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LIQUID-LIQUID EXTRACTION

Liquid extraction is the removal of solute from a solution using solvent.

Separation results when the solubility of solute is different in the two liquids.
This is a liquid-liquid operation.
M’;klkfdaqs
..l.’vc [[]

This is preferred over distillation for the following reasons:

[Link] of close boiling liquids GJ

2. Separation of liquids of poor relative volatility . Example – Separation of

acetic acid water mixture using ethyl acetate.

3. As a substitute for high vacuum or molecular distillation for mixtures

whose boiling Points are high.
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4. As a substitute for expensive evaporation

5. Separation of mixtures that form azeotropes

Three components A,B,C are involved in the operation. A and B are

solvents and C is the solute. The components A and B should be liquids.
Initially there will be a solution of A and C from which C is to be removed.
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Feed is a mixture of A+C and it is contacted with solvent B which may be a pure
solvent B or a mixture of B+C in the extractor. After sufficient time of agitation , the
mixture is allowed to separate and two layers are separated namely the extract
layer which is B+C and raffinate layer which is A+C.

Extract B+C

Feed A+C Raffinate A+C

Solvent B or B+C
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It is always not possible to select a solvent B which is immiscible with A, therefore we consider
two cases in general

Partially miscible system:

In this case A and B are slightly soluble with each other and C is soluble in both A and B

Immiscible system:
In this case A and B are immiscible with each other and C is soluble in A and B.

When the system is partially miscible the extract and raffinate will have three components
Extract B+C+
small A

Feed A+C
Raffinate A+C+
Small B

Solvent B or B+C
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DEFINITIONS:

Feed: In extraction operation the solution which is to be extracted is called the feed

Solvent: The liquid with which the feed is contacted is called the solvent.

Extract: The solvent rich product of the operation is the extract.

Raffinate: The residual liquid from which solute has been removed or diluent rich product is
the raffinate.
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PARTIALLY MISCIBLE SYSTEM:

Since A and B are slightly soluble in each other, after contacting A+C and B and separating the
mixture, we get two layers. They are A+C+ small B and B+C+ small A.

They are respectively called A rich layer or the raffinate layer or aqueous layer and B rich layer
or the extract layer or organic layer.

It is clear that both extract and raffinate layers contain all the three components in smaller or
larger compositions.
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NOTATION USED

F = quantity of feed, A+C in kg or kg/sec

S = quantity of solvent, B or B+C in kg or kg/s
R = quantity of A rich layer or raffinate in kg or kg/s of A+C+B
E = quantity of B rich or extract in kg or kg/s of B+C+A
M= quantity of mixture = F+S=R+E in kg or kg/s of A+B +C
x = mass fraction of C (solute) in raffinate kg C / kg (A+B+C)
y = mass of fraction of C (solute) in extract kg C / kg (A+B+C)
xm= mass of fraction of C (solute) in mixture kg C / kg (A+B+C)

In feed and solvent the concentration of solute is expressed as xF and ys respectively.

The quantities and concentrations of streams leaving a stage are denoted by stage subscripts.
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NOTATION USED

F = quantity of feed, A+C in kg or kg/sec

S = quantity of solvent, B or B+C in kg or kg/s
R = quantity of A rich layer or raffinate in kg or kg/s of A+C+B
E = quantity of B rich or extract in kg or kg/s of B+C+A
M= quantity of mixture = F+S=R+E in kg or kg/s of A+B +C
x = mass fraction of C (solute) in raffinate kg C / kg (A+B+C)
y = mass of fraction of C (solute) in extract kg C / kg (A+B+C)
xm= mass of fraction of C (solute) in mixture kg C / kg (A+B+C)

In feed and solvent the concentration of solute is expressed as xF and ys respectively.

The quantities and concentrations of streams leaving a stage are denoted by stage subscripts.
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SELECTIVITY β:

This is defined as the ratio of the mass ratios of C to A in extract phase to that ratio in the
raffinate phase.

β= (mass of C / mass of A) extract

(mass of c/ mass of A)raffinate

= (mass fraction C / mass fraction A) extract

(mass fraction C / mass fraction A) raffinate
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Construction of phase diagrams on equilateral triangular coordinates:

In this case the three sides are taken as 100% , the three apexes A,B and C represent
pure A,B and C respectively. A point on the AB represents a mixture of A and B, similarly
a point on AC represents a mixture of A and C and a point on BC represent a mixture of
B and C. Any point inside the triangle represents a mixture of A, B and C. Since the % of
one component can be obtained from the % of the other two, to locate a point, the
information of the % of two of the components are sufficient.
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PHASE DIAGRAMS:
For a given system the equilibrium concentrations y* and x can be obtained at a
given temperature. The data can be plotted on a graph to get the equilibrium curve
as usual. Since the two phases involve three components it is not possible to solve
the problem only with equilibrium curve and so phase diagram is considered. Since
the two layers contain the three components, it is convenient to use a triangular
diagram.
Fix a point on the triangular diagram for the mixture
having composition 40% A, 20% B, 40% C. Fix 40% A
on AB line and draw a line parallel to the opposite
base of A that is BC. Fix 40% C on AC line and draw a
parallel to AB (opposite base of C). The two lines
intersect at a point and the point of intersection is
the required point.
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When the solvent B is added to A+C, a mixture of ABC is obtained. The mixture
can be homogeneous or heterogeneous. When the heterogeneous mixture is
settled, two equilibrium homogenous liquid layers are obtained R (A rich) and E
(B rich). The concentration of C in R and E are respectively x and y*. The point
corresponding to M, R, E can be located on triangular graph.

The property of the equilateral triangle which is used

for the construction of binodal curve is the altitude of
the triangle is equal to the sum of the perpendiculars
drawn to the three sides from any point inside the
triangle.
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PLAIT POINT:
For a given system the tie lines are normally sloping in one direction and need
not be parallel. Innumerable tie lines can be drawn for a bi nodal curve. The tie
lines merges at a point called plait point.

SOLUTROPIC SYSTEM:

If the tie lines are changing their slope (direction) a particular tie line is
horizontal and such a system is called solutropic system.
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RIGHT ANGLE TRIANGLE DIAGRAM:

The binodal curve can be drawn on a right angle triangle graph (by transforming
the equilateral triangle to a right angle triangle). Since a point can be located
from the composition of B and C, the %B and %C are taken on the two sides of
right angles.

F Raffinate curve
%C Extract curve
R M E
A S,100% B
%B

On the graph F is located on AC since it is a mixture of A and C. The solvent point

is fixed at 100 % B because normally the solvent is pure B. The mixture, raffinate
and extract points are located as shown at M, R and E respectively.
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ADVANTAGES OF RIGHT ANGLE TRIANGLE DIAGRAM:

Easy to draw and can be drawn on the ordinary graph
The scales can be changed

EQUILIBRIUM CURVE:
The relation between x and y* can be plotted to get the equilibrium curve.
Different shapes of equilibrium curve are shown
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STAGE WISE OPERATION:

The extraction operation can be one of the following types

Single stage operation

Multistage cross-current operation
Multistage counter-current operation

If the stage is ideal the layers separated are in equilibrium as shown by the
points R and E and the point (x, y*) is located on the equilibrium curve.
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OVERALL MATERIAL BALANCE:

F+S = M = E+R (1)

Equation (1) shows that M is located on FS line and also
on RE line, or the tie line RE should pass through M for
ideal stage.
Mixtures
SOLUTE BALANCE:
FxF+ Sys= Mxm= Rx+ Ey (2)
All streams can be plotted as points on the phase
diagram using their composition. If two streams are
xm = (FxF + SYs) / M (3) added to get a mixed stream, both the streams can
From 1, R = M – E (4) be plotted as points and the points may be joined
From 2 and 4
to get a straight line. The mixer point will be on the
M (xm-x) = E (y-x )
line and is fixed based on its composition. The
E = M (xm-x) / (y-x) (5) mixer rule is valid.
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PROCEDURE TO FIND R ,E AND THEIR CONCENTRATIONS:

Draw the binodal curve and the equilibrium curve.
Locate F,S and join F and S
Calculate xm from equation 3 and locate M on FS line
By trial and error with the help of the equilibrium curve
draw the tie line RE and obtain x and y values

Calculate E from equation 5 and R from equation 4

For R and E the %B is taken from x axis and hence
the complete composition of raffinate and extract
are known.
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Water A 98.1 95.5 84.4 71.1 59.8 37.1

layer B 1.2 1.6 2.3 3.4 4.4 16.5
C 0.7 2.9 13.3 25.5 35.8 46.4
Ether A 0.5 0.8 1.9 3.9 6.9 15.1
layer B 99.3 98.4 93.3 84.7 71.5 48.7
C 0.2 0.8 4.8 11.4 21.6 36.2
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MULTISTAGE CROSS CURRENT OPERATION:

In this operation fresh solvent is used in each stage and the raffinate of
I stage enters the II stage. The raffinate of II stage enters the third stage
and so on.
The operation is shown below
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MATERIAL BALANCE:

I stage

F+S1 =M1=E1+R1 1.1

F xF + Sys = M1xM1=E1y1+R1x1 1.2

xm1 = (FxF + S1 ys) /M1 1.3

R1=E1- M 1 1.4
M1xm1=E1y1+ (M1-E1) x1

E1=M1 (xm1- x1)/( y1- x1) 1.5

The construction is the same as in a single stage operation. M1 is located on FS1 line
at xm1. The tie line E1R1 is drawn through M1 by trial and error and x1 and y1 values are
found. E1 and R1 are calculated from eqn.5 and 4 respectively
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II stage
R1 is the feed for the 2nd stage
R2+S2=M2=E2 +R2 2.1
R1x1+S2ys=M2xm2=E2y2+R2x2 2.2
xm2 = (R1x1+S2ys)/M2 2.3
R2= M2-E2 2.4
E2=M2 (xm2- x2)/( y2-x2) 2.5

For the second stage M2 is located on R1S2 and tie line E2R2 passes through M2. The
remaining procedure is the same. The solvent concentration ys is the same for all the
stages the points S1, S2,…. Etc. coincides. This procedure can be extended to any
number of stages.
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Multistage counter current extraction:

The flow sheet for this type of operation is shown in the above figure. Let the feed be
F kg and the Solvent used be S kg. Let the feed concentration be xF. Extract and
raffinate streams flow from stage to stage in counter current and provide two final
products, raffinate RNp and extract E1.
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Immiscible system:
In this case, two pairs are soluble and one pair is completely immiscible.
Raffinate A, Solvent B, Solute C Where AC and BC are soluble and AB is insoluble.
When a feed containing A+C is treated with B and settled, two homogeneous
layers are obtained. The raffinate contains A and C only and the extract phase B
and C only. For this case solute free concentrations are useful. i.e., the amount
of solute per amount of solute free liquid.
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Notations used:

A Kg or kg/s of component A in feed or raffinate

B Kg or Kg/s of component B in solvent or extract
x’- Kg of C / Kg of A [ mass of C/mass of A]
y’- Kg of C/ Kg of B [mass of C/ mass of B]
A x’ gives the amount of C in feed or raffinate
B y’ gives the amount of C in solvent or extract

The operation can be any one of the following:

Single stage operation

Multistage cross-current operation
Multistage counter-current operation
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Single Stage operation

Solute in feed = Ax’F
Total feed = A+ AxF’ = A(1+xF’)
Solvent B and total solvent = B(1+ys’)
Total Raffinate = A(1+x’),
Total Extract = B(1+y’)
If the stage is ideal, x’ and y’ are the
equilibrium concentrations. To solve
problems of immiscible systems, only
the equilibrium data between x’ and y’
is necessary. Phase diagram is not
necessary.
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Solute Balance:
AxF’+Bys’= Ax’+By’
A(xF’-x’) = B(y’-ys’)
(y’-ys’)/(x’-xF’) = -(A/B)

The above equation is a straight line

connecting (x’,y’) and (xF’, ys’) with a
slope of –(A/B). For an ideal stage
(x’,y’) is located on the equilibrium
curve.
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If B1 = B2= B3 , all the stages are equal

and the operating lines are parallel.
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Multistage counter current extraction

Solute balance:
A(xF’-xNp’) = B(y1’-ys’)

(y1’-ys’)/(xF’-xNp’) = (A/B)

This is the equation of a straight line

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Multistage counter current extraction

Solute balance:
A(xF’-xNp’) = B(y1’-ys’) or (y1’-ys’)/(xF’-xNp’) = (A/B)

This is the equation for the operating line connecting (xF’,y1’) and (xNp’,ys’) with
slope A/B. The line along with the equilibrium curve is shown below. The
number of theoretical stages can be obtained by the usual step construction.
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Minimum Solvent Rate:

This can be found from the slope of the operating line which touches the equilibrium
curve within the operating range.
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200 kg of aqueous acetic acid solution containing 25% acetic acid is to be extracted
with 150kg of isopropyl ether solvent at 20˚C. Two batch extractions are to be done
with fresh and pure solvent. Estimate the quantities and compositions of the extract
and raffinate products.
Water layer A 98.1 95.5 84.4 71.1 59.8 37.1
B 1.2 1.6 2.3 3.4 4.4 16.5
C 0.7 2.9 13.3 25.5 35.8 46.4

Ether layer A 0.5 0.8 1.9 3.9 6.9 15.1

B 99.3 98.4 93.3 84.7 71.5 48.7
C 0.2 0.8 4.8 11.4 21.6 36.2
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Raffinate Extract
Stage Quantity % C % B %A Quantity % C % B %A
(kg) x From graph From graph (kg) y From graph From graph

First 189.2 22 3 7.5 85.8 9.5 87 3.5

Second 183.8 19.5 2.5 7.8 80.31 7 90 3

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45 kg of solution of acetic acid (C) and water (A) containing 30% acid is to be
extracted three times with the isopropyl ether (B) at 20˚C using 80 kg of solvent
in each stage. Determine the quantities of and the composition of various
streams. How much solvent will be required if the final raffinate concentration is
to be obtained in one stage?

Water layer % Acid (C) 0.69 1.41 2.89 6.42 15.3 25.5 44.3 46.4
(Raffinate) % Water (A) 98.1 97.1 95.5 91.7 84.4 71.1 45.1 37.1

% Ether (B) 1.2 1.5 1.6 1.9 2.3 3.4 10.6 16.5
Ether layer % Acid (C) 0.18 0.37 0.79 1.93 4.82 11.4 31.1 36.2
(Extract) % Water (A) 0.50 0.7 0.8 1 1.9 3.9 10.8 15.1

% Ether (B) 99.3 98.9 98.4 97.1 93.3 84.7 58.1 48.7
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100 kg of a solution of acetic acid( C ) and water (A) containing 30% acid is to be
extracted in three stages with isopropyl ether( B ) at 20 C, using 40 kg of solvent on each
stage. Determine the quantities and compositions of each stream. How much solvent
would be required if the same raffinate concentration were to be obtained with one
stage? How many ideal stages are required for a counter current operation if the solvent
used is 1.5 times the minimum and the raffinate is to contain no more than 1% acetic
acid. Water layer Isopropyl ether layer
Wt.% Wt.% Wt. % Wt. % Wt.% Wt.%
acetic Water Isopropyl acetic water Isopropyl
acid ether acid Ether
0.69 98.1 1.2 0.18 0.5 99.3
1.41 97.1 1.5 0.37 0.7 98.9
2.89 95.5 1.6 0.79 0.8 98.4
6.42 91.7 1.9 1.93 1.0 97.1
13.3 84.4 2.3 4.82 1.9 93.3
25.5 71.1 3.4 11.4 3.9 84.7
44.3 45.1 10.6 31.3 10.8 58.1
46.4 37.1 16.5 36.2 15.1 48.7
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Solute A is to be extracted counter currently from a mixture of A and B containing 40%

by weight of A using solvent C. Raffinate should not contain more than 5% of A. Evaluate
minimum solvent rate per kg of feed and actual number of stages required when actual
solvent rate is twice the minimum and stage efficiency is 75 %. The equilibrium test data
available are

Extract layer wt.% C 95 89 75 65 55

B 2.9 3.5 5 10
2.5
Raffinate layer wt.% C 2.5 3.0 5.5 8.5 15
B 92.5 87 65 50 40
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This is a problem of partially miscible system. The equilibrium data given is only for two
components. But total is not 100.
Operation is counter current. The system A- Solute B-Diluent C- Solvent

Data for equilibrium curve

y 2.5 8.1 21.8 30 35 ( solute)

x 5 10 29.5 41.5 45 ( solute)

Data for Phase diagram

A ( Solute) 2.5 8.1 21.8 30 35
Extract Phase C ( Solvent) 95 89 75 65 55

Raffinate Phase A ( Solute) 5 10 29.5 41.5 45

C ( Solvent) 2.5 3 5.5 8.5 15
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Assume F=100 xF= 0.4 xNP =0.05

Draw equilibrium curve and phase diagram Fix F, S points. Draw a tile line through F by trial
( Trail value x=37.5 y=28) to find E1 min.

Join E1 min and RNP to get x min. From graph x min= 0.215 , Xm min= (F xF + Sys)/ (F + S min)

0.215= (100x 0.4 + Sx0)/ (100 + S min) Smin= 86 S actual = 2x86= 172 kg

X m= (100x0.4)/ 100+ 172 = 0.15

Fix M point through xm = 0.15 Join RNP and M and extend to get E1 actual.
Join FE1, RNP S and extend them to get ΔR.
Draw tie line E1R1
Join R1 Δ R to get E2. Draw tie line E2R2. Join R2 ΔR to get [Link] E3 R3.
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Nicotine in a water solution containing 1 % nicotine is to be extracted with

kerosene at 20oC. Determine the percentage extraction of nicotine if 100 kg of
feed solution is extracted once with 150 kg solvent. What will be percentage of
extraction of nicotine if it is carried in three stages and solvent used in each
stage is 50 kg?

Equilibrium data at 20oC:

0 0.001011 0.00246 0.00502 0.00998 0.0204

0 0.000807 0.001961 0.00456 0.009130. 0.0187

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Nicotine in water containing 2% Nicotine is to be extracted by kerosene. Water

and kerosene are essentially insoluble. Determine the percentage of extraction
of nicotine if 200 kg of feed solution is extracted once by 300 kg solvent.
Compare the extraction with a three stage extraction using 100 kg in each stage.

Equilibrium data
Kg nicotine / kg water x 103 :0 1.01 2.46 5.02 7.51 9.98
Kg nicotine / kg kerosene x103 :0 0.8 1.96 4.56 6.86 9.13
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1000 kg/h of 25 % solution of dioxane in water is to be extracted continuously in

a counter current fashion using benzene to remove 95 % of dioxane. Water and
benzene are insoluble. What is the minimum solvent required? If 900 kg /h of
solvent is used, how many theoretical stages are required?

Equilibrium data:

Wt. % dioxane in water 5.1 18.9 25.2

Wt. % of dioxane in benzene 5.2 22.5 32.0
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A 10% by weight aqueous solution of acetic acid is to be treated with iso- propyl
ether to reduce the concentration of the acid in the raffinate to 1 % by weight by
liquid –liquid extraction. Determine the number of counter current stages
required if the solvent rate is 2 times the minimum.

Equilibrium data:
Kg acetic acid / kg water : 0.0197 0.0400 0.0827 0.1290 0.1790
Kg acetic acid / kg ether : 0.00403 0.01030 0.02270 0.03790 0.05580
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If 1000 kg / hr. of nicotine (C) – water (A) solution containing 1 % nicotine is to

be Counter currently extracted with kerosene at 20℃ to reduce the nicotine
content to 0.1% .Determine minimum kerosene rate and the number of stages
required if 1150 kg of kerosene is used per hour.

Equilibrium data:

Kg nicotine / kg water: 0.001011 0.00246 0.005202 0.00751 0.00998 0.0204

Kg nicotine/ kerosene : 0.000807 0.001961 0.00456 0.00686 0.00913

0.01870

Water and kerosene are insoluble in each other.

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500 kg of nicotine water solution n containing 1.2 5 nicotine is to be extracted

counter currently with kerosene at 25℃ to reduce the nicotine content to 0.15%.
Determine a) minimum kerosene rate b) Number of theoretical stages required if
1500 kg / hr. of kerosene is used

Kg nicotine / kg water : 0.001 0.00246 0.00502 0.00751 0.00998 0.0204

Kg nicotine / kg kerosene : 0.0081 0.00196 0.00156 0.00686 0.00913 0.0187