Separation Process I

CDB2013
Dr Chew Thiam Leng

Chapter
Liquid-Liquid
Extraction

Lesson outline
Introduction

Working principles of liquid-liquid processes

General design considerations

Liquid-liquid equilibrium/equilibrium relation in

extraction processes
Single-stage equilibrium extraction
Continuous multiple stage countercurrent
extraction

Lesson outcome
At the end of the session, the students are able to:
1. Discuss the principles of liquid-liquid processes and
basic design considerations.
2. Able to estimate the exit stream amounts and
compositions of single stage extractor.
3. Able to conduct total and component material balance
on multistage liquid-liquid extraction equipment.

4. Able to estimate the number of stages required to

achieve the desired separation in liquid-liquid
extraction processes.

Recap of pervious lesson

Working principles of absorption and desorption
(stripping)
General design considerations

Gas-liquid equilibrium
Countercurrent Multiple-Contact Stages
Determination of multiple stages required for a desired
separation using
Material balance and graphical method
Analytical Equations (Kremser Equation)

Introduction
Liquid-liquid extraction (solvent extraction): is the separation of the
constituents of a liquid solution by contact with another insoluble
liquid.
It is a mass transfer operation in which a liquid solution (feed) is
contacted with an immiscible or nearly immiscible liquid (solvent)
that exhibits preferential affinity or selectivity towards one or more
of the components in the feed.

Important terms
The solution which is to be extracted is called the feed,
the liquid with which the feed is contacted is called the solvent.
The solvent rich product of the operation is called the extract,
the residual liquid from which the solute has been removed is
the raffinate.

Working Principles of Liquid-liquid

extraction
When Liquid-liquid extraction is carried out in a test tube or flask
the two immiscible phases are shaken together to allow molecules
to partition (dissolve) into the preferred solvent phase.
C
SOLVENT

C+A+B

EXTRACT
RAFFINATE
B+A+C
A+B
FEED

 In liquid-liquid extraction, a soluble component (the

solute) moves from one liquid phase to another.

The two liquid phases must be either immiscible, or

partially miscible.
usually isothermal and isobaric

can be done at low temperature

(good for thermally fragile solutes, such as large organic molecules or
biomolecules)

extracting solvent is usually recycled, often by

distillation.
can be single stage (mixer-settler) or multistage
(cascade)

 An example of extraction:

Extract (C+A+B)
Acetic acid (A)
in Water (B)
+
Ethyl acetate
(C)

Organic layer contains most of

acetic acid in ethyl acetate with a
small amount of water.

Raffinate (B+C+A)
Aqueous layer contains a weak
acetic acid solution with a small
amount of ethyl acetate.

The amount of water in the extract and ethyl

acetate in the raffinate depends upon their
solubility's in one another.

10

Typical liquid-liquid extraction

equipment

Laboratory separation funnel

Typical liquid-liquid extraction

equipment
Mixer-settler for Extraction

a) Separate mixer-settler

b) Combined mixer-settler
12

Typical liquid-liquid extraction

equipment
Mixer-settler for Extraction

13

Typical liquid-liquid extraction

equipment
Mixer-settler for Extraction

Advantages

Disadvantages

Reliable scale up techniques.

Large amounts of floor space

required.

Can handle high flow rates.

Only systems with a few stages

are economical.

Ideal for processes with slow

mass transfer.

Large amounts of valuable

material, such as the solvent, are
tied up during the process.

Intense mixing, resulting in small

droplets for good mass transfer.

Poor solvent conservation.

14

Typical liquid-liquid extraction

equipment
Spray Extraction Tower

Spray Extraction Tower

Vessel in which the mixing
is done by the flow of the
fluid themselves,
mixing
and
settling
proceed continuously and
simultaneously.

Typical liquid-liquid extraction

equipment
Spray Extraction Tower
Advantages
It has no internal parts except for
the spray nozzles and hence
eliminate the scale buildup and
plugging problem.
Low cost

Disadvantages
Inefficient.

Typical liquid-liquid extraction

equipment
Packed Extraction Tower

The column consists of

a packed bed,
distributors for
the two liquid

Typical liquid-liquid extraction

equipment
Packed Extraction Tower
Advantages

Disadvantages

Highly efficient when only a few

stages are needed.

Suffer from solids plugging

The random packings in the tower

cause the droplets to coalesce and
redisperse at frequent intervals
throughout the tower

The initial dispersion is a concern

for packed columns, to avoid
channeling

Reduced axial mixing

Hard to scale up accurately

Typical liquid-liquid extraction

equipment
Mechanically agitated extraction tower
Drive Motor

Gearbox
Light
Phase Out

Heavy
Phase In

Vessel Shaft
Walls

Stators Rotors

Light
Phase In
Interface

rotating-disk contactor
a. agitator; b. stator disk
Interface
Control

Heavy
Phase Out

Mixer-settlers operate with a purely stage-wise contact.

After every mixer there is a settler. Mixer-settlers can be
operated in a multistage, co- or countercurrent fashion.

Typical liquid-liquid extraction

equipment
Mechanically agitated extraction tower
Advantages
Mechanical parts result in good
dispersion.
Little axial mixing compared to
non-agitated columns

Disadvantages
Repair of internal mechanical
parts can cause process delays.

General Design Considerations

Some factors that influence extraction processes are:
Type of stage configurations

Minimum solvent flow rate and actual flow as multiple of

minimum flow rate (or reflux for more than one stage system)
Operating conditions
Choice of liquid solvents

Number of equilibrium stages

Emulsification and scum formation tendencies
Phase-density difference
Interfacial tension
Type of extractor

General Design Considerations

Some characteristics of an ideal solvent:
High selectivity for targeted solute to be extracted
High capacity for dissolving solute
Mininum or no corrosion problem.
Large density difference with carrier
High thermal and chemical stability
No or low toxicity
Low price

Equilibrium relations in extraction

Extraction involves the use of systems of at least
three substances. The most important notation
scheme for extraction are:
1. Liquid B and C are pure, substantially insoluble
liquids, and A is the distributed solute.
2. Mixtures to be separated by extraction composed of A
and B where as C is the extracting solvent.
3. Equilateral triangular coordinates are often used to
represent the equilibrium data for a three component
systems as shown in the figure;

Ternary relationship
1.

Each altitude of the triangle

represents 100% pure component
and the distance to the three sides
represents the percentages or the
fractions of the three components.

2.

Point M represents the mixture of

the three components
Any point on the side of the triangle
represents a binary mixture
Point D for example contains a
fraction of 0.8 A and 0.2 B.

3.
Fig.: Triangular diagram

4.

The perpendicular distance from any point such as M to the base AB

represents the mass fraction of C in the mixture at M, the distance to
the base AC of B, and that to the base CB the mass fraction of A. Thus,
at point M;
xA + xB + xC = 0.40 + 0.20 + 0.40 = 1.0

Ternary relationship when A and B are

partially miscible phase
This is the most common type of systems in extraction

Example:
i.

water (A)-chloroform(B)-acetone (C) and

ii. methyl isobutyl ketone (A)-water (B)- acetone (C)

iii. benzene (A)-water (B)-acetic acid (C)

Fig.: Liquid-liquid phase diagram where components A & B are partially miscible

Liquid C dissolves completely in A and B, but Liquid A is only slightly

soluble in B and B slightly soluble in A.
The two phase region is included inside below the curved envelope.
Point M represents a mixture of the two phases.
The more insoluble the liquid A and B , the nearer the apexes of the
triangle will points L and K be located.
26

 Curve LPK is a bimodal solubility

curve indicating the change in solubility
of the A-and B-rich phases upon addition
of C.

Any mixture outside the curve is a

homogenous mixture of one phase liquid.
Any ternary mixture underneath the curve, such as M, will form two
insoluble saturated liquid phase of equilibrium compositions indicated
by a (A-rich) and b (B-rich).

An original mixture of composition M will separate into two

phases a and b which are on the equilibrium tie line through
point M.

The two phases are identical at point P, the Plait point.

Reading ternary phase diagram

Example: Define the composition of point A, B, C, M, E, R, P and DEPRG
in the ternary-mixture.

28

Example 5.1
Any point on the side of the triangle represents a binary mixture
Define the composition of point A, B, C, M, E, R, P and DEPRG in the ternary-mixture.
Point A = 100% Water
Point B = 100% Ethylene Glycol
Point C = 100% Furfural
Point

30% Ethylene glycol,

40% water, 30% furfural

Point E = 43.8% glycol, 10% water,

46.2% furfural
Point R = 11% glycol, 81% water,
8% furfural

The miscibility limits for the furfuralwater binary system are at point D and
G.
Point P (Plait point), the two liquid phases
have identical compositions.

DEPRG is saturation curve or bimodal

curve
29

Example 5.2
From the diagram below determine the concentrations (mole fractions) at
Point M, E and R?

30

Solution
Consider the point M:

water content (xA) :

0.19

Ethylene glycol content (xB):

0.20

Furfural content (xC):

0.61

check: xA + xB + xC = 1

Do the same for point E, R and P.

31

Equilibrium data on rectangular

coordinates
Since triangular coordinates have some disadvantage due to the special
coordinates, in order to be able to expand one concentration scale relative
to the other, a more useful method of plotting the three-component data is
to use rectangular coordinates.

The system acetic acid (A) water (B) isopropyl ether solvent (C).

The solvent pair B and C are partially miscible.

Raffinate compositions are represented by
coordinates: (xA, xC)
Extract compositions are represented by
coordinates: (yA, yC)
The concentration of B is obtained by
differences from equation below

xB = 1.0 - xA - xC
yB = 1.0 - yA - yC

The two phase region is inside the envelop.

The tie line gi is connecting the water-rich layer i
called the raffinate, x layer and the ether-rich
layer, g called the extract layer, y

Liquid-liquid Equilibrium
phase diagram

To construct the tie line gi using the equilibrium

yA-xA plot below the phase diagram , vertical
line to g and I are drawn

Overview of solution using

Rectangular diagram:
1. Find mixing point, h
2. Find tie-line through
and error);
3. Find

and

h (trial

at either end

(co-linear with h).

4. Find flow rates of g and i.

34

Example 5.3
An original mixture weighing 100 kg and containing 30 kg of
isopropyl ether (C), 10 kg of acetic acid (A), and 60 kg water (B) is
equilibrated and the equilibrium phases separated. What are the
compositions of the two equilibrium phases?

Solution:
Composition of original mixture is xc= 0.3, xA = 0.10, and xB = 0.60.

35

Solution
1. Plot the composition of xC =
0.30, xA = 0.10 and xB on the
equilibrium diagram as at
point h.
2. The tie line gi is drawn
through point h by trial and
error.
3. The composition of the
extract (ether) layer at g is yA
= 0.04, yC = 0.94, and yB =
1.00 - 0.04 - 0.94 = 0.02
mass fraction.
4. The raffinate (water) layer
composition at i is xA = 0.12,
xC = 0.02, and xB = 1.00
0.12 0.02 = 0.86.
36

Equilibrium contact stages

Single stage equilibrium extraction
As shown in Figure below the equation can be derived using
rectangular coordinates.
Two streams containing L kg and V kg containing component A,
B, and C are mixed to give a resulting mixture M total mass.
Writing an overall mass balance and balance on A and on C
V
L

L+V=M

VyA + LxA = MxA,M = (V + L)xAM

mixer

VyC + LxC = MxCM = (V + L)xCM

5.2

5.3
5.4

 Combining Eqns (5.2) and (5.3)

y A x AM
L

V
x AM x A

(5.5)

Similarly combining Eqs (5.2) and (5.4)

yC xC M

V
xC M xC

V
M

(5.6)

Equating 5.5 and 5.6 and rearranging

xC xC M
x A x AM

xC M y C
x AM y A

(5.7)

mixer

Eqn. 5.7 shows that points L, M, and V must lie on a straight line.
By using the properties of similar right triangles,
Lever arms rule

L( kg)
VM

V ( kg)
LM

L(kg)
VM

M (kg)
LV

(5.8)

(5.9)

similar triangles

Example 5.4
The compositions of the two equilibrium layers in Example 5.1 are
for the extract layer (V2) yA = 0.04, yB = 0.02, and yC = 0.94, and for
the raffinate layer (L1) xA = 0.12, xB = 0.86, and xC = 0.02. The original
mixture contained 100 kg and xAM = 0.10. Determine the amounts of
V1 and L0.

Given:

M= 100 kg, xAM = 0.10

extract layer (V2): yA = 0.04, yB = 0.02,

V1

raffinate layer (L1) xA = 0.12, xB = 0.86,

L0

Solution:

V2

L1

mixer

Substituting into eq. 5.2

V2 L1 M 100

Substituting into eq. 5.3, where M = 100 kg and xAM = 0.10,

V2 (0.04) L1 (0.12) 100(0.10)
40

Given:

M= 100 kg, xAM = 0.10

Extract layer (V2):

yA = 0.04, yB = 0.02,

Raffinate layer (L1) xA = 0.12, xB = 0.86,

V2

V1
L0

Required: V1 and L0
Solution:

L1

mixer

Substituting into eq. 5.2

V2 L1 M 100

( a)

Substituting into eq. 5.3, where M = 100 kg and xAM = 0.10,

V2 (0.04) L1 (0.12) 100(0.10)
0.04V2 0.121L1 10

(b)
41

Solving eqns (a) and (b) simultaneously,

L1 = 75.0 and V2 = 25.0.

Alternatively, using the lever-arm rule,

the distance hg in Figure below is
measured as 4.2 units and gi as 5.8 units.
Then by eq. 5.8,
L
L
h g 4.2

M 100 gi 5.8

Solving, L = 72.5 kg and V = 27.5

kg, which is a reasonably close
check on the material-balance
method.

similar triangles

Single-stage liquid-liquid extraction processes

Single-state equilibrium extraction
We now study the separation of A from a mixture
of A and B by a solvent C in a single equilibrium
stage.
An overall mass balance:
A balance on A:
A balance on C:

V1

V2

L0

L1

L0 V2 L1 V1 M

5.10

L0 x A0 V2 y A2 L1 x A1 V1 y A1 Mx AM

5.11

L0 xC 0 V2 yC 2 L1 xC1 V1 yC1 MxC M

5.12

x A x B xC 1.0

43

To solve the three equations, the equilibrium-phase-diagram is used.

V1

V2

L0

L1

1. L0 and V2 are known.

2. We calculate M, xAM, and xCM by using
equation 5.10-5.12.

3. Plot L0, V2, M in the Figure.

4. Using trial and error a tie line is drawn
through the point M, which locates the
compositions of L1 and V1.
5. The amounts of L1 and V1 can be
determined by substitution in Equation
5.10-5.12 or by using lever-arm rule.

44

Example 5.5
A mixture weighing 1000 kg contains 23.5 wt% acetic acid
(A) and 76.5 wt% water (B) and is to be extracted by 500
kg isopropyl ether (C) in a single-stage extraction.
Determine the amounts and compositions of the extract and
raffinate phases.

45

Solution
Given:

L0 1000kg , x Ao 0.235, xBo 0.765 and xCo 0

V2 500kg y A2 0, yB 2 0 and yC 2 1

V1

V2

L0

L1

L0 V2 1000 500 M 1500kg

L0 x A0 V2 y A2 Mx AM
(1000)(0.235) (500)(0) (1500) xAM

x AM 0.157
Similarly

xc0 1 xA0 xB0 1.0 0.235 0.765 0

L0 xC 0 V2 yC 2 MxC M

(1000)(0) (500)(1) (1500) xC M

xCM 0.33

V2 (0,1) = (yA2, yC2)

V1 (0.1,0.89) = (yA1, yC1)
M(0.157,0.33) = (xAM, xCM)
L1(0.2,0.03) = (xA1, xC1)
1. L0 and V2 are known.
2. We calculate M, xAM, and xCM
by using equation 5.10-5.12.

L0(0.235,0) = (xA0, xC

3. Plot L0, V2, M in the Figure.

4. Using trial and error a tie

line is drawn through the
point M, which locates the
compositions of L1 and V1.
5. The amounts of L1 and V1
can be determined by
substitution in Equation 5.105.12 or
Alternatively, by using leverarm rule.
47

From the graph: xA1 = 0.2 and yA1 = 0.1;

L1 xA1 V1 y A1 MxAM
L1 (0.2) V1 (0.1) (1500)(0.157)
L1 0.5V1 1,177.5

(1)

From the graph: xC1 = 0.03 and yC1 = 0.89;

L1 xC1 V1 yC1 MxC M

L1 (0.03) V1 (0.89) (1500)(0.33)

L1 29.67V1 16,500

(2)

Solving eq(1) and eq(2) to get L1 and V1;

L1 914.86kg and V1 525.28kg

xA1 0.2, y A1 0.1, xC1 0.03 and yC1 0.89

Answer
48

Exercise
A single-stage extraction is performed in which 400 kg of a solution
containing 35 wt% acetic acid in water is contacted with 400 kg of pure
isopropyl ether. Calculate the amounts and compositions of the extract
and raffinate layers. Solve for the amounts both algebraically and by
the lever-arm rule. What percent of the acetic acid is removed? Use
equilibrium data given below.

49

Solution
Given:

L0 V2 400 400 M 800kg

xA0 0.35, xB 0 0.65 and y A2 1.0

L0 x A0 V2 y A2 MxAM
(400)(0.35) (400)(0) (800) xAM
xAM 0.175
Given:

xc 0 1 xA0 xB 0 1.0 0.35 0.65 0

L0 xC 0 V2 yC 2 MxC M
(400)(0) (400)(1) (800) xC M

xCM 0.5
Draw the equilibrium diagram and Locate point,
L0, V1 and M
50

 Using trial and error, the tie

line is drawn through point
M that determines the
composition of LN and V1

V2 (0,1) = (yA2, yC2)

V1 (0.12,0.87) = (yA1, yC1)
M(0.175,0.5) = (xAM, xCM)
L1(0.22,0.03) = (xA1, xC1)

From the graph:

xA1 = 0.22 and
yA1 = 0.12;

M
L0(0.35,0) = (xA0,

L1 xA1 V1 y A1 MxAM
L1 (0.22) V1 (0.12) (800)(0.175)
L1 0.54V1 636.36

(i)

51

From the graph:

xC1 = 0.03 and
yC1 = 0.87;

L1 xC1 V1 yC1 MxC M

L1 (0.03) V1 (0.87) (800)(0.5)

L1 29V1 1,333.33

(ii)

Solving eq(i) and eq(ii) to get L1 and V1;

L1 623.12kg

and

V1 24.49kg

xA1 0.23, y A1 0.12, xC1 0.03 and yC1 0.88

52

V1 (0.12,0.88) = (yA1, yC1)

M(0.175,0.5) = (xAM, xCM)
L1(0.23,0.03) = (xA1, xC1)

Lever arms rule

L1 (kg) V1M

M (kg) L1V1

L1 (kg) 0.38

0.44
M (kg) 0.86

L1 (kg) V1M

V1 (kg) L1M

L1 (kg) 0.38

0.81
V1 (kg) 0.47

L1 (kg) 0.44 800kg 352kg

V1 (kg) 352kg / 0.81 434.57kg

53

The amount and composition of extract are

L1 325kg *

xA1 0.23, xC1 0.03 and xB1 0.74

The amount and composition of raffinate are

V1 434.57kg *
y A1 0.12,
yC1 0.88

and

yB1 0
*The correction of amount of extract and raffinate depends on the
identification of points on the graph (setting the pint). The value
obtained from Lever arms rule is more reliable.

54

The percent of acetic acid removed is about

%

=

% =

(400x0.35325x0.23)x100%
= . %
4000.35

55

3. A feed mixture weighing 200 kg of unknown composition

containing water, acetic acid, and isopropyl ether is contacted

in a single stage with 280 kg of a mixture containing 40 wt %
acetic acid, 10 wt % water, and 50 wt. % isopropyl ether. The

resulting raffinate layer weighs 230 kg and contains 29.5 wt. %

acetic acid,66.5 wt. % water, and 4 wt. % isopropyl ether.
Determine the original composition of the feed mixture and the
composition of the resulting extract layer.

(Use Equilibrium

data Given below

56

TABLE : Acetic acid-water-isopropanol ether liquid-liquid

equilibrium data
Water layer (wt%)

Acetic
acid

Isopropyl layer (wt%)

Water

Isopropyl
ether

Acetic acid

Water

Isopropyl
ether

98.8

1.2

0.6

99.4

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

13.30

84.4

2.3

4.82

1.9

93.3

25.50

71.1

3.4

11.4

3.9

84.7

36.70

58.9

4.4

21.6

6.9

71.5

44.30

45.1

10.6

31.10

10.8

58.1

46.40

37.1

16.5

36.20

15.1

48.7
57