Mass Transfer (ChE - 392)

5-liquid-Liquid Extraction (Solvent Extraction)

Saeed GUL, Dr.Techn, M.Sc. Engg.

Associate Professor and Chairman

Department of Chemical Engineering,

University of Engineering & Technology Peshawar, PAKISTAN
 Introduction
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
The component balances will be essentially identical to those for
leaching, but there are two major differences that complicate
the calculations:
 the carrier phase is a liquid, not a solid, so the physical
separation techniques will change, and
 two distinct phases develop, so the simplicity of uniform
solution is lost.

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 Introduction
Three Steps are Involved in Liq-Liq Extraction
1. Bringing the feed mixture and the solvent into intimate
contact,
2. Separation of the resulting two phases, and
3. Removal and recovery of the solvent from each phase.

It is possible to combine stages 1 and 2 into a single piece of

equipment such as a column which is then operated continuously.
Such an operation is known as differential contacting.
Liquid–liquid extraction is also carried out in stagewise
equipment, the prime example being a mixer–settler unit in which
the main features are the mixing of the two liquid phases by
agitation, followed by settling in a separate vessel by gravity

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 Introduction

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 Extraction is in many ways complementary to distillation and is
preferable in the following cases:
 Where distillation would require excessive amounts of heat, such
as, for example, when the relative volatility is near unity.
 When the formation of azeotropes limits the degree of separation
obtainable in distillation.
 When heating must be avoided.
 When the components to be separated are quite different in
nature.

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 Solvent Selection
One of the key decisions when designing an extraction process is
the choice of the solvent to be used. Issues include:
Selectivity: compare the equilibrium ratio of solute in each phase
Distribution Coefficients: K = y/x at equilibrium; large values
preferable
Insolubility: solvent should not be soluble in carrier liquid
Recoverability: consider constraints (i.e. azeotropes)

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 Solvent Selection
Density: must be different so that phases can be separated
by settling
Interfacial Tension: if too high, liquids will be difficult to mix
Chemical Reactivity: solvent should be inert and stable
Viscosity, Vapor Pressure, Freezing Point: low values make
storage easier
Safety: toxicity, flammability Cost

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 EXTRACTION PROCESSES
The three steps in all liquid–liquid extraction operations, may
be carried out either as a batch or as a continuous process:

 In the single-stage batch process

illustrated in Figure, the solvent and Solvent
solution are mixed together and then Extract E
allowed to separate into the two
phases: Mix and
 the extract E containing the required Separate
solute in the added solvent and the Raffinate R
 raffinate R, the weaker solution
with some associated solvent.
 With this simple arrangement mixing
Solution
and separation occur in the same
vessel.

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 Multiple-contact system with
fresh solvent
Mixers and separators are shown as separate vessels. There are
three main forms of equipment. First there is the mixer-settler as
shown in 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
In all cases, the extraction units are followed by distillation or a
similar operation in order to recover the solvent and the solute

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 Selectivity Ratio
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
defined in terms of either mass or mole fractions as:

where xA and xB are the mass or mole fractions of A and B in the

two phases E and R. For a few systems β tends to be substantially
constant, although it more usually varies with concentration. 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 β. As β approaches unity, a larger
number of stages is necessary for a given degree of separation and
the capital and operating costs increase correspondingly.
When β = 1 any separation is impossible.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 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 accurately only if both solvents are
immiscible, and if 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.
 Where the concentrations are small, the distribution law usually
holds provided no chemical reaction occurs.

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 Equilibrium Data
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.

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 Compositions in Ternary Diagrams

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 Compositions in Ternary Diagrams
Triangular Grid Method

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 Compositions in Ternary Diagrams
Triangular Grid Method

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 Compositions in Ternary Diagrams
Triangular Grid Method

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 Compositions in Ternary Diagrams

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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 Compositions in Ternary Diagrams
Two lines are drawn Two Line Method
through composition 1
parallel to any two sides of
the triangle- here AB and
AC. The intersection of
these two lines with the
third side (BC) divides this
side into three line
segments. The lengths of
the individual line segments
are proportional to the
relative amounts of the
three components A, B and
C.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
 The three corners represent
three pure components, A, B
and C. The point M is a
mixture. The perpendicular
distance from the point M to
any base line is the mass
fraction of the component at
the corner opposite to that
base line. For example, the
distance from M to base AB is
the mass fraction of C (xC=
0.40).

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