LIQUID-LIQUID EXTRACTION

(LLE)
 Definition & Application

The separation of constituents (solutes) of a liquid solution by contact with another insoluble
liquid.

Solutes are separated based on their different solubilities in different liquid.

The separation process of the components of a liquid mixture by treatment with a solvent in
which one or more desired components is soluble.

The purpose of LLE is to separate closed-boiling point mixture [e.g. acetic acid (118°C) – water
(100°C)]

There are two requirements for liquid – liquid extraction to be feasible:

component (s) to be removed from the feed must preferentially distribute in the solvent.

the feed and solvent phases must be substantially immiscible

 Definition & Application

The simplest LLE involves only a ternary (i.e 3 component system)

Important terms you need to know:

Solute - The solution which is to be extracted

(denoted by component A)

Solvent - The liquid with which the feed is contacted

(denoted by component C)

Diluent - ‘Carrier’ liquid

(denoted by component B)

Extract - The solvent – rich product of the operation

Raffinate - The residual liquid from which solutes has been removed.
 Definition & Application

In some operations, the solutes are the desired product, hence the extract stream is the
desirable stream. In other applications, the solutes my be contaminants that need to be
removed, and in this instance the raffinate is the desirable product stream.

Extraction processes are well suited to the petroleum industry because of the need to
separate heat – sensitive liquid feeds according to chemical type (e.g aromatic, naphthenic)
rather than by molecular weight or vapor pressure.

Application:

Major applications exist in the biochemical or pharmaceutical industry, where emphasis

is on the separation of antibiotics and protein recovery.

In the inorganic chemical industry, they are used to recover high – boiling components
such as phosphoric acid, boric acid and sodium hydroxide from aqueous solution.
 Definition & Application

Examples:

Extraction of nitrobenzene after reaction of HNO3 with toluene in H2SO4

Extraction of methylacrylate from organic solution with perchlorethylene

Extraction of benzylalcohol from a salt solution with toluene.

Removing of H2S from LPG with MDEA

Extraction of caprolactam from ammonium sulfate solution with benzene

Extraction of acrylic acid from wastewater with butanol

Removing residual alkalis from dichlorohydrazobenzene with water

 Definition & Application

Examples:

Extraction of methanol from LPG with water

Extraction of chloroacetic acid from methylchloroacetate with water.

The difference between LLE and distillation process in the separation of liquid mixtures:

LLE depends on solubilities between the liquid components and produces new
solution which in turn has to be separated again, whereas;

Distillation depends on the differences in relative volatilities / vapor pressures of

substances. Furthermore, it requires heat addition.
 Definition & Application

Advantages of LLE over distillation process:

Where distillation requires excessive amount of heat

Presence of azeotropes or low relative volatilities are involved (α value near unity and
distillation cannot be used)

Dissolved or complex inorganic substances in organic or aqueous solution

Removal of a component present in small concentrations, e.g hormones in animal oil.

Recovery of a high – boiling point component present in small quantities in waste

stream, e.g acetic acid from cellulose acetate.

Recovery of heat – sensitive materials (e.g food) where low to moderate processing
temperatures are needed. Thermal decomposition might occur.

Solvent recovery is easy and energy savings can be realized.

 Solvent selectivity

The solvent criterias:

• Distribution Coefficient.

This is the ratio (at equilibrium) of the concentration of solute in the extract and
raffinate phases. It gives a measure of the affinity of the solute for the two phases.

A distribution coefficient other than unity implies that the solute must have different
affinity in the two phases. If only one solute is involved (such as in the recovery of an
impurity from an effluent stream), only the distribution coefficient need to be considered,
and it is desirable for this to be as large as possible.
 Solvent selectivity

Selectivity (Separation factor).

If there are more than one solutes (sat two solutes A and B), then consideration should be
given to the selectivity of the solvent for solutes A against B.

The selectivity between two solutes A and B is defined as the ratio of the distribution
coefficient of A to the distribution coefficient of B. For all useful extraction operation the
selectivity must exceed unity. If the selectivity is unity, no separation is possible.

Insolubility of Solvent.

The solvent should have low solubility in the feed solution, otherwise the separation is
not ‚clean‛. For example, if there is significant solubility of solvent in the raffinate stream, an
additional separation step is required to recover the solvent.
 Solvent selectivity

Recoverability.

It is always necessary to recover the solvent for re-use, and this must ordinarily be done
by other means, e.g distillation. If distillation is to be used, the solvent should form no
azeotrope with the extracted solute and mixtures should show high relative volatility. The
solvent should also be thermally – stable under the distillation temperature.

Density.

A large difference in density between extract and raffinate phases permits high
capacities in equipment. This is especially important for extraction devices utilizing
gravity for phase separation.
 Solvent selectivity

Interfacial tension.

The larger the interfacial tension, the more readily coalescence of emulsions will occur
but the more difficult the dispersion of one liquid in the other will be. The more readily
coalesces the emulsions the easier phase separation will be.

Low interfacial tension aids dispersion and thus improves contacting mass transfer
efficiency. Coalescence is usually of greater importance, and interfacial tension should
therefore high.

Chemical Reactivity.

The solvent should be stable chemically and inert toward the other components of the
system and toward the common materials of construction.
 Solvent selectivity

Viscosity, Vapor pressure, Freezing Point.

These should be low for ease in handling and storage, for example, a high viscosity
leads to difficulties with pumping, dispersion and mass transfer rate.

Availability and Cost.

An excellent solvent may not commercially available. Or it may represent a large initial
cost for charging the system, and a heavy continuing expense for replacing inevitable
operating losses.

Other Criteria.

Toxicity and flammability of the solvent are important occupational health and safety
consideration.

Stability of the solvent (i.e resistance to breakdown), particularly in the recovery steps,
is significant, especially if the breakdown products might contaminate the products of the
main separation.
LIQUID-LIQUID EXTRACTION: THE CONCEPT
LLE : HOW IT IS DONE IN THE LAB
 Single – stage Counter-current Extraction

Solvent and the solution are in contact with each other only once and thus the raffinate and
extract are in equilibrium only once.

The solution – normally binary solution containing solute (A) dissolved in a diluent or
carrier (B). The extracting solvent can be either pure solvent C or may content little A.
Raffinate (R) is the exiting phase rich in carrier (B) while extract is exiting phase rich in
solvent (C).

When liquid solution mixed with solvent (C), an intermediate phase M momentarily forms
as the light liquid moves through the heavy liquid in the form of bubbles. These bubbles
provide a large surface area for contact between the solution and the solvent that speed up
mass transfer process.

The raffinate and extract are in equilibrium with each other.

 Single – stage Counter-current Extraction

Extract, V1 Solvent, V2

yA1, yC1 yA2, yC2

Feed, Lo Raffinate, L1
xA0 , xC0 xA1 , xC1

L0 Mass of feed solution V2 Mass of extracting solvent

V1 Mass of extract phase L1 Mass of raffinate phase
M Mass of intermediate xAM Mass fraction of A in intermediate
xA0 Mass fraction of A in feed
yA1 Mass fraction of A in extract xC0 Mass fraction of C in feed
yC1 Mass fraction of C in extract xA1 Mass fraction of A in raffinate
yA2 Mass fraction of A in solvent xC1 Mass fraction of C in raffinate
yC2 Mass fraction of C in solvent
 Single – stage Counter-current Extraction

In most single – extraction, we are interested to determine the equilibrium composition

and masses of raffinate and extract phases by using ternary phase diagram and simple
material balances.

Using material balance,

Overall: L0 + V2 = L1 + V1 = M (1)

(A): L0xA0 +V2yA2 = L1xA1 + V1yA1 = MxAM (2)

(C): L0xC0 +V2yC2 = L1xC1 +V1yC1 = MxCM (3)

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

To find the final compositions in the two phases, it is required to know the mixture total
mass and composition (point M).

After point M is identified, the product composition can be found by the equilibrium tie
line.
 Single – stage Counter-current Extraction

Plot ternary phase diagram/right angle triangular diagram

Plot point M at xAM and xCM on graph
Plot point V2 at yA2 and yC2
Plot point L0 at xA0 and xC0
L1 and V1 are obtained by drawing a tie line through point M
To draw a tie line, simply from any point at extract layer, move vertically downwards through
45° line, them move horizontally to the equilibrium line.
Finally, move vertically to point at raffinate layer. A line connecting the points (at extract &
raffinate layer) is the tie line.
In order to determine tie line, the trial and error technique should be used. This is done by
drawing as much as possible tie lines that cross the point M until the right tie line is obtained.
Hence, the extract and raffinate compositions for the mixture (M) is at point ‘g’ and ‘i’,
respectively.
Single – stage Counter-current Extraction

0.9
Point g
0.8

0.7
Extract layer
0.6

0.5

0.4
Point M
0.3
tie line
0.2
Point i
0.1

0
Raffinate layer
0 0.1 0.2 0.3 0.4 0.5 0.6

0.6 45° line

0.5

0.4

0.3

0.2
equilibrium line
0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6
 Example 12.5-2

• 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. What percent of the acetic acid is
removed? Use equilibrium data from Appendix A.3-24.
Appendix A.3-24
Acetic acid (A) - Water (B) - Isopropyl Ether (C) System
Mol and mass fraction
Water layer (wt%) Ether (wt%) Water layer, x Ether layer, y
A B C A B C A B C A B C
0 98.8 1.2 0 0.6 99.4 0 0.988 0.012 0 0.006 0.994
0.69 98.1 1.2 0.18 0.5 99.3 0.0069 0.981 0.012 0.0018 0.005 0.993
1.41 97.1 1.5 0.37 0.7 98.9 0.0141 0.971 0.015 0.0037 0.007 0.989
2.89 95.5 1.6 0.79 0.8 98.4 0.0289 0.955 0.016 0.0079 0.008 0.984
6.42 91.7 1.9 1.93 1 97.1 0.0642 0.917 0.019 0.0193 0.01 0.971
13.3 84.4 2.3 4.82 1.9 93.3 0.133 0.844 0.023 0.0482 0.019 0.933
25.5 71.1 3.4 11.4 3.9 84.7 0.255 0.711 0.034 0.114 0.039 0.847
36.7 58.9 4.4 21.6 6.9 71.5 0.367 0.589 0.044 0.216 0.069 0.715
44.3 45.1 10.6 31.1 10.8 58.1 0.443 0.451 0.106 0.311 0.108 0.581
46.4 37.1 16.5 36.2 15.1 48.7 0.464 0.371 0.165 0.362 0.151 0.487
0.464 0.165
Example 12.5-2

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6

0.6

0.5

0.4

0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6
 Ternary Phase Equilibrium Diagram

Equilibrium relationship can be presented in triangular diagram.

Two types of triangular diagram: 1) Right-angle triangular diagram 2) Equilateral triangular

diagram

Liquid-liquid system have 3 components: A (Solute), B (Carrier) and C (Solvent) and two
phases in equilibrium: 1) Extract 2) Raffinate

Example:
1) Methyl isobutyl ketone (A) – Water (B) – Acetone (C)
2) Water (A) – Chloroform (B) – Acetone (C)
3) Benzene (A) – Water (B) – Acetic Acid (C)
4) Acetic Acid (A) – Water (B) – Isopropyl ether (C)
5) Acetone (A) – Water (B) – Trichloroethylene (C)
6) Acetone (A) – Water (B) – Methyl isobutyl ketone (C)
 Ternary Phase Equilibrium Diagram

Right-angle triangular diagram

The solvent pair B and C are partially miscible

The concentration of component C is plotted on the vertical
axis and component A is plotted on horizontal axis
The two phase region is inside the envelope and one phase
region is outside the envelope
A tie line ‘gi’ connecting the extract layer (solvent rich) with
raffinate layer (diluent rich)
The solute-solvent rich layer, ‘g’ is called extract layer and
designated by ‘y’
The diluent rich layer, ‘i’ is called raffinate layer and
designated by ‘x’
For example: the mass fraction (concentration) of C is
designated as yC in the extract layer and as xC in the raffinate
layer
 Ternary Phase Equilibrium Diagram

Equilateral triangular diagram

Each vertex of the triangle represents a pure component.

The top vertex represents pure component B; the right vertex represents pure C; and the left vertex represents pure A.
Each of the three sides of the triangle represents a binary (two-component) mixture.
For example, the right side of the triangle represents mixtures of B and C; the left side represents mixtures of A and B;
and the base represents mixtures of A and C. Inside the triangle we have mixtures containing all three components.
The mole fraction (or mass fraction, as the case may be) for each component is found by reading the distance from the
base of the triangle opposite the vertex for that component.
So, for example, component B is the top vertex and anywhere on the first blue line from the bottom base will be 10% B;
anywhere on the next higher blue line will be 20 % B; and so on until 100% B is reached at the vertex.
Likewise, C is the right vertex and so any of the red lines parallel with the base opposite C tells us the mol% of C in
the mixture. Thus the first line up from the base opposite C represents 10 mol% C, etc.
The green lines represent mol% of A starting from the base opposite pure A being 0% A and increasing the amount of
A as the green lines get closer to the left vertex. A point on the right side of the triangle where the blue 30% line intersects
the side represents 30% B and 70% C.
The point where the red, blue and green lines cross just above the grey area represents a ternary mixture containing
60% B, 20% A and 20% C.
 Ternary Phase Equilibrium Diagram

Equilateral triangular diagram (Diluent)

wt% of B
Tie lines:
Show the compositions of the
equilibrium phases
wt% of A

(Solute) (Solvent)
wt% of C
EXERCISE 1
 Continuous Multi – stage Counter-current Extraction
Single-stage equilibrium contact was used to transfer solute A from one liquid to another liquid
phase.
To transfer more solute, single-stage contact can be repeated by bringing the exit L1 stream into
contact with fresh solvent, V2.
Therefore, a greater percentage removal of solute A is obtained. However, this is wasteful of the
solvent stream as well as giving a dilute product of A in the outlet solvent extract streams.
In order to use less solvent and to obtained more concentrated exit extract stream, counter-current
multistage is used.
Solvent and solution which flow opposite (countercurrent) to each other, come into contact more than
once and mix on stages inside the reactor.
Normally numbering of the stages begin at the top down to the bottom. Thus the top most stage is
named as stage 1, stage directly below stage 1 is stage 2 and so on.
The analysis of multistage extraction can be performed using right – angle or equilateral triangular
diagram to determine the number of ideal stages required for a specified separation.
 Continuous Multi – stage Counter-current Extraction

Using material balance,

The overall balance on all N stages is

L0 + VN+1 = LN + V1 = M (1)

where M is the total mass (kg/h) and is a constant, L0 the inlet feed flow rate (kg/h), VN+1 the inlet
solvent flow rate (kg/h), V1 the exit extract stream, and LN the exit raffinate stream. Material balance
on C gives

L0xC0 + VN+1 yCN+1 = LN xCN + V1 yC1 = MxCM (2)

xAM and xCM is obtained by solving Eqs. (1) & (2):

 Continuous Multi – stage Counter-current Extraction

To find the compositions and the amount of extract and raffinate streams:
1. Plot ternary phase diagram (equilateral/right-angle)
2. Find the values of yAN+1, yCN+1 (composition of A&C in solvent), xA0, xC0 (composition of
A&C in feed), xAN, xCN (composition of A&C in raffinate) and xAM, xCM (composition of
A&C in mixture)
3. Plot VN+1 (yAN+1, yCN+1), L0 (xA0, xC0), LN (xAN, xCN) and M (xAM, xCM)
4. V1 is located by drawing a line from LN through M & extending it until it intersects the
phase boundary in the extract phase. This give yA1 and yC1 (compositions of A&C in
extract stream)
5. Find the amount of extract (V1) and raffinate (LN) using material balance.

Stage-to-stage calculation for countercurrent extraction:

1. The line L0V1 and LNVN+1 are drawn and the intersection is the operating point, Δ.
2. Draw an equilibrium tie line through V1 to locate L1
• Construct with equilibrium line and 45° line – for right angle triangular diagram
• Using the nearest tie line – for equilateral triangular diagram
3. Draw a line L1Δ to give V2 at the extract phase boundary.
4. A tie line from V2 gives L2. This is continued until the desired LN is reached.
 Continuous Multi – stage Counter-current Extraction

Right-angle triangular diagram

VN+1
(yAN+1, yCN+1)

V1
(yA1, yC1)

L0
LN (xA0, xC0)
(xAN, xCN)
 Continuous Multi – stage Counter-current Extraction

Equilateral triangular diagram

(Solute)

M
(xAM, xBM, xCM)

V1 Plait Point
(yA1, yB1, yC1) L0
V1 (xA0, xB0, xC0)

L0
VN+1 M Operating Point
(yAN+1, yBN+1, yCN+1) Δ

LN LN
VN+1 (xAN, xBN, xCN)

(Solvent) (Carrier/Diluent)
 Example 12.7-1

Pure solvent isopropyl ether (C) at the rate of VN+1 = 600 kg/h is being used to extract an aqueous
solution of L0 = 200 kg/h containing 30 wt % acetic acid (A) and 70 wt % water (B) by countercurrent
multistage extraction. The desired exit acetic acid concentration in the aqueous phase is 4%. Calculate
the compositions and amounts of the ether extract V1 and the aqueous raffinate LN. Use equilibrium
data from Appendix A.3-24.

Appendix A.3-24
Acetic acid (A) - Water (B) - Isopropyl Ether (C) System
Mol and mass fraction
Water layer (wt%) Ether (wt%) Water layer, x Ether layer, y
A B C A B C A B C A B C
0 98.8 1.2 0 0.6 99.4 0 0.988 0.012 0 0.006 0.994
0.69 98.1 1.2 0.18 0.5 99.3 0.0069 0.981 0.012 0.0018 0.005 0.993
1.41 97.1 1.5 0.37 0.7 98.9 0.0141 0.971 0.015 0.0037 0.007 0.989
2.89 95.5 1.6 0.79 0.8 98.4 0.0289 0.955 0.016 0.0079 0.008 0.984
6.42 91.7 1.9 1.93 1 97.1 0.0642 0.917 0.019 0.0193 0.01 0.971
13.3 84.4 2.3 4.82 1.9 93.3 0.133 0.844 0.023 0.0482 0.019 0.933
25.5 71.1 3.4 11.4 3.9 84.7 0.255 0.711 0.034 0.114 0.039 0.847
36.7 58.9 4.4 21.6 6.9 71.5 0.367 0.589 0.044 0.216 0.069 0.715
44.3 45.1 10.6 31.1 10.8 58.1 0.443 0.451 0.106 0.311 0.108 0.581
46.4 37.1 16.5 36.2 15.1 48.7 0.464 0.371 0.165 0.362 0.151 0.487
0.464 0.165
 Example 12.7-2

Pure isopropyl ether (C) of 450 kg/h is being used to extract an aqueous solution of 150 kg/h with 30
wt % acetic acid (A) and 70 wt % water (B) by countercurrent multistage extraction. The exit acid
concentration in the aqueous phase is 10 wt %. Calculate the number of stages required.
Example 12.7-1 & 2

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6

0.6

0.5

0.4

0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6
 Example – using equilateral triangular diagram

A 1000 kg/h mixture of 30 wt% acetic acid and 70 wt % water is to be fed to a countercurrent
extraction process. The solvent is 99 wt% isopropyl ether and 1 wt % acetic acid and has an inlet flow
rate of 2500 kg/h. The raffinate stream should contain 5 wt % acetic acid.

a) Calculate the raffinate and extract stream flow rates.

b) Find the number of equilibrium stages.
 Example – using equilateral triangular diagram

Acetic Acid (A)

Water(B) Ether(C)
 Minimum Solvent Rate

Right-angle triangular diagram

If a solvent rate VN+1 is selected at too low a value, a limiting case

will be reached with an operating line through Δ and a tie line
being the same.
Then an infinite number of stages will be needed to reach the
desired separation and the minimum amount of solvent is reached.
For actual operation a greater amount of solvent must be used.
The procedure to obtain this minimum solvent rate is as follows:
1. Plot VN+1 (yAN+1, yCN+1), L0 (xA0, xC0) and LN (xAN, xCN)
2. Draw tie line from L0 to locate V1min. The tie line through
the feed, L0 represents the condition for minimum solvent
flow rate.
3. Draw line LNV1min and L0VN+1 . The intersection between
these lines give the mixture point Mmin (xAMmin)
4. The intersection between lines L0V1min and LNVN+1 give
operating point, Δmin.
5. For minimum solvent, a line through Δ and a tie line being
the same. Therefore, infinite number of stages will be
needed to reach the desired separation.
 Minimum Solvent Rate

Equilateral triangular diagram

The procedure to obtain this minimum solvent

rate is as follows:
1. Locate position of solvent, VN+1 (yAN+1, yCN+1)
and feed, L0 (xA0, xC0).
2. Draw tie line from point L0 until intersect the
equilibrium line (extract line) and locate
V1min
V1min.
3. Draw line LNV1min and L0VN+1 . The
intersection between these lines give the Mmin L0
mixture point Mmin (xAMmin)
4. The intersection between lines L0V1min and
LNVN+1 give operating point, Δmin. LN
5. After locating Δmin, V1min, and Mmin, the stages
can be stepped off. VN+1
 Problem 12.7-3

An aqueous feed solution of 1000 kg/h containing 23.5 wt % acetone and 76.5 wt % water is being
extracted by countercurrent multistage extraction using pure MIK solvent at 298 K. The outlet water
raffinate will contain 2.5 wt % acetone. Calculate the minimum solvent that can be used. Using a
solvent flowrate of 1.5 times the minimum, calculate the number of stages required.

Acetone-water-methyl isobutyl ketone system

Composition data (wt%) Acetone Distribution data (wt%) Mass fraction Mass fraction of acetone
MIK (C ) Acetone (A) Water (B) Water phase MIK phase MIK (C ) Acetone (A) Water (B) Water phase (xA) MIK phase (yA)
98 0 2 0 0 0.98 0 0.02 0 0
93.2 4.6 2.33 2.5 4.5 0.932 0.046 0.0233 0.025 0.045
77.3 18.95 3.86 5.5 10 0.773 0.1895 0.0386 0.055 0.1
71 24.4 4.66 7.5 13.5 0.71 0.244 0.0466 0.075 0.135
65.5 28.9 5.53 10 17.5 0.655 0.289 0.0553 0.1 0.175
54.7 37.6 7.82 12.5 21.3 0.547 0.376 0.0782 0.125 0.213
46.2 43.2 10.7 15.5 25.5 0.462 0.432 0.107 0.155 0.255
12.4 42.7 45 17.5 28.2 0.124 0.427 0.45 0.175 0.282
5.01 30.9 64.2 20 31.2 0.0501 0.309 0.642 0.2 0.312
3.23 20.9 75.8 22.5 34 0.0323 0.209 0.758 0.225 0.34
2.12 3.73 94.2 25 36.5 0.0212 0.0373 0.942 0.25 0.365
2.2 0 97.8 26 37.5 0.022 0 0.978 0.26 0.375
 Problem 12.7-3
Acetone-water-MIK System Acetone-water-MIK System (Minimum Solvent)
1.2 1.2
1 1
0.8 0.8
xC, yC

xC, yC
0.6 0.6
0.4 0.4
0.2 0.2
0 0
0 0.1 0.2 0.3 0.4 0.5 0 0.1 0.2 0.3 0.4 0.5
xA, yA xA, yA

Equilibrium diagram Equilibrium diagram

0.45 0.45
0.4 0.4
0.35 0.35
0.3 0.3
0.25 0.25
yA

yA
0.2 0.2
0.15 0.15
0.1 0.1
0.05 0.05
0 0
0 0.1 0.2 0.3 0.4 0.5 0 0.1 0.2 0.3 0.4 0.5
xA xA
Problem 12.7-3
Problem 12.7-3
 Counter-current Stage Extraction with Immiscible Liquid

If the component stream VN+1 contains components A and C and feed stream L0 contains A and B and
if components B and C are relatively immiscible in each other, the stage calculations may be made more
easily.
The solute A is relatively dilute and is being transferred from L0 to VN+1.
Overall balance for A:
L’ = kg inert B/h (pure B)
V’= kg inert C/h (pure C)
y = mass fraction A in V stream
x = mass fraction A in L stream

= LN (1 – xN) = V1 (1 – y1)
• Operating line is plotted at
(xAN, yAN+1) and (xA0, yA1)
Kremser equation • If diluted solution, operating
line is a straight line
𝑦𝑁+1 𝐴1 = 𝐿0 𝑚1 𝑉1 • If not diluted solution,
𝑥0 − 𝑚
ln 𝑦𝑁+1 1−𝐴 +𝐴 𝐴2 = 𝐿𝑁 𝑚2 𝑉𝑁+1
operating line is slightly curve
line
𝑥𝑁 − 𝑚
N=
ln(1 𝐴) 𝐴= 𝐴1 𝐴2
 Example 12.7-3

An inlet water solution of 100 kg/h containing 0.010 wt fraction nicotine in water is stripped with a
kerosene stream of 200 kg/h containing 0.0005 wt fraction nicotine in a countercurrent stage tower.
The water and kerosene are essentially immiscible in each other. It is desired to reduce the
concentration of the exit water to 0.0010 wt fraction nicotine. Calculate the flow rate of the nicotine in
both of the exit streams. Determine the theoretical number of stages needed. The equilibrium data are
as follows with x the weight fraction of nicotine in the water solution and y in the kerosene.

Plot the equilibrium data and graphically determine the number of stages
Use Kremser equation to determine the number of stages

x 0.001010 0.00246 0.00500 0.00746 0.00988 0.0202

y 0.000806 0.001959 0.00454 0.00682 0.00904 0.0185
 Example 12.7-3

Figure 12.7-6. Solution for extraction with immiscible liquids in Example 12.7-3.
 Counter-current Stage Extraction with Immiscible Liquid –
Minimum Solvent

In extraction process, the inlet feed flow (L0) and its solute
composition (xA0) are usually set.
The solute concentration in raffinate (xAN) is often set by
the designer.
The solute concentration in solvent (yAN+1) is generally
fixed by the process requirements in regenerating the solvent
for recycle back to the tower.
Hence, the amount of the entering solvent (VN+1) is open to
choose.
Minimum solvent (V’min) is when the operating line has a
maximum slope and touches the equilibrium line at point P
(point xA0).
The value of yA1 is at a maximum (yA1max).
Optimum flowrate is taken at 1.2-1.5 times V’min with 1.5
normally used.
Example 12.7-4
Example 12.7-4

Figure 12.7-8. Operating and equilibrium line for Example 12.7-4.

 Liquid – liquid Extraction Equipment

Mixer – Settlers for Extraction

A mechanical mixer is often used to provide intimate contact between the two liquid
phases – to provide efficient mass transfer.
One phase is usually dispersed into the other in the form of small droplet.
In figure 12.6 – 1(a) for typical mixer settler, mixer or agitator is entirely separate from
the settler. The feed of aqueous phase and organic phase are mixed in the mixer, and
then the mixed phases are separated in the settler.
In figure 12.6 – 1(b) for combined mixer settler, sometimes used in extraction of
uranium salts or copper salts from aqueous solution.
 Liquid – liquid extraction equipment

Spray Extraction Towers

In Figure 12.6–2 the heavy liquid enters at

the top of the spray tower, fills the tower
as the continuous phase, and flows out
through the bottom.

The light liquid enters through a nozzle

distributor at the bottom, which disperses
or sprays the droplets upward.

The light liquid coalesces at the top and

flows out.

In some cases the heavy liquid is sprayed

downward into a rising, light continuous
phase.
 Liquid – liquid extraction equipment

Packed Extraction Towers

More effective tower – made by packing

the column with random packing such
as Raschig rings, Berl saddles, Pall rings
and so on

Packings cause the droplets to coalesce

and redisperse at frequent intervals
through the tower.

Packed tower is more efficient than

spray tower.

Table 12.6 – 1 shows typical

performance for several types of
commercial extraction towers.
 Liquid – liquid extraction equipment
Packed Extraction Towers
 Liquid – liquid extraction equipment

Agitated Extraction Towers

It depends on gravity flow for mixing and for separation.

Mechanical energy is provided by internal turbines or other
agitators, mounted on a central rotating shaft.
In the York-Scheibel extractor (Fig. a), the region surrounding the
agitators are packed with wire mesh to encounter coalescence and
separation of the phases.
Most of the extraction takes place in the mixing sections, but some
also occurs in the calming sections.
The efficiency of each mixer-settler unit is sometimes greater than
100 percent.
Fig (b), flat disks disperse the liquids and impel them outward
toward the tower wall, where stator rings create quite zones in
which the two phases can separate.
In other designs, set of impellers are separated by calming
sections to give, in effect, a stack of mixer-settlers one above the
other.
LLE EQUIPMENT
Appendix
Appendix
Appendix