg) Wc(kg) WA(kg) Wp(kg) wó(kg

0.3 99.7 0.0 67.2 32.8 0.0

0.45 90.6 8.95 67.1 29.94 2.96
0.54 84.54 14.92 66.93 28.11 4.96
0.70 74.47 24.83 66.58 25.06 8.36
0.77 69.46 29.77 66.26 23.62 10.12
0.91 60.44 38.65 65.75 20.9 13.35
0.99 54.45 44.56 65.33 19.07 15.6
1.19 44.46 54.35 64.39 16.02 19.59
1.28 38.50 60.22 63.77 14.13 22.10
1.28 34.55 64.17 63.23 12.87 23.90
1.48 24.63 73.89 61.54 9.61 28.85

Plot the 'equilibrium data'(a)as the right-triangular plot,and (b)as the 'Ponchon-Savarit'
diagram
Solution
(a)Right-triangular diagram: The mass fraction of a component in the overflow
is denoted
by y and that in the underflow by x.In the given case,the values are directly obtainable from
the above table.For example,from the last row of the table,mass fractions in the overflow are
y₄=0.0148,yg=0.2463,yc =0.7389;the corresponding concentrations in the underflow
are x₄=0.6154,xg=0.0961,xc=0.2885.'Equilibrium'plots of the two streams are shown in
Figure 9.11(a).The vertices of the right-angled triangle ABC
represent:A(100%‘inerts',i.e.the solid free from oil and
solvent);B(100%solvent);C(100%‘solute').The plot of yc versus yg represents the
overflow stream;that of xc versus xg represents the underflow streams (xc and yc are taken
along the horizontal axis;xg and yg are taken along the vertical axis).The lines joining the
corresponding points on the underflow and overflow curves are the tie lines.The tie lines
pass through the origin.

Note: The solution phase contains traces of the inert solid (the meal).This occurs in many
cases because settling is hardly perfect in practice.The entrained solid in the overflow
increases with the oil concentrations(this occurs because of the increased density and
viscosity of the solutions with increasing oil concentration).For this reason,the overflow
curve lies slightly below the hypotenuse.If there is no entrained solid in the overflow,the curve
should be a straight line along the hypotenuse.
490 Chapter 9 Solid-Liquid Extraction

The data show that the solution retained in the underflow per unit mass of inert increases
with the concentration of the solution.For this reason the underflow line is slightly curved.If
the fraction of solution retained is constant,the underflow line should be a straight
line.However, the concentrations of oil (solid-free basis)in both the overflow and the underflow
are the same. This indicates that the oil (solute)is not preferentially retained or adsorbed by the
inert solid or meal.
(b)‘Ponchon-Savarit'diagram: The given data are used to calculate Yc =Wcl(wc +wg),
Z=w₄/(wc+wg)for the overflow;Xc=wc/(wc+wb),Z=wí/(wc+wb)for the
underflow. The calculated values of Z for both overflow and underflow are plotted versus Xc or
Yc to give the 'Ponchon-Savarit'type diagram,Figure 9.11(b).The values (tie-line data)are
given below:

Yc 0 0.09 0.15 0.25 0.30 0.39 0.45 0.55 0.61 0.65 0.75
Z 0.003 0.0045 0.0054 0.007 0.0078 0.0092 0.010 0.012 0.013 0.013 0.015

Xc 0 0.09 0.15 0.25 0.30 0.39 0.45 0.55 0.61 0.65 0.75
Z 2.05 2.04 2.02 1.99 1.965 1.93 1.90 1.80 1.76 1.72 1.6

Note: Since the overflow contains traces of the suspended solid,the overflow curve lies a
little above the horizontal axis.If the overflow is absolutely clear,the overflow line will lie
along the horizontal axis.The underflow line bends a little at higher concentrations Xc of the
entrained solution.If the solution retained in the underflow(slurry)is independent of Xc,the
line will be parallel to the horizontal axis.
The tie lines are also shown in Figure 9.11(b).Since the concentrations of the solution
on 'solid-free basis'in the two streams are equal,the tie lines are parallel vertical lines.If the
solution concentrations in the two streams are different,the tie lines will not be parallel.

xg,YB
Xc Yc
(a) (b)
490 Chapter 9 Solid-Liquid Extraction
Figure 9.11 Leaching equilibrium data'plotted (a)on the triangular diagram,and (b)on the Ponchon-Savarit diagram.
 Solid-Liquid Extraction Calculations 491

9.6 SOLID-LIQUID EXTRACTION CALCULATIONS

Solid-liquid extraction calculations are often based on the concept of 'ideal stage'.If the
clear solution leaving a contact stage has the same composition as that of the liquid retained
in the sludge(or underflow),the stage is called ideal'.
As in the case of many other mass transfer operations,the common strategies of solid-liquid
contacting for extraction or leaching are:(i)batch contact,(ii)cross-current contact,and
(ii)countercurrent contact.The important variables and parameters are:(i)the rate of
processing of the solid feed;(ii)the solute content of the feed;(iii)the allowable solute
concentration in the lean sludge leaving the extractor(or the fractional recovery of the
solute);and(iv)the solvent rate and the concentration of solute in it,if any.Design calculations are
based on material balance equations and the 'equilibrium data'for the particular system.The
number of contact stages can be determined graphically using the right-triangular diagram
or the Ponchon-Savarit type diagram.Analytical determination of the number of stages is
possible under certain restrictive situations.

9.6.1 Batch Contact

In single-stage batch contact,the solid feed and the solvent

are charged into an agitated vessel and kept in intimate con-
tact for some time.The mixture is then allowed to settle.
The clear solution(overflow)and the
sludge(underflow) are separated.This is schematically
shown in Figure 9.12. The flow rates and the
concentrations of the input and output streams are also
shown.Given the mass and the concentrations of the two Figure 9.12 Single-stage batch contact.
input streams and the 'extraction
equilibrium data',it is possible to calculate the concentrations and amounts of the two output
streams (the overflow and the underflow)and also the fraction of the solute extracted.Graphical
calculations are generally done,although algebraic calculations are possible in certain
cases.The right-triangular diagram or the Ponchon-Savarit diagram can be used for graphical
calculations.

Use of the right-triangular diagram

Here the total mass of a stream and the concentrations in mass fraction are used.Refer
to Figure 9.12.We write the following balance equations:
Total mass balance: F+S=V+L=M (M is the total mass of the two streams)(9.3)
Solute balance: F(xc)p+S(yc)s =L(xc)t+Vyc)v =M(xc)n (9.4)

This does not mean that the solution is saturated'or in equilibrium with the solute present in the
solid,since the contact time allowed in a stage may not always be sufficient for establishment of such an
equilibrium. Phenomena like the adsorption of the solute on the inerts or the imperfect settling of the
sludge maybe taken into account by incorporating a 'stage efficiency'.If experimental solid-
liquid'equilibrium data'collected in the laboratory are used for design of an industrial equipment
operated under similar conditions,the stage efficiency is automatically taken into account.
492 Chapter 9 Solid-Liquid Extraction

The overall solute concentration of the mixture can be obtained from Eqs.(9.3)and (9.4)as

(9.5)

The equilibrium data are plotted on the right-triangular diagram.The points F and S giving
the concentrations of these two streams are located on the diagram.The point M representing
the mixture is also located on the line SF at (xc)m.Alternatively,the point M can be located
on the line SF using the Lever Arm Rule.The terminals of the tie line through the point M give
the solute concentrations(xc)t and (yc)v in the two output streams,L and V.The amounts of
the output streams can be obtained by using the Lever Arm Rule or by material
balance.The procedure is illustrated in Example 9.2.

Use of the Ponchon-Savarit diagram

The procedure is very similar to that described above.However,the mass of the streams are
taken on 'solid-free basis',and their concentrations Z are taken as the mass of solid per unit
mass of non-solid.The flow rates of the various streams are F',S',L',and V',all on 'solid-free
basis'. We write the following material equations.
Total material balance: F'+S'=L'+V'=M' (9.6)
Solid balance: F'Zp+S'Zs=L'Zr+V'Zy,=M'Zu (9.7)

From the above two equations, (9.8)

The equilibrium data are plotted on the Ponchon-Savarit diagram and the points F'and
S' are located on it.The point M'is also located on the line S'F',and the tie line through M'is
drawn. The solid concentrations in the overflow Zy,and in the underflow Z,,are obtained
from the extremities of the tie line (the subscript of Z indicates the stream concerned).The
quantities of the overflow and the underflow are obtained by solving the material balance Eqs.
(9.6)and (9.7). The procedure is illustrated in Example 9.2.

EXAMPLE 9.2(Solid-liquid extraction in a single-stage batch contactor) One

thousand
kilograms of crushed oil seeds(19.5%oil,80.5%meal)is extracted with 1500 kg of 'pure’
hexane in a batch extraction vessel.Calculate the fraction of the oil extracted
using(a)the right-triangular diagram and (b)the ‘Ponchon-Savarit diagram'.The equilibrium
data given in Example 9.1 are applicable.
Solution
(a)Calculation using the right-triangular diagram
Refer to Figure 9.12.Given:F=1000 kg;S=1500 kg;(xc)r=0.195;(yc)s =0.
Total material balance:F+S=M=L+V→M=1000+1500 =2500.
Solute balance:F(xc)r+S(yc)s =M(xc)m→(xc)m =[(1000)(0.195)+(1500)(0)]/2500 =0.078.

The points F(x₄=0.805,xg=0,xc=0.195)and S(y₄=0,yg=1,yc=0)are located

on the diagram [see Figure 9.13(a)]in which the extraction 'equilibrium data'are also
plotted.The
 Solid-Liquid Extraction Calculations 493

point M representing the mixture of F and S lies on the line SF at(xc)m =0.078.The tie
line through the point M is drawn.The terminals of the tie line are the points
L(xc=0.0403,xg =
0.29)and V(yc =0.114,yg =0.884).
Total material balance [see Eq (9.3)]:V+L=M=1000+1500 =2500
Solute balance [see Eq.(9.4)]:Vyc +Lxc =M(xc)m
→ (0.114)V+(0.0403)L=(0.078)(2500)→V+0.3535L =1710.5 (ii)
Solving Eqs.(i)and (ii),L=1221 kg,and V=1279 kg
Amount of oil extracted =Vyc =(1279)(0.114)=145.8 kg
Initial amount of oil in the feed =(1000)(0.195)=195 kg.Fraction extracted =
74.8%
(b)Calculation using the Ponchon-Savarit diagram

Given:F'=amount of 'non-solid'in the feed =(1000)(0.195)=195 kg;(Xc)p,=mass fraction

of the solute in the feed on 'solid-free basis'=195/195=1;Zp,=kg solid/kg non-solid =805/
195 =4.13.
Similarly,S′=1500,(Yc)s=0(because the feed solvent is 'pure'or oil-free);Zs =0.
By material balance,M'=195+1500=1695;Zy,=(F'Zp+S'Zs)/M'=0.475.
The 'equilibrium'data are plotted in Figure 9.13(b).The points F'(1,4.13)and S(0,0)are
located on the diagram.The point M'is located on the line S'F'at Zw=0.475.The tie line
through the point M'is drawn.This is a vertical line with the terminal points L'and V".It is found
from the plot that

Z=2.03;Zw≈0; M',L and V'are on the same vertical

(Xc)=0.115=(Xc)x=(Yc)v(since line).

Xg,Yg

xc,Yc Xc,Yc
(a) (b)
Figure 9.13 Single-stage batch leaching:(a)triangular diagram,and(b)Ponchon-Savarit diagram.
494 Chapter 9 Solid-Liquid Extraction

Putting the values of different quantities in the material balance Eqs.(9.6)and (9.7),we
get L′=396.6 kg;mass of the underflow=L(1+Zy)=396.6(1+2.03)=1201.7
kg
V′=M'-L'=1695-396.6 =1298.4 kg
Mass of the overflow =V(1+Zy)=(1298.4)(1+0)=1298.4 kg(this is virtually solid-free).

Fraction of the oil extracted =(V)(Yc)v/F'=(1298.4)(0.115)/195 =0.736,i.e.

76.6
%
The small difference between the fractional extraction figures in parts (a)and (b)arises from
the error in reading the values on the plots.

9.6.2 Cross-current Contact

The schematic of a three-stage cross-current contact unit is shown in Figure 9.14(this is
similar to Figure 4.16).The flow rates and the concentrations of the input and output streams
to and from different stages are also shown.The underflow from the first stage is pumped to the
second stage and so on.Extraction calculations can be done graphically as illustrated in
Example 9.3.

Figure 9.14 Multi-stage cross-current solid-liquid contact.

EXAMPLE 9.3 (Cross-current solid-liquid extraction)

Refer to Example 9.2.Instead of using the solvent
at one time,it is planned to carry out the extraction
in a three-stage cross-current unit using one-third
of the solvent (i.e.500 kg)in each stage.Using the
'equilib- rium data'given in Example 9.1,calculate
the fraction of oil that can be extracted.

Solution
We shall solve the problem by graphical
construction using the X-Y-Z diagram.Consider
stage 1(see
Figure 9.14).The input streams are:
F=1000 kg,(xc)r=0.195;S=500 kg,(yc)s =
0.The quantities expressed on solid-free basis are:
F′=195 kg,Zp=805/195 =4.13;S
′=500, Zs,=0(no solid in the feed solvent).The
mass and solid content of the mixed stream in
stage 1,M1=F’ +S Xc Yc
′=195+500=695;Zw;=(805+0)/695=1.16. Figure 9.15 Three-stage cross-current batch'leaching'
The points F'and S'are located on the 'Ponchon- calculation on the'Ponchon-Savarit diagram.
Savarit'diagram(Figure 9.15).The point Mi
is located on the line S'F'such that Zw;=1.16.The
tie