Lecture

Liquid-Liquid extraction
1- Definition:
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 is known as liquid–liquid Extraction
2- Application:
1. Processing of coal tar liquids and in the production of fuels in
the nuclear industry.
2. Separation of hydrocarbons in the petroleum industry.
3. Separation of aromatics from Kerosene-based fuel oils to
improve their burning qualities.
4. Separation of aromatics from Paraffins and
naphtenes to improve viscosity of lubricating oils.
5. Prepare Benzene, Toluene and Xylene.
6. Production of anhydrous acetic acid.
7. Extraction of phenol from coal tar
8. Purification of Pencillin.
3- Cases of using Liquid-Liquid Extraction

1. When distillation is difficult and would require

excessive amounts of heat (α=1).
2. When the mixture form azeotrope.
3. When heat must be avoided.
4. When the components to be separated are different
in nature.
4-Comparison between Liquid-Liquid Extraction
and distillation:
Liquid –Liquid Extraction Distillation
Depends on difference in solubility Depends on difference in relative
volatility

Low Temperature Operation High Temperature Operation

It is not affected with pressure It is affected with pressure

(One way diffusion) (Two way diffusion)
5- Steps of Liquid Liquid Extraction:

(a) Bringing the feed mixture and the solvent into intimate contact,
(b) Separation of the resulting two phases, and
(c) Removal and recovery of the solvent from each phase.

6- Types of Liquid Liquid Extraction operations:

Liquid Liquid extraction could be classified according to the
nature of solute and new solvent to physical and chemical
operation.
• Chemical operations have been classified as
follows:
(a) Those involving cation exchange such as, for example, the
extraction of metals by carboxylic acids;

(b) Those involving anion exchange, such as the extraction of

anions involving a metal with amines, and

(c) Those involving the formation of an additive compound, for

example, extraction with neutral organo-phosphorus compounds.
An important operation of this type is the purification of uranium
from the nitrate with tri-n-butyl phosphate.
 7- EXTRACTION PROCESSES:
➢ The three steps , necessary in all liquid–liquid extraction
operations, may be carried out either as a batch or as a continuous
process.

A) Batch Process: In the single-stage batch process illustrated in the

following Figure ,the solvent and solution are mixed together and
then allowed to separate into the two phases.
The extract E containing the required solute in the added solvent
and The raffinate R, the weaker solution with some associated
solvent. With this simple arrangement mixing and separation occur
in the same vessel.
B- Continuous Process :
• A continuous two-stage operation is shown in the following
Figure , where the mixers and separators are shown as separate
vessels.
• There are three main forms of equipment. First there is the
mixer-settler as shown in the following Figure , secondly, there
is the column type of design with trays or packing as in
distillation and, thirdly, there are a variety of units
incorporating rotating devices such as the Scheibel and the
Podbielniak extractors.
• In all cases, the extraction units are followed by distillation or
a similar operation in order to recover the solvent and the
solute. This Process could be classified to co-current and
counter current operation.
8-The transfer rate Equation:
Is given by the accepted equation:

➢ where k is a mass transfer coefficient and C a concentration

driving force.

➢ A high value of k can be obtained only if turbulent or eddy

conditions prevail and, although these may be readily achieved in
the continuous phase by some form of agitation, it is very difficult
to generate eddies in the drops which constitute the dispersed.
 9-EQUILIBRIUM DATA:

The equilibrium condition for the distribution of one solute between two liquid
phases is conveniently 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 :
CE/CR = K
Where :K is the distribution constant.
This relation will apply if:
❖ Both solvents are completely immiscible.
❖ No chemical reaction occurs.
❖ The concentration are small.
❖ There is no association or dissociation of the solute.
The addition of a new solvent to a binary mixture of a solute in a
solvent may lead to the formation of several types of mixture:

(a) A homogeneous solution may be formed and the selected solvent

is then unsuitable.

(b) The solvent may be completely immiscible with the initial

solvent.

(c) The solvent may be partially miscible with the original solvent
resulting in the formation of one pair of partially miscible liquids.

(d) The new solvent may lead to the formation of two or three
partially miscible liquids.
• Of these possibilities, types (b), (c), and (d) all give rise to
systems that may be used, although those of types (b) and (c)
are the most promising. With conditions of type (b), the
equilibrium relation is conveniently shown by a plot of the
concentration of solute in one phase against the concentration
in the second phase. Conditions given by (c) and (d) are
usually represented by triangular diagrams
10- Triangular Diagram:
• The system, acetone (A)–Water (B)–
methyl isobutyl ketone (C), as
shown in the Figure is of type (c).
Here the solute A is completely
miscible with the two solvents B and
C, although the two solvents are
only partially miscible with each
other. A mixture indicated by point H
consists of the three components A, B
and C in the ratio of the
perpendiculars HL, HJ, HK (divided
by the addition of all of them). The
distance BN represents the solubility
of solvent C in B, and MC that of B in
C. The area under the curved line
NPFQM, the binodal solubility
curve, represents a two-phase region
which will split up into two layers in
equilibrium with each other.
• These layers have compositions
represented by points P and Q,
and PQ is known as a “tie line”.
Such lines, two of which are
shown in the diagram, connect the
compositions of two phases in
equilibrium with each other, and
these compositions must be found
by practical measurement. There
is one point on the binodal curve
at F which represents a single
phase that does not split into two
phases. F is known as a plait
point, and this must also be found
by experimental measurement.
The plait point is fixed if either
the temperature or the pressure is
fixed.
Within the area under the curve, the temperature and composition
of one phase will fix the composition of the other.
Applying the phase rule to the three-components system at
constant temperature and pressure, the number of degrees of
freedom is equal to 3 minus the number of phases.
In the area where there is only one liquid phase, there are two
degrees of freedom and two compositions must be stated. In a
system where there are two liquid phases, there is only one
degree of freedom.
One of the most useful features of this method of representation
is that, if a solution of composition X is mixed with one of
composition Y, then the resulting mixture will have a
composition shown by Z on a line XY, such that:

XZ/ZY = (amount of Y)/(amount of X).

Similarly, if an extract Y is removed, from a mixture Z the

remaining liquor will have composition X.
11-Calculation of the number of theoretical stages: Co-current
contact with immiscible solvents
➢ Triangular diagrams are not required. If the initial solution
contains a mass A of solvent A with a mass ratio Xf of solute, then
the selective solvent to be added will be a mass S of solvent S.

➢ On mixing and separating, a raffinate is obtained with the solvent

A containing a mass ratio X1 of solute, and an extract with the
solvent S containing a mass ratio Y1 of solute.
A material balance on the solute gives:
➢ This process may be illustrated by allowing the point F to represent
the feed solution and drawing a line FE1, of slope −(A/S)1, to cut
the equilibrium curve at E1. This then gives composition Y1 of the
extract and X1 of the raffinate.
➢ If a further stage is then carried out by the addition of solvent S to
the stream AX1, then point E2 is found on the equilibrium curve by
drawing GE2 of slope −(A/S)2. Point E2 then gives the
compositions X2 and Y2 of the final extract and raffinate.
➢ This system may be used for any number of stages, with any
assumed variation in the proportion of solvent S to raffinate from
stage to stage. If the distribution law is followed, then the
equilibrium curve becomes a straight line given by Y = mX.
The material balance on the solute may then be rewritten as:
Example 1:

• A solution of 5 per cent acetaldehyde in toluene is to be

extracted with water in a five stage co-current unit. If 25 kg
water/100 kg feed is used, what is the mass of acetaldehyde
extracted and the final concentration, For co-current contact
with immiscible solvents, where the equilibrium curve is a
straight line as in the present case:
• The equilibrium relation is given by:
(kg acetaldehyde/kg water)= 2.20 (kg acetaldehyde/kg toluene)

Solution:
• For co-current contact with immiscible solvents where the
equilibrium curve is a straight line as in the present case:
 Xn = [A/(A + S*m)]n Xf
On the basis of 100 kg feed:
mass of solvent in the feed, A = 95 kg,
mass of solvent added, S = 25 kg,
slope of the equilibrium line, m = 2.20 kg/kg,
number of stages, n = 5, and
mass ratio of solute in the feed Xf = (5/95) = 0.0527 kg/kg.
Thus: mass ratio of solute in raffinate,Xn = [95/(95 + 2.2 × 25)]5 ×
0.0527 = 0.00538 kg/kg solvent
Thus, the final solution consists of 0.00538 kg acetaldehyde in
1.00538 kg solution and the concentration = (100 ×
0.00538)/1.00538 = 0.536 per cent
With 95 kg toluene in the raffinate, the mass of
acetaldehyde = (0.00538 × 95) = 0.511 kg.
and the mass of acetaldehyde extracted = (5.0 − 0.511)
= 4.489 kg/100 kg feed.
 12-Calculation of the number of theoretical stages:
Co-current contact with partially miscible solvents

• In calculating the number of ideal stages required for a given

degree of separation, Triangular diagrams are required.
• For the general case where the solvents are partially miscible, the
feed solution F is brought into contact with the selective solvent
S, to give raffinate R1 and an extract E1. The addition of streams F
and S is shown on the triangular diagram in the following Figure,
by the point M, where FM/MS = S/F. This mixture M breaks
down to give extract E1 and and raffinate R1, at opposite ends of a
tie line through M.
• If a second stage is used, then the raffinate R1 is treated with a
further quantity of solvent S, and extract E2 and raffinate R2 are
obtained as shown in the same figure.
• The complete process consists in carrying out the extraction, and
recovering the solvent from the raffinate and extract obtained.
Thus, for a single-stage system as shown in the Figure, the
raffinate R is passed into the distillation column where it is
separated to give purified raffinate R and solvent SR. The extract
E is passed to another distillation unit to give extract E and a
solvent stream SE.
• These recovered solvents SR and SE are pumped back to the
extraction process as shown. This cycle may be represented on a
diagram, as shown in the Figure, by showing the removal of SR
from R to give composition R, and the removal of SE from E to
give composition E.
Example 2:
50% solution of solute C (acetaldehyde) in solvent A
(Water) is to be extracted with a second solvent S in a
Co-current extraction unit. The weight of solvent is
25% that of feed solution in all stages.

Determine:
Theoretical stages required if the final raffinate has 15%
of solute C assuming Co-current contact with partially
miscible solvents
Solution Steps
• 1- Determine point F on the line
between water and acetaldeyhde
by the composition of xf.
• Draw line between F and S (new
solvent)
• Determine the point M by Phase
rule f/s=ms/mf
• After determining M take
parallel line to tie lines in
triangle to determine E1 and R1
• Connect R1 with S to determine
M2 by lever rule also
r1/s=m2S/m2R
• After determining M2
take parallel line to tie
lines in triangle to
determine E2 and R2.
• Continuing the previous
steps until reaching a
value of R equals xn
• The number of steps
equals the total drawn
lines
13-Calculation of the number of theoretical stages:
Counter current contact with immiscible solvents:
✓ If a series of mixing and separating vessels is arranged so that
the flow is countercurrent, then the conditions of flow may be
represented as shown in the Figure, where each circle
corresponds to a mixer and a separator.

✓ The initial solution F of the solute B in solvent A is fed to the

first unit and leaves as raffinate R1.

✓ This stream passes through the units and leaves from the nth
unit as stream Rn. The fresh solvent S enters the nth unit and
passes in the reverse direction through the units, leaving as
extract E1.
 • If the two solvents are immiscible, the solvent in the raffinate
streams remains as A, and the added solvent in the extract
streams as S. The material balances for the solute may then be
written as

This is the equation of a straight line of slope A/S, known as the

operating line, which passes through the points (Xf , Y1) and (Xn, Yn+1).
14-Calculation of the number of theoretical stages:
Counter-current contact with partially miscible
solvents
➢ In this case the arrangement of the equipment is the same as
for immiscible solvents although, as the amounts of solvent in
the extract and raffinate streams are varying, the material
balance is taken for the total streams entering and leaving each
stage.
• the final extract E1, the fresh solvent S = stream En+1 and, the
final raffinate Rn are fixed, then making material balances:
➢ Thus the difference in quantity between the raffinate leaving a
stage Rn, and the extract entering from next stage En+1, is
constant. Similarly, it can be shown that the difference
between the amounts of each component in the raffinate and
the extract streams is constant.

➢ This means that, with the notation of a triangular diagram,

lines joining any two points representing Rn and En+1 pass
through a common pole. The number of stages required to so
from an initial concentration F to a final raffinate
concentration Rn may then be foundusing a triangular diagram,
Example 3:
It is proposed to reduce the concentration of
acetaldehyde in aqueous solution from 50 per cent to 5
per cent by mass, by extraction with solvent S at 293 K.
If a countercurrent multiple-contact process is adopted
and 0.025 kg/s of the solution is treated with an equal
quantity of solvent, determine the number of theoretical
stages required and the mass flow-rate of the extract
from the first stage.
Solution:
• The data are replotted
in Figure and the
point F, representing
the feed, is drawn in
at 50 per cent
acetaldehyde, 50 per
cent water. Similarly,
Rn, the raffinate from
stage n located on the
curve corresponding
to 5 per cent
acetaldehyde.
• FS is joined and point M
located such that FM = MS,
since the ratio of feed solution
to solvent is unity. M is
determined and projected to
meet the equilibrium curve at
E1 and FE1 and RnS are
projected to meet at P. The
tie-line E1R1 is drawn in and
the line R1P then meets the
curve at E2. The working is
continued in this way and it is
found that R4 is below Rn
and hence four theoretical
stages are required