Liquid-Liquid Extraction

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
liquidliquid extraction.

For example, it is applied in the processing of coal tar liquids, in the production of
fuels in the nuclear industry and extensively used for the separation of hydrocarbons
in the petroleum industry.

Principle of separation:
Liquid extraction is based on the differences in solubility rather than the differences in vapour
pressures of the components to be separated out.

Liquid-liquid extraction is usually preferred in the following

circumstances:

When separation by distillation is ineffective or difficult, liquid extraction is the most

important choice.
Where distillation would require excessive amounts of heat, for example,
when the relative volatility is near unity.
When the formation of azeotropes limits the degree of separation obtainable in
distillation
Substances that cannot withstand the temperatures of distillation even under vacuum.
In addition, for the cases when heating must be avoided.
When the components to be separated are quite different in nature.

Conditions to be fulfilled:
The liquid-mixture feed and solvent should be completely miscible or at least partially
miscible.
Three stages are carried out for carrying out liquid -liquid extraction:

1) Bringing the feed mixture and the solvent into intimate contact by dispersing one
phase into the other as droplets
2) Separation of the resulting two phases that have different densities
3) Removal and recovery of the solvent from each phase.

Why distillation is preferred for a binary mixture?

1. Distillation is operationally simple than extraction because a binary mixture can be

easily separated out into two components in a column whereas for the liquid-liquid
extraction, in addition to an extractor a distillation column is also required. Therefore,
the combined operation is normally more complicated and expensive. This is inspite
of the fact that heating and cooling is required even when the distillation is carried out
alone.

2. Very often, more than one distillation column is required for the recovery of solvent
from the aqueous phase.

3. Phase separation of the two phases may not be easy if the difference in their densities
is small and the interfacial tension is low

4. Loss of solvent may also occur in some cases

Despite all these limitations, solvent extraction is an attractive alternative in some cases
as discussed below:

1. Components to be separated have close boiling points

2. Separation of heat sensitive materials e.g antibiotics
3. Recovery of solute from very dilute solution

In addition, extraction does offer great flexibility in choice of the operating conditions, since
the type and amount of solvent can be varied as well as the operating temperature.
Applications/ Examples of Liquid-liquid extraction:

1. Penicillin is recovered from the fermentation broth by extraction with a solvent such
as butyl acetate, after lowering the pH to get a favourable partition coefficient. The
solvent is then treated with a buffered phosphate solution to extract the penicillin from
the solvent and give a purified aqueous solution, from which penicillin is eventually
produced by drying

2. One of the major uses of extraction is to separate petroleum products that have
different chemical structures but about the same boiling range. Lube oil fractions
(bpt>300C) are treated with low-boiling polar solvents such as phenol, furfural, or
methyl pyrrolidone to extract the aromatics and leave an oil that contains mostly
paraffins and naphthenes. The aromatics have poor viscosity-temperature
characteristics, but they cannot be removed by distillation because of the overlapping
boiling-point ranges. In addition, the separation of aromatics from kerosene-based
fuel oils are also carried out by the same technique to improve their burning qualities

3. Separation of benzene, toluene and xylene from catalytically produced reformates in

the oil industry
4. Extraction of phenol from aqueous wastes (coal carbonization plants, phenolic
resin plants)
5. Purification of the Uranium fuel
6. In the production of anhydrous acetic acid from aqueous solutions

Extraction Processes:
Liquidliquid extraction operations are being carried out either as a batch or as a continuous
process.

Single Stage Batch Process:

In the single-stage batch process (Figure 1), 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 rafnate R, the weaker solution with some associated solvent. With
this simple arrangement mixing and separation occur in the same vessel.
 Figure 1: Single Stage Batch Process

Continuous Two Stage Operation:

In a continuous two-stage operation (Figure 2), the mixers and separators are shown as
separate vessels.

Figure 2: Multiple contact system with fresh solvent

There are three main forms of equipment.
1. First there is the mixer-settler as shown above,
2. secondly, there is the column type of design with trays or packing as in distillation
and,
3. thirdly, there are a variety of units incorporating rotating devices.

In all cases, the extraction units are followed by distillation or a similar operation in order
to recover the solvent and the solute.

Equilibrium Data:
The equilibrium condition for the distribution of one solute between two liquid phases is
conveniently considered in terms of the distribution law.

At equilibrium, the ratio of the concentrations of the solute in the two phases is given by:

Where K is the distribution constant. This relation will apply accurately only if:

Both solvents are immiscible

There is no association or dissociation of the solute
If the solute forms molecules of different molecular weights, then the distribution law
holds for each molecular species
The distribution law holds when there is no chemical reaction of the solute with
solvent

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.

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.

Example of triangular diagram:

The system, acetone (A)Water (B) methyl isobutyl ketone (C), as shown in Figure 3 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. It is the property of an equilateral
triangle that the sum of the perpendicular distances from any point within the triangle to the
three sides equals the altitude of the triangle. We can therefore let the altitude represent 100
percent composition and the distances to the three sides the percentages or fractions of the
three components.
Therefore, each of the three corners represents a pure component A, B or C. A mixture
indicated by point H consists of the three components A, B and C in the ratio of the
perpendiculars HL, HJ, HK.

When solvent is added to a mixture of acetone and water, the composition of the resulting
mixture lies on a straight line between the point for pure solvent and the point for the original
binary mixture. When enough solvent is added so that the overall composition falls under the
dome-shaped curve (NPFQM), the mixture separates into two phases (two layers). This curve
is called the bimodal solubility curve. The points representing the phase compositions can be
joined by a straight tie line, which passes through the overall mixture composition (e.g line
PQ). 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. The distance BN represents the solubility of solvent C in B, and MC that of B
in C. 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.
Figure 3: Equilibrium relationship for acetone distributed between water and methyl
isobutyl ketone.
 Figure 3(a): System acetone-MIK-water at 25C

The line ACE shows compositions of the MIK layer (extract), and line BDE shows
compositions of the water layer (raffinate). As the overall acetone content of the mixture
increases, the compositions of the two phases approach each other, and they become equal at
the point E, the plait point.

The tie lines in Figure 3(a) slope up to the left, and the extract phase is richer in acetone than
the raffinate phase. This suggests that most of the acetone could be extracted from the water
phase using only a moderate amount of solvent. If the tie lines were horizontal or sloped up to
the right, extraction would still be possible, but more solvent would have to be used, since the
final extract would not be as rich in acetone. The ratio of desired product (acetone) to diluent
(water) should be high for a practical extraction process. The solubility of water in MIK
solvent is only 2 percent, but as the acetone concentration increases, the water content of the
extract phase also increases. A higher concentration of acetone could be obtained, but the
greater amount of water in the extract product would probably make operation at these
conditions undesirable.
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.

In Figure 4, two separate two-phase regions are formed, whilst in Figure 5 the two-phase
regions merge on varying the temperature. Aniline (A), water (B), and phenol (C) represent a
system of the latter type. Under the conditions shown in Figures 4 and 5, A and C are
miscible in all proportions, although B and A, and B and C are only partially miscible.

Figure 4. Equilibrium relationship for the anilinewaterphenol system

Figure 5. Equilibrium relationship for the anilinewaterphenol system at
a higher temperature

These diagrams are of considerable use in presenting equilibrium data. However, Figure 6
is in many ways more useful for determining the selectivity of a solvent, and the number of
stages that are likely to be required. In Figure 6, the percentage of solute in one phase is
plotted against the percentage in the second phase in equilibrium with it. This is equivalent to
plotting the compositions at either end of a tie line. The important factor in assessing the
value of a solvent is the ratio of the concentrations of the desired component in the two
phases, rather than the actual concentrations.
A selectivity ratio may be dened in terms of either mass or mole fractions as:

Where xA and xB the mass or mole fractions of A and B in the two phases E and R.
Figure 6: Equilibrium distribution of solute A in phases B and C
The selectivity ratio has the same significance in extraction as relative volatility has in
distillation, so that the ease of separation is directly related to the numerical value of . As
approaches unity, a larger number of stages is necessary for given degree of separation and
the capital and operating costs increase correspondingly. When = 1 any separation is
impossible.