CE-508 SEPARATION PROCESS

July 2023 Semester

LIQUID-LIQUID EXTRACTION
• Introduction
• Equilibrium Data
• Number of theoretical stages
• Co current and counter current operations
• Classification of extraction equipments
LIQUID-LIQUID EXTRACTION
Introduction
• Liquid-liquid extraction (sometimes abbreviated LLX) is a mass transfer
operation also called solvent extraction
• A solution (called the feed which is a mixture of a solute and a carrier liquid) is
brought into intimate contact with a second immiscible or slightly miscible liquid
(called the solvent)
• The two liquid phases that have different densities are then separated.
• The solute-rich phase (this is the solvent stream, now enriched with the solute) is
called the extract
• The residual feed stream that may have a little of the solute left in it is called the
raffinate.
A: carrier
B: solvent
C: solute
LIQUID-LIQUID EXTRACTION
A liquid-liquid extraction process generally involved 4 steps:
1. Bringing the feed and the solvent into intimate contact by
dispersing one phase into the other as droplets.
2. Separation of the extract and the raffinate phases that have
different densities.
3. Removal and recovery of the solute from the extract phase in
a relatively pure form (by distillation, evaporation,
crystallization, etc.).
4. Removal and recovery of the solvent from each phase, usually
by distillation.
Why Liquid-Liquid Extraction?
a) The components to be separated have close boiling points.
For example, aromatics are extracted from paraffinic feedstocks in the refineries by using a
solvent like sulphur dioxide, n-methyl pyrolidone, sulpholane, etc. The number of distillation
trays becomes prohibitively large if the relative volatility is close to unity (say less than 1.2),
and solvent extraction, therefore, may be an attractive alternative for such a mixture.
a) Separation of heat-sensitive materials such as antibiotics, vitamins, etc. Penicillin is
recovered from the fermentation broth by using a suitable solvent such as butyl
acetate.
b) Recovery of non-volatile solutes, usually from aqueous solutions, in hydro-metallurgy.
c) Recovery of a solute from a very dilute solution-for example, bioseparation (proteins,
antibiotics, high-value bioproducts).
d) Removal of organics from aqueous streams-for example, removal of phenol from
aqueous wastes.
Equilibrium Data
LIQUID-LIQUID EQUILIBRIA (LLE) or Equilibrium Data is of vital
importance for the design of an extraction equipment
Ternary Systems comprising a carrier (A), a solvent (B), and a
solute (C).
Three binary mixtures can be formed out of these components:
A-B, B-C and C-A.
The mutual miscibility behaviour of the components in each of
these binaries determines the nature of the equilibrium diagram
for the ternary system
Equilibrium Data
Most of the ternary systems fall in one of the following categories:
a) The carrier (A) and the solvent (B) are practically immiscible. The equilibrium
in such a system may be represented in the form of a x-y plot as in the case of
distribution of a solute between a carrier gas and a solvent. If the solute
concentration is small, a Henry's law-type linear distribution law applies.
b) The solute is miscible with the carrier and with the solvent in all proportions,
but the carrier and the solvent are only partially miscible (A-C and B-C are
miscible pairs; the pair A-B is partially miscible). Such a system is called a
Type-I ternary system. About 75% of ternary liquid systems fall in this category.
c) The solute is completely miscible with the carrier; but both the solute and the
carrier have limited miscibility with the solvent (the binary A-C is miscible in all
proportions; the pairs B-C and A-B are only partially miscible). A ternary mixture
of this type is called a Type II system.
Experimental Determination of Liquid-liquid Equilibrium
Data
As in the case of determination of gas-liquid or vapour-liquid equilibria, liquid-liquid
equilibrium data are obtained by measuring the concentrations of the three
components in the two liquid phases in equilibrium at a given temperature. The
following steps are followed:
a) Suitable quantities of purified A, B, and C are taken in an equilibrium cell
maintained at a constant temperature. The content is mixed vigorously for a
sufficient time to ensure attainment of equilibrium.
b) The content is allowed to separate into two phases.
c) Samples are drawn from the two phases and analyzed for the concentrations
(expressed as mass fractions or mole fractions) of A, B, and C.
A set of such experiments conducted with varying amounts of the three
components at a constant temperature yields the data for the construction of a
liquid-liquid equilibrium diagram.
Graphical Representation of Liquid-liquid Equilibrium
Data
It is not possible to describe a phase or the equilibrium of two phases
in contact in terms of the three concentrations using the normal
rectangular coordinate system.
But this can be done conveniently on an 'equilateral triangular graph’.
Also there are two other techniques of representation of ternary
equilibrium data using the rectangular coordinate system: (a) a 'right-
angled triangular diagram' in which only two concentrations are
plotted, and (b) using rectangular coordinates and plotting the mass
fractions (or mole fractions) of the solute and of the solvent in the two
phases on 'solvent-free basis'.
The equilateral triangular
diagram
The basis of the technique of
presentation of equilibrium data on an
equilateral triangular graph paper is that
the sum of the distances of a point within
an equilateral triangle from the three
sides is equal to the height of the triangle.
On the equilateral triangle ABC in Figure,
the vertices A, B and C represent the
'pure components' A, B and C
respectively; the sides AB, BC and CA
represent mixtures of A and B, B and C,
and C and A respectively. A point within
the ΔABC represents a mixture of the
components A, B and C.
The equilateral triangular
diagram
Consider the point M, for example.
A mixture of A, B and C having 16% A,
24% B, and 60% C is represented by the
point M on the triangular diagram. The
sum of its distances from the three sides
is MN1 + MN2 + MN3 = CT, which is equal
to the altitude of the triangle. From
Figure it is found that the point M lies on
the dotted line representing 60% C (MN1
= 0.6CT, CT being the altitude). Also, the
point M lies on the dotted lines
representing 16% A and 24% B
respectively.
The equilateral triangular
diagram
The LLE diagram of a ternary system is
depicted in Figure. Here the solute C is
miscible with the carrier A and with the
solvent B in all proportions, but the carrier
and the solvent are only partially miscible
(Type I system). The curve RPS is the
equilibrium diagram in the equilateral
triangular coordinate system. It is obtained
by plotting the data points representing the
two liquid phases in equilibrium. The point R
on the line AB represents the solubility of the
solvent B in the carrier A; the point S
represents that of the carrier A in the solvent
B if there is no solute.