Unit Operations of Chemical Engineering

LIQUID-LIQUID
EXTRACTION
Liquid-liquid extraction (1)

Introduction

Introduction

This subject deals with the separation of the components of a liquid mixture by treatment with a solvent in which one or more of
the desired components is preferentially soluble. After this, two immiscible phases of different density are obtained.
Basic Nomenclature:
Feed: solution to be treated.
Solvent: liquid which is added to the feed (it may contain some solute).

When the feed and solvent are mixed, two phases are obtained:
Extract (E): the richest phase in solvent.
Raffinate (R): the poorest phase in solvent.

Distillation is either uneconomic or

impracticable in the following
cases:
1. When an excessive amount of
steam must be applied
2. When the relative volatility of the
two main components is near unity.
3. When azeotropes are formed.

Extracted product: is the remaining mixture after separating the solvent from the extract.
Raffinate product: is the remaining after separating the solvent from the raffinate.
It is fundamental an easy recovery of the solvent which has been added (by distillation, evaporation, etc.)
The addition of a solvent to a binary mixture of the solute in a solvent may lead to the formation of several types of mixture:
a. A homogeneous solution may be formed, then the solvent selected is unsuitable.
b. The solvent may be completely immiscible with the initial solvent
c. The solvent may be partially miscible wilt the original solvent, resulting in the formation of two or three pair of partially miscible
liquids.
d. The types b), and c) generate systems that may be useful.
Generally, it can be said that for carrying out a liquid-liquid extraction the following conditions are necessary:
1. Contact between the original solution with the solvent.
2. Separation of the obtained liquid phases (extract and raffinate).
3. Recovery of the solvent.
The first two previous sections constitute the stage or extraction unit, and it is called ideal or theoretic when the contact between
the solution and the solvent has been deep enough to consider that the separated phases have the concentrations corresponding
with equilibrium conditions.
Liquid-liquid extraction (2)

Equilibrium Conditions in Liquid-Liquid Extraction

The equilibrium condition for the distribution of one solute between two liquid phases may be considered in
terms of the distribution law. Thus, at equilibrium, the ratio of the concentrations of the solute in the two
phases is given by:
Distribution constant K i

Concentration of the component i in E CE

Concentration of the component i in R CR

The Ki value depends on the solvent, the mixture composition and the temperature.
In many cases the two solvents are partially miscible and the concentration of the solute influences the
solubility; in any case the experimental data are essential.

Sequence of study
Introductory exercises
a.- Single Contact (In one stage)
a1- Solvent partially miscible in one of the feed components and completely miscible in the other
one.
a2- Immiscible solvents.
b.- Co-current Multiple Contact
b1- Co-current contact with partially miscible solvents
b2- Immiscible solvents.
c.- Countercurrent Multiple Contact
c1- Solvent partially miscible in one of the feed components and completely miscible in the other
one.
c2-Immiscible solvents.

Liquid-liquid extraction (3)

Ternary Systems

Three-component systems and their graphical representation

a) Equilateral triangular coordinates
Each of the three corners represents a pure component. On each side there are all the binary mixtures of the two components
placed on the corners of this side. The points placed inside represent the ternary mixtures, and the relative amount in relation
to the mixture of each component is proportional to the distance from the point to the opposite side (a, b, c). Because of the
triangle height is equal to the sum of the three distances, relative amounts can be found when dividing each distance by the
sum of the three ones.
The segments a, b, c are proportional to the segments a, b, c (parallel to the triangle sides) and their sum is equal to the
triangle side value, and the following expressions can be assumed:

%A

a'
b'
c'
x100 %B
x100 %C
x100
triangle side
triangle side
triangle side

Properties:
1.- The compositions of mixtures which are represented by points belonging
to a straight line which is parallel to a triangle side have the same
concentration corresponding to the component placed on the opposite
vertex.
2.- All the points belonging to the segment which links a vertex to a opposite
side point represent mixtures which have the same ratio between the
concentrations of the components placed on the other two vertexes.
3.- When a pure component or a mixture (represented by P2) are added to a
mixture (represented by P1) the point P which represents the final
composition must be found of the segment P1P2 which links the points P1
and P2 and determines the segments P1P and P2P, which are inversely
proportional to the amounts of each point (lever rule), such that:

P1P amount of P2

PP2 amount of P1
Some problems where the previous properties are applied will be stated
below.
Liquid-liquid extraction (4)

Ternary Systems (Problems)

LLE-1. In order to prepare 500 kg of a solution which must contain 35% of HNO3 by weight, 20% of H2SO4 by weight and 45%
of H2O by weight there are available sulphuric acid of 98% by weight, nitric acid of 68% by weight and water. Calculate the
necessary amounts of each component, using the triangular diagram.
Solution:
On the triangular diagram the points corresponding with H2SO4 of 98% (point S on the side AB), with HNO3 of 68% (point N on
the side BC), with H2O (on the vertex B) and with the solution to be prepared (point P) are represented on the graph.
The intersection of the straight lines BP and SN gives the point M corresponding with the mixture of S and N, in such a way
that on adding B it can be reached the point P (xM = 0,4865).
C
HNO3

It is accomplished that:

M PB
0,35 0,00

2,564
B MP 0,4865 0,35
M= 2,564 B
M+B = 500 B= 140,3 kg ; M = 359,7 kg

S MN 0,68 0,4865

0,3983
N SM 0,4865 0,00
S= 0,3983 N

S+N = M 359,7 N= 257,3 kg

A
H2SO4

S = 102,4 kg

B
H2O

Liquid-liquid extraction (5)

Ternary Systems (Problems)

LLE-2. 1000 kg of an acid mixture whose composition by weight is 30% of H2SO4, 20% of HNO3 and 50% of water must be
changed for another whose composition by weight is 30% of HNO3, 50% of H2SO4 and 20% of H2O by adding H2SO4 of 98%
and HNO3 of 90%. Calculate the necessary amounts of the two acids which must be added, using the triangular diagram.
Solution:
The values are placed on the triangular diagram and having into account the above statement.

C
HNO3

F FP M MP M=F

FP
0,30- 0,20
= 1000
2000
MP
0,35 0,30

S SM N NM S N

0,90 0,35
1,58N
0,35

and the following system must be solved:

S N 2000

S 1,58N
The solution is: S = 1225 kg H2SO4 and N = 775 kg HNO3

A
H2SO4

B
H2O

Liquid-liquid extraction (6)

Ternary Systems

When the solvent is partially miscible with one component of the mixture and completely miscible with the
other component the ternary systems of the figure are obtained. With the aim of simplify the study of ternary
systems, the following nomenclature will be followed: on the vertex C is placed the solute to be extracted,
on the vertex A is placed the original solvent partially miscible with the solvent (added later), placed on the
vertex B. It may be considered the ternary system most frequently found.
When dealing with a mixture of A and B, represented by D, the
mixture will separate into two liquid phases, represented by E and
R, if the two solvents were totally immiscible E and R match B
and A.
If C (miscible in A and B) is added to the mixture D, C will
distribute between the two phases and conjugate ternary
solutions will be formed (E1,R1); (E2, R2),...the relative proportion
of the two phases is varying according to the relations D1R1/D1E1,
D2R2/D2E2, etc., until reaching the point D where the two phases
will disappear.

When starting from mixtures like F, G and H, and C

is added, the points F, G i H are obtained and they
determine the binodal solubility curve. All the
mixtures with overall compositions placed inside the
binodal solubility curve will split into two conjugate
phases with compositions placed on the binodal
solubility curve. The straight lines which link pairs of
points corresponding with conjugate phases are
called tie lines.

Liquid-liquid extraction (7)

Ternary Systems

The slope of the tie lines is function of the concentrations and the mixture components. According to the
below figures it may be stated the following:
Case a) The phase E is richer in C than the phase R.
Case b) The phases E and R have a similar concentration in C.
Case c) The phase R is richer in C that the phase R.

If C increases the concentrations of the two phases come closer until reaching the point P where the two
phases have the same concentration and they turn into one phase (critical point or plait point).
Also, there are more complex ternary systems as shown in the figures below:

Liquid-liquid extraction (8)

Ternary Systems

Interpolation of tie lines

Alders Method:
When the binodal solubility curve and the tie lines have been drawn from the experimental data, parallel
straight lines to the triangle sides are drawn as shown in the below figure. Points where the straight lines cut
make the curve ILMKHLM (conjugate line) which cuts the binodal curve at the plait point. To draw a tie line
passing through the point S, it must be drawn a parallel straight line to CB which will cut the conjugate line
at the point R from where the parallel straight line to AC is drawn, its intersection with the binodal curve
gives the point S, which is the conjugate phase of the point S.

Sherwood Method:
The conjugate line is found in a similar way that by applying the Alders
Method.

Liquid-liquid extraction (9)

Calculations in Ternary Systems

All such processes require:

1.- Bringing the solvent and solution into intimate contact.
2.- Separation of the resulting two phases.
3.- Removal and recovery of the solvent from each phase.

Single-stage batch extraction

Solvent partially miscible with one of the feed components and completely miscible with the other
one.
This extraction system is drawn in the figure below:

The evolution of this kind of extraction has been drawn on a ternary diagram. From the figure it can be seen
that for having two phases it is necessary to be inside the binodal curve. If the overall composition M1 must
be obtained, the necessary amount of solvent can be calculated by means of a mass balance on the
component C:
F xF xM1
FxF
B1
that is
xM1
xM1
F B1

Liquid-liquid extraction (10)

Calculations in Ternary Systems

The point M1 may be graphically calculated taking into account that M1 must be on the straight line FB and it
must be accomplished:
amount of B M1F

amount of F M1B

E1 and R1 may be calculated applying a mass balance if their compositions x1 and y1 are known and which
can be read where the tie line which passes through M1 intersects the binodal curve.
The values are:
M(1 x M1 x 1 )
y 1 x M1
E1
R1 F B1 E 1 M1
y1 x1
y1 x1
The above equations can be used to calculate E and R gives:

E '

F( x F X )
Y X

R' F E '

If the solvent is not a pure component (S) and the mixture is not
a binary composition (it may contain an amount of solvent used
in the extraction, F), the evolution of this case may be on the
ternary diagram. It can be inferred:

x M1

Fx F S1x s
F S1

S1

F( x F x M1 )
x M1 x s

Also, the remainder quantities can be calculated in the same way.

1

Liquid-liquid extraction (11)

Single stage batch extraction (Problems)

LLE-3. A mixture of acetic acid (30%) and chloroform weighting 100 kg is treated with water at 18C with the
aim of extracting the acetic acid. Calculate:
a) The amounts of water, minimum and maximum, to be added.
b) The maximum concentration reached by the acetic acid in the extracted product.
c) The amount of water to be added to obtain the maximum concentration of the extracted product.
Equilibrium data of the liquid phases at 18C corresponding to the tie line ends are shown on the below
table.
Solution:
Heavy phase (% by weight)
Light phase (% by weight)
a) The minimum amount of solvent will be the needed
CHCl3
H2O
CH3COOH CHCl3
H2O
CH3COOH
one to saturate the mixture. In other words, to reach
99.01
0.99
0.00
0.84
99.16
0.00
the two phases zone (punt D), where its composition
read on the ternary diagram is xD = 0.283. Applying a
91.85
1.38
6.77
1.21
73.69
25.10
mass balance on the component C (acetic acid):
80.00
2.28
17.72
7.30
48.58
44.12
70.13

4.12

25.75

15.11

34.71

50.18

FxF = DxD = F + Bmn xD

67.15

5.20

27.65

18.33

31.11

50.56

59.99

7.93

32.08

25.20

25.39

49.41

100 x 0.30 = 100 + Bmn 0.283 Bmn = 6 kg

55.81

9.53

34.61

28.85

23.28

47.87

Taking this minimum amount of B, the amount of

extract would be infinitesimal and the extract one

would be maximum.
The maximum amount of solvent to be used would be that one which gives an infinitesimal amount of
raffinate (maximum amount of extract), i.e. the necessary amount for reaching the point G on the binodal
curve, where the composition value is xG = 0.005.
Applying a mass balance on the component C (acetic acid) gives:
Fx F = GxG = F + Bmx xG
100 x 0.30 = 100 + Bmx 0.005 Bmx = 5900 kg
Liquid-liquid extraction (12)

Single stage batch extraction (Problems)

b) The straight line BE must be tangent to the binodal curve and the point of tangency will give the
maximum composition of the extracted product. On the ternary diagram may be read:
Y = 0.955; i.e. 95.5% by weight of acetic acid

y = 0.28

c) A tie line is drawn passing through the tangency point T and its intersection with the straight line FB gives
the point M where the composition read on the ternary diagram is xM = 0.185. The necessary amount of
water will be:
B

100 0.30 - 0.185

62.2 kg
0.185

Liquid-liquid extraction (13)

Single stage batch extraction with immiscible solvents

Immiscible solvents
If the components A i B are completely immiscible each other the calculations are easier. The
concentrations of each phase will be referred to the component whose amount does not change:
x '(

weight of C mol of C
,
)
weight of A mol of A

y '(

weight of C mol of C
,
)
weight of B mol of B

Applying a mass balance on the component C gives:

AxF' By s' Ax1' By1'

Rearranging gives:

A( x1' xF' ) B( y1' ys' )

y 1' y s'
A

'
'
B
x1 x F

The above straight line equation (operating line) allows

to calculate the equilibrium concentrations on the point where
intersects the equilibrium curve.
'
'
If the equilibrium line is a straight liney 1 mx 1
Substituting the straight line equation in the operating line
gives:
x1'

A
A mB

xF'

1
xF'
1 m(B / A)

In case of dealing with a pure solvent (above).

Dealing with a recycled solvent with concentration ys gives:

x 1' x F'

y s'
m

1
y S'

m
1 B

Liquid-liquid extraction (14)

Single stage batch extraction with immiscible solvents (Problems)

LLE-4. Acetone must be separated from an aqueous solution whose concentration in acetone is 20% by
weight. The extraction must be carried out using pure benzene at 15C. Calculate:
a) The extract and raffinate compositions if the amount of benzene used is 2 kg per kg of mixture to be
extracted.
b) The amount of benzene needed when extracting 100 kg of mixture if the acetone concentration in
raffinate should not exceed 3% by weight.
The equilibrium data for this system at 15C and corresponding to the ends of the tie lines are shown on the
below table.
Aqueous phase

Benzene phase

Solution:

Benzene

Acetone

Water

Benzene

Acetone

Water

0.1

5.0

94.9

95.2

4.7

0.1

0.1

10

89.9

89.0

10.8

0.2

0.3

20

79.7

73.4

26.1

0.5

0.7

30

69.3

55.2

43.0

1.8

1.4

40

58.6

39.1

56.5

4.4

3.2

50

46.8

27.6

63.9

8.5

a) Calculating the values of x (kg of acetone/kg of

water) and y (kg acetone/kg benzene) from the
equilibrium data gives:
x' =

5
4.7
0.0526 y' =
0.0494
94.9
95.2

x' =

10
10.8
0.1112 y' =
0.1213
89.9
89.0

Calculating the remainder values in the same way

gives:
x

The composition of the mixture to be extracted is:

0.0526

0.0494

0.1112

0.1213

xF'

0.2509

0.3556

0.4329

0.7789

0.6826

1.4450

1.0684

2.3152

20
0.25
80

The solvent is pure benzene:

y 's 0

The A/B ratio will be: A/B = 0.80/2 = 0.40

Liquid-liquid extraction (15)

Single stage batch extraction with immiscible solvents (Problems)

Using x-y coordinates the following lines are drawn: the equilibrium curve and the straight line of slope
-0.40 passing through the point (0.25; 0). Their intersection gives the extract and raffinate concentrations:
x1' 0.070
y1' 0.070

b) The extract concentration in equilibrium with 3/97 = 0.031 is

calculated from the equilibrium curve or by interpolating in the
data table:
'
y1 0.033

Applying the equation below:

y '1 y 's
A

'
'
B
x1 x F

Substituting the values gives:

B xF' - x1' 0.25 0.031

6.63 kg of benzene / kg of water

A
y1'
0.033

The total amount of benzene needed to extract 100 kg of mixture, where there are 80 kg of water, will be:
B = 6.63x80 = 530.4 kg of benzene

Liquid-liquid extraction (16)

Co-current multiple contact with partially miscible solvents

Co-current Multiple Contact

It is the repetition of the single stage extraction when the raffinate leaving the stage is brought into contact
by adding new solvent in the following stage and so on. Finally, the extracts obtained are joined together.

Co-current contact with partially miscible solvents

Representation on the ternary diagram is similar to that
obtained by a single stage. Applying a mass balance on the n-stage gives:

x Mn

Rn 1x n 1 Rn 1x n 1

Mn
Rn 1 Bn

Bn

Rn (1 x n 1 x M n )
M n( x M n x n )
En
x Mn
ym xn

The raffinate is the corresponding to that leaving the last stage.

The raffinate product is calculated by using the intersection
of the straight line which passes through B and
R3 (corresponding to the last raffinate) and its intersection
with the side AC. The amount and composition of the extract E
is calculated by applying mass balances and the extracted product
is found on the intersection of the straight line BE and the side AC.

Liquid-liquid extraction (17)

Co-current contact with partially miscible solvents (Problems)

LLE-5. A mixture of A and C weighting 100 kg and containing 30% of C is extracted in co-current contact
adding the solvent B . The extraction is carried out in three stages adding 50 kg of B to each one.
Calculate:
a) The amount and composition of the extract and raffinate in each stage.
b) The amount and composition of the extracted and raffinate product.
c) The maximum composition of C which can be obtained when using this extraction method.
The compositions of the conjugate phases expressed in percent by weight are shown on the table below.
Extract

Raffinate

A
95.0

B
5.0

C
0.0

A
10.0

B
90.0

C
0.0

0.00

0.053

0.00

9.000

92.5

5.0

2.5

10.1

82.0

7.9

0.026

0.053

0.44

4.555

89.9

5.1

5.0

10.8

74.2

15.0

0.053

0.054

0.58

2.876

87.3

5.2

7.5

11.5

67.5

21.0

0.079

0.055

0.646

1.985

84.6

5.4

10.0

12.7

61.1

26.2

0.106

0.057

0.674

1.570

81.9

5.6

12.5

14.2

55.8

30.0

0.132

0.059

0.679

1.263

79.1

5.9

15.0

15.9

50.3

33.8

0.159

0.063

0.680

1.012

78.3

6.2

17.5

17.8

45.7

36.5

0.186

0.066

0.672

0.850

73.4

6.6

20.0

19.6

41.4

39.0

0.221

0.071

0.665

0.690

67.5

7.5

25.0

24.6

32.9

42.5

0.270

0.081

0.643

0.513

61.1

8.9

30.0

28.0

27.5

44.5

0.329

0.098

0.614

0.379

54.4

10.6

35.0

33.3

21.7

45.0

0.391

0.119

0.575

0.277

46.6

13.4

40.0

40.5

16.5

43.0

0.461

0.155

0.515

0.198

43.4

15.0

41.6

43.4

15.0

41.6

0.492

0.176

0.492

0.176
Liquid-liquid extraction (18)

Co-current contact with partially miscible solvents (Problems)

Solution:
The data of the previous table are drawn on a ternary diagram as below.
1st stage.- The straight line BF is drawn on the ternary diagram and the point M1 is found on this straight
line, considering that:
M1 = F + B1 = 100 + 50= 150 kg
FxF + B1 0 = 150xM1 1000.3 + B10 = 150xM1

xM1 =

1000.30
0.20
150

Look out!:There is a
mistake when drawing
the straight line

Liquid-liquid extraction (19)

Co-current contact with partially miscible solvents (Problems)

The compositions of extract and raffinate are read on the points where the tie line that passes through the
point M1 intersects the binodal curve, their values are:
y1 = 0.28
x1 = 0.11
The amounts of extract and raffinate will be:
R1(0.20 0.11) E1(0.28 0.20) E1 79.41kg

E1 R1 150
R1 70.59 kg

2nd Stage.- The straight line BR1 is drawn and on the point M2 on this straight line:
M2 = R1 + B2 = 70.59 + 50= 120.59 kg
M2xM2 = R1 0.11+ B20

xM2 =

70.59 x 0,11
0.064
120.59

The extract and raffinate compositions leaving this stage are read on the intersections of the tie line which
passes through the point M2 and the binodal curve; their values are:
y2 = 0.100

x2 = 0.031

The amounts of raffinate and extract will be:

R2 (0.064 0,031) E2 (0.10 0.064) E2 57.63 kg

E2 R2 120.59
R2 62.96 kg

Liquid-liquid extraction (20)

Co-current contact with partially miscible solvents (Problems)

3th Stage.- Proceeding in the same way that in the previous stages:
M3 = R2 + B3 = 62.96 + 50 = 112.96 kg

y3 = 0.023

x M3 =

62.96 x 0.031
0.017
112.96

x3 = 0.008

R3 (0.017 0.008) E3 (0.023 0.017) E3 67.77 kg

E3 R3 112.96
R3 45.19 kg

b) The composition of the solvent read on the diagram (point R3) is 0.050; so, the amount of raffinate product
will be:
R = 45.19 (1-0.050) = 42.93 kg
The composition of raffinate product is read on the intersection of the straight line BR3 and the side AC, the
value is: X = 0,009.
The total amount of extract will be: 79.41 + 57.63 + 67.77 = 204.81 kg
The amount of C in the extract will be:
79.41x0.28 + 57.63x0.100 + 67.77x0.023 = 29.55 kg
The amount of A in the extracted product will be:
Amount of A in the feed amount of A in the raffinate product:
100(1 - 0,30) 42.93(1 - 0,009) = 27,45 kg
The total amount of extracted product will be:
E = 29,55 + 27.45 = 57.0 kg
The extract composition will be:
xE = 29.55/204.81 = 0.144
The composition of extracted product will be:
Y = 29,55/57.0 = 0,518
c) The maximum concentration of C which can be obtained in the extracted product is that is read on the point
of the side AC intercepted by the straight line BE tangent to the binodal curve, in this case the value will be
68% and it is reached when applying the first stage.
Liquid-liquid extraction (21)

Co-current contact with immiscible solvents

Co-current contact with immiscible solvents

In this case the solvent B is miscible with the component to be extracted C and completely immiscible with
A. The equilibrium concentrations of the point (x1, y1) are found on the intersection of the straight line
calculated before:
y 1' y s'
A

B
x 1' x F'
and the equilibrium curve. If the raffinate R1 is extracted using new solvent B2, the new equilibrium
concentrations are found on the intersection of the straight line with slope A/B2 and the equilibrium curve
and so on for each stage until reaching the required raffinate concentration.

When the equilibrium line is a straight line y = mx, the solute which has not been extracted in the raffinate
leaving the last stage is:
x'
log n'
1
'
xF
x n'
x

n F
1 Bm
1 Bm
log

where n is the number of stages.

Liquid-liquid extraction (22)

Co-current contact with immiscible solvents (Problems)

LLE-6. An aqueous solution weighting 1000 kg contains 0,3% of benzoic acid which must be extracted by
means of an co-current extraction process consisting in two stages at 20C using 1800 kg of benzene as
solvent in each stage. Calculate the percent of benzoic acid extracted. The equilibrium data at 20C are
shown on the below table.
x (g of benzoic acid/kg of water)

0.915

1.135

1.525

2.04

2.56

3.99

5.23

y (g of benzoic acid/kg of benzene)

1.025

1.60

2.91

5.33

7.94

20.1

36.0

Solution:

Considering that benzene is immiscible in water the diagram x (g of benzoic acid/kg of water), y (g of
benzoic acid/kg of benzene). Using the data of the table the equilibrium curve can be drawn. On the x-axis
the point corresponding to the feed is drawn:
xF' =

3
g cid
3
1 - 0.003
kg aigua

The slope of the operating line passing through this point is:
-A/B1 = -997/1800 = -0.555
The intersection of this straight line and the equilibrium curve gives the extract and raffinate concentrations
leaving the first stage:

x1' 0.00096 kg benzoic acid/kg water

y1' 0.00113 kg benzoic acid/kg benzene

The feed of the second stage is the raffinate of the first stagex1' 0.00096 which is extracted using 1800 kg
of benzene. Consequently, for this stage the operating line is drawn passing through the point 0.00096 on
the x-axis and whose slope is:
-A/B2 = -0.555
Liquid-liquid extraction (23)

Co-current contact with immiscible solvents (Problems)

The intersections of this straight line with the equilibrium curve are:
x2' 0.00042

y 2' 0.00030

Calculating the benzoic acid extracted gives:

Before starting the extration: 3

After ending the extraction :

0.42

g of benzoic acid
x997 kg of water = 2991g of benzoic acid
kg of water

g of benzenic acid
x 997 kg of water = 418.74 g of benzoic acid
kg of water

Amount of benzoic acid extracted = 2991 g 418.74 g = 2572.26 g

And the percent of benzoic acid extracted will be: 2572.26/3000 = 0.857 (85.7%)
Liquid-liquid extraction (24)

Countercurrent multiple contact with partially miscible solvents

Countercurrent Multiple Contact

Feed and solvent enter through the opposite ends of the extraction system. In the first stage the feed
comes into contact with the solvent which is rich in solute. In the following stages the raffinates are
extracted with solvents whose concentration in solute is decreasing. Thus, the concentration in solute of the
raffinate is decreasing from the first stage to the last one while the concentration in solute of the extract is
increasing from the last stage to the first one. This layout uses less solvent than the co-current extraction
method.

Countercurrent contact with partially miscible solvents

Applying a mass balance on the overall system:

F B E1 Rn M
The point M must be found on the ternary diagram.
It must be on the straight line FB and it must be accomplished:
FxF F B xM xM

FxF
F B

Rearranging the balance equation gives

F E1 Rn B P
The above equation points out that the difference between the inlet and outlet flows which enter through the
opposite ends is constant.
Liquid-liquid extraction (25)

Countercurrent multiple contact with partially miscible solvents

Applying a mass balance on any stage it can be seen that the difference between the inlet and outlet flows
of this stage is the same that the corresponding to the ends of the extraction system, i.e. the difference
keeps constant in the whole system:
R1 B E2 Rn R1 E2 Rn B P

The equation F E1 Rn B P points out that the straight lines which link F with E1 and Rn with B must
have a common point P (Pole or operating common point). The straight lines PE intersect points on the
binodal curve which are the extract and the raffinate of two adjacent stages. Once the point P is set the
number of stages are calculated graphically.
The points F, E1, Rn, M and P are set and the tie line passing through E1 is drawn giving R1. The straight
line PR1 is drawn and E2 is obtained. Taking the tie line which passes through E2 gives R2 and so on, until
reaching the value of R corresponding to Rn.
The composition of the extracted product will be the intersection of BE1
and AC, the composition of the raffinate product will be the intersection
of BRn and AC.

To calculate E1 i Rn:

E1y1 M E1xn MxM

E1

M xM x n
y1 x n

Rn F B E1 M E1

Liquid-liquid extraction (26)

Countercurrent multiple contact with partially miscible solvents (Problems)

LLE-7. In order to reduce the content of diphenylhexane from 50% by weight in the mixture to less than
10% by weight in the raffinate product, a mixture of diphenylhexane-docosane is extracted in countercurrent
with furfurol at 45C. Calculate the number of theoretical stages required to achieve the concentration of
diphenylhexane indicated if 800kg furfurol/500kg feed are used.
The table below shows the concentrations which define the points of the binodal curve for the mixture at
45C.
Furfurol

Diphenylhexane

Docosane

Furfurol

Diphenylhexane

Docosane

0.040

0.000

0.960

0.500

0.423

0.077

0.050

0.110

0.840

0.600

0.356

0.044

0.070

0.260

0.670

0.700

0.274

0.026

0.100

0.375

0.525

0.800

0.185

0.015

0.200

0.474

0.326

0.900

0.090

0.010

0.300

0.487

0.213

0.993

0.000

0.007

0.400

0.468

0.132

The below table shows the equilibrium compositions which determine tie lines.
Furfurol

Difenilhex

Docos

Furfurol

Difenilhex

Docos

0.048

0.100

0.852

0.891

0.098

0.011

0.065

0.245

0.690

0.736

0.242

0.022

0.133

0.426

0.439

0.523

0.409

0.068

Solution:
Using the above tables the binodal curve and tie lines are drawn. The point M is set on the straight line FB
considering:
xM =

500 x 0,50
0.192
800 + 500

Liquid-liquid extraction (27)

Countercurrent multiple contact with partially miscible solvents (Problems)

The composition of the raffinate leaving the last stage Rn, is read on the intersection of the straight line RB
and the binodal curve in the zone corresponding to the raffinate, its value is xn = 0.093.
The composition of the extract leaving the first stage y1, is found on the intersection of the straight line RnM
and the binodal curve in the zone corresponding to the extract, its value is y1 = 0.216.
The pole P is set on the intersection of the straight lines FE1 and RB. The composition of the raffinate
leaving the first stage is set on the intersection of the binodal curve and the tie line which passes through
E1; its value is x1 = 0.215.
If the straight line R1P is drawn the point E2 is located where y2 = 0,050. Drawing the tie line which passes
through the point E2 the value of R2 is found: x2 = 0,052. This value is lower than that of the raffinate to be
obtained. Consequently, two theoretical stages are required.

Liquid-liquid extraction (28)

Countercurrent multiple contact with immiscible solvents

Countercurrent contact with immiscible solvents

In this case the solvent B is immiscible with the solvent A.

x' weight of C

weight of A

y ' weight of C

weight of B

Applying a mass balance on the overall extraction process:

A y1' y 0'
'
'
'
'
AxF By 0 Ax n By1
B xF' xn'

On the x-y axis the operating line is a straight line whose slope is A/B and passing through the points
xF' , y1' and xn.' , y 0' . The number of theoretical stages is the number of steps traced between the
equilibrium curve and the operating line.

Liquid-liquid extraction (29)

Countercurrent multiple contact with immiscible solvents (Problems)

LLE-08. 100 kg of a 20% solution of acetone (by weight) in water are extracted at 25C in countercurrent
with monochlorobenzene which contains 0.4% of acetone with the aim of decreasing the content of
acetone. Considering that the monochlorobenzene and water are immiscible in the extraction conditions,
calculate:
a) The minimum amount of solvent required if the acetone concentration in the raffinate should not exceed
2%.
b) The number of theoretical stages required if the amount of solvent to be used is 25% higher than the
minimum.
Equilibrium data for this ternary system at 25C are shown in the below table.

Solution:
a)
xF'

x (kg acetone/kg water)

0.0258

0.0739

0.1605

0.267

y(kgacetone/kg monochlorobenzene)

0.0258

0.0754

0.156

0.236

F = 100 kg

xF = 0.20

0.20
0.25 kg acetone/kg water
1 - 0.20

y 0' =

water = 100( 1 0.20 ) = 80 kg

xn' =

0.02
0, 020 kg acetone/kg water
1 - 0.02

0.004
0.004 kg acetone / kg monochlorobenzene
1 - 0.004

The operating line must pass through the point:

xn' 0.0204

y 0' 0.004

If the minimum amount of solvent is used, the number of stages must be infinite, this condition is
'
accomplished if the straight line intersects the equilibrium curve on the point M when xF 0.25 ; at this point
the value of y is y = 0.224.
Liquid-liquid extraction (30)

Countercurrent multiple contact with immiscible solvents (Problems)

Applying the equation corresponding to this extraction process gives:

A
0.224 0.004

0.958
Bmn 0.25 0.0204
A
80
Bmn =

83.5 kg
0.958 0.958

b) If the amount of solvent used is 25% higher than the minimum: B = 83.5x1.25 = 104.4 kg

A
80

0.776
B 104.4
y1' 0.766 0.25 0.0204 ) 0.004 0.187

The equilibrium stages are drawn on the graph and

approximately 5.5 theoretical stages are obtained.

Liquid-liquid extraction (31)