Liquid Liquid Extraction

Recommended Book
Richardson, J. F., Harker, J. H. and
Buckhurst, J. R., “Coulson &
Richardson's Chemical Engineering”,
Vol. 2, 5th Ed., Elsevier, 2002.
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”

In this operation, it is essential that the liquid-mixture feed

and solvent are at least partially if not completely immiscible

2
Three stages are involved
1. Bringing the feed mixture and the solvent into intimate contact
2. Separation of the resulting two phases
3. Removal and recovery of the solvent from each phase

L-L extraction can also be carried out in stagewise equipment, prime

example being a mixer-settler unit where
Mixing of two liquid phases occur by agitation, followed by
Settling in a separate vessel by gravity

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Extraction vs Distillation

Extraction is preferred when:

• 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

• Recovery of solute from a dilute solution

• Temperature sensitive or heat sensitive

• Different nature of components

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Introduction

Can be carried out either as a batch

or continuous process

 Extract
containing the required solute in the
added solvent
Single-stage batch extraction
 Raffinate
the weaker solution with some
associated solvent

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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.

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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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Equilibrium Data

 acetone (A)–Water (B)–methyl

isobutyl ketone (C)

 solute A is completely miscible

with the two solvents

 B and C solvents are only partially

miscible with each other

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Equilibrium Data

 A mixture indicated by point H

consists of the three components
A, B and C in the ratio of the
perpendiculars HL, HJ, HK.

 The distance BN represents the

solubility of solvent C in B and MC
that of B in C

 Tie line (PQ)

 Plait point (F)

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 Equilibrium Data

 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.
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Equilibrium Data

 In Figure two separate two-phase

regions are formed.

 Under the conditions shown in

Figure, A and C are miscible in all
proportions, although B and A,
and B and C are only partially
miscible.

 Aniline (A), water (B), and phenol

(C) represent a system

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Equilibrium Data

 in Figure the two-phase regions

merge on varying the
temperature.

 Aniline (A), water (B), and phenol

(C) represent a system.

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Equilibrium Data

Selectivity Ratio

where xA and xB are the mass or mole fractions of A and B in the two phases E
and R.

• 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 given
degree of separation and the capital and operating costs increase
correspondingly.
• When β = 1 any separation is impossible.
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Calculation of Number of Theoretical Stages

 Co-current contact with partially miscible solvents

 Co-current contact with immiscible solvents

 Countercurrent contact with immiscible solvents

 Countercurrent contact with partially miscible solvents

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Co-current contact with partially miscible solvents

 F = feed

 E = extract

 R = Raffinate

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Co-current contact with partially miscible solvents

 F = feed

 E = extract

 R = Raffinate

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Co-current contact with immiscible solvents

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Co-current contact with immiscible solvents

 For n stages

 For number of stage

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Countercurrent contact with immiscible solvents

 F = Initial feed

 B = solute , A = solvent R1 = raffinate for first unit

 Rn = Raffinate from nth unit.

 S = Solvent added to nth unit and passes countercurrently and

leave extract E1 from 1st unit. 19
Countercurrent contact with immiscible solvents

 X = the ratio of solute to solvent in the raffinate streams

 Y = the ratio of the solute to solvent in the extract streams

Since the solvents are immiscible, apply the material balance

 For the 1st stage:

 For the nth stage:

 For the whole unit:

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 Countercurrent contact with immiscible solvents

 Equation of operating line

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 Problem Statement
a. 160 cm3/s of a solvent S is used to treat 400cm3/s of a 10 per
cent by mass solution of A in B, in a three-stage
countercurrent multiple-contact liquid–liquid extraction
plant. What is the composition of the final raffinate?
b. Using the same total amount of solvent, evenly distributed
between the three stages, what would the composition of
the final raffinate if the equipment were used in a simple
multiple-contact arrangement?

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23
Countercurrent contact with partially miscible solvents

 F = Initial feed

 E1 = Final extract

 S = solvent stream En+1

 Rn = raffinate

Applying material balances: 24

Countercurrent contact with partially miscible solvents

 Over the first unit

 Over stages 1 to n

 Over the unit n

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Countercurrent contact with partially miscible solvents

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Classification of Extraction Equipment's

 Stage-wise Equipment

 Differential Contact Equipment

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28
29
STAGE-WISE EQUIPMENT FOR EXTRACTION

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The mixer–settler

• In the mixer-settler, the solution and solvent are

mixed by some form of agitator in the mixer, and then
transferred to the settler where the two phases
separate to give an extract and a raffinate.

• The mixer. As a result of the agitation achieved in a

mixer, the two phases are brought to, or near to,
equilibrium so that one theoretical stage is frequently
obtained in a single mixer where a physical extraction
process is taking place.

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 The mixer–settler
• For a circular vessel, baffles are required to give the optimum
degree of agitation and the propeller should be mounted just
below the interface.
• The two key parameters determining power of agitator are the
Reynolds number and the power number.

• The settler. In this unit, gravitational settling frequently occurs

and, in addition, coalescence of droplets must take place.
Baffles are fitted at the inlet in order to aid distribution.
• The rates of sedimentation and coalescence increase with drop
size, and therefore excessive agitation resulting in the
formation of very small drops should be avoided.

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Combined mixer–settler units

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 Combined mixer–settler units

• The impeller has swept-back vanes with double shrouds, and the two
phases meet in the draught tube.

• A baffle on top of the agitator reduces air intake and a baffle on the inlet
to the settler is important in controlling the flow pattern. This
arrangement gives a good performance and is mechanically neat.

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Raising the impeller
above the draught tube
increases internal
recirculation which in
turn improves the
stage efficiency, as
shown in Figure

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• The effect of agitation on
the thickness of the
dispersion band is shown
in Figure.
• The depth of the
dispersion band ZB
varies with the total flow
per unit area. Whilst this
work was primarily
aimed at a design for
copper-extraction
processes

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Segmented mixer–settler

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 Segmented mixer–settler

• Novel features for a combined mixer–settler are incorporated in a unit

where specially designed Knit Mesh pads are used to speed up the rate
of coalescence.

• The centrally situated mixer is designed to give the required holdup, and
the mixture is pumped at the required rate to the settler which is
formed in segments around the mixer, each fed by individual pipework.

• One key advantage of this design is that the holdup of the dispersed
phase in the settler is reduced to about 20 per cent of that in the mixer,
as compared with 50 per cent with simple gravity settlers

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 Knit Mesh Separator
• The use of KnitMesh in a
coalescer for liquid–liquid
separation applications is
illustrated in Figure where an
oil–water mixture enters the
unit and passes through the
coalescer element.
• As it does so, the water droplets
coalesce and separation occurs
between the oil and the water.
After passing through the
KnitMesh, the two phases are
readily removed from the top
and bottom of the unit

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 Kuhni mixer–settler column
• It is a series of mixer–settlers in the form of a
column. The unit consists of a number of
stages installed one on top of another, each
hydraulically separated, and each with a
mixing and settling zone as shown in Figure.

• With this design, it is possible to eliminate

some of the main disadvantages of
conventional mixer–settlers whilst maintaining
stage wise phase contact.

• As the mixer turbines do not need to transport

the liquids from stage to stage, the speed of
rotation can be adjusted so as to achieve
optimum droplet sizes
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 Baffle-plate columns
• These are simple cylindrical columns
provided with baffles to direct the
flow of the dispersed phase, as shown
in Figure.

• The efficiency of each plate is very low,

though since the baffles can be
positioned very close together at 75–
150 mm, it is possible to obtain several
theoretical stages in a reasonable
height

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 The Scheibel column
• One of the problems with perforated
plate and indeed packed columns is
that re-dispersion of the liquids after
each stage is very poor.

• To overcome this, SCHEIBEL introduced

a unit, shown in Figure, in which a
series of agitators is mounted on a
central rotating shaft. Between the
agitators is fitted a wire mesh section
which successfully breaks up any
emulsions.

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DIFFERENTIAL CONTACT EQUIPMENT FOR
EXTRACTION

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 Spray columns
• Two methods of operating spray
columns are shown in Figure. Either
the light or heavy phase may be
dispersed.

• In the Fig (a) the light phase enters

from a distributor at the bottom of
the column and the droplets rise
through the heavier phase, finally
coalescing to form a liquid–liquid
interface at the top of the tower.

• Alternatively, the heavier phase may

be dispersed, in which case the
interface is held at the bottom of the
tower as shown in (b). 44
 Spray columns

• Although spray towers are simple in construction, they are inefficient

because considerable recirculation of the continuous phase takes place.

• There is very little turbulence in the continuous phase and lack of

interface renewal, and appreciable axial mixing results in poor
performance.

• Because the droplets of dispersed phase rise or fall through the

continuous phase under the influence of gravity, it will be apparent that
there is a limit to the amount of dispersed phase that can pass through
the tower for any given flowrate of continuous phase.

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 Spray columns

• Thus referring to Figure (a), any additional light phase fed to the bottom
of the tower, in excess of that which can pass upwards under the
influence of gravity, will be rejected from the bottom of the unit and the
tower is then said to be flooded.

• It is therefore important to be able to predict the conditions under

which flooding will occur, so that the diameter of tower may be
calculated for any required throughput.

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 Dispersed phase hold-up
• Figure represents a section of a spray
tower of unit cross-sectional area.

• The light phase is assumed to be

dispersed, and the volumetric flowrates
per unit area of the two phases are L’d and
L’c respectively. The superficial velocities ud
, uc of the phases are therefore also equal
to L’d and L’c.

• Under steady-state conditions the amount

of dispersed phase held up in the tower in
the form of droplets is conveniently
expressed in terms of the fractional hold-
up j , that is the fractional volume of the
two-phase dispersion occupied by the
dispersed phase 47
• The velocity of the dispersed phase relative to the tower is
therefore L’d /j . Similarly, the relative velocity of the continuous
phase is equal to L’c /(1 − j).
• If the overall flow is regarded as strictly countercurrent, the
sum of these two velocities will be equal to the velocity of the
dispersed phase relative to the continuous phase, ur or:

• In case of spray towers ur is well represented by u0(1 − j)

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Contd.

• Where u0 is the velocity of a single droplet relative to the

continuous phase, and is termed the droplet characteristic
velocity.

• This equation relates the hold-up to the flowrates of the

phases and column diameter through the characteristic
velocity, u0. It therefore gives a method of calculating the
holdup for a given set of flowrates if u0 is known

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 Flooding-point condition
• A plot of previous equation in the
form of ud and uc against j for a
typical value of u0 = 0.042 m/s is
shown in Figure.

• Only the root which lies between

zero and the flooding-point values
of ud and uc is realizable in practice.
These portions of the hold-up
curves are shown by full lines in
Figure.

• If the flowrate of one of the phases

is kept constant, an increase in the
flowrate of the other phase will
result in an increased value of the
hold-up until the flooding-point is
reached 50
 Interfacial area
• The interfacial area per unit volume of tower, or
specific area, is given by:

• Where j is the fractional hold-up and ds is the mean

droplet size, defined as:

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Contd.

where n1 is the number of droplets of diameter d1 in a

population.

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 Rotary annular columns
• With these columns mechanical
energy is provided to form the
dispersed phase.

• The equipment is particularly

suitable for installations where
a moderate number of stages is
required, and where the
throughput is considerable.

• A well dispersed system is

obtained with this arrangement

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 Centrifugal extractors

• If separation is difficult in a mixer–settler unit, a centrifugal extractor

may be used in which the mixing and the separation stages are
contained in the same unit which operates as a differential contactor.

• In the Podbielniak contactor, the first of the rotating machines to be

developed, the heavy phase is driven outwards by centrifugal force and
the light phase is displaced inwards.

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• Referring to Figure, the heavy phases enters at D, passes to J and is driven out at B.
• The light phase enters at A and is displaced inwards towards the shaft and leaves at C.
• The two liquids intermix in zone E where they are flowing counter currently through
the perforated concentric elements and are separated in the spaces between.
• In zones F and G the perforated elements are surfaces on which the small droplets of
entrained liquid can coalesce, the large drops then being driven out by centrifugal
force.
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• The contactor finds extensive use where high performance phase
separation and countercurrent extraction or washing in the one
unit are required.
• Particularly important applications are the removal of acid sludges
from hydrocarbons, shown in Figure hydrogen peroxide
extraction, sulphonate soap and antibiotics extraction, the
extraction of rare earths such as uranium and vanadium from
leach liquors, and the washing of refined edible oils.

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 Alfa-Laval Centrifugal Extractor
• The Alfa-Laval contactor shown in
Figure has a vertical spindle and the
rotor is fitted with concentric cylindrical
inserts with helical wings forming a
series of spiral passages.

• The two phases are fed into the bottom,

the light phase being led to the
periphery from which it flows inwards
along the spiral, with the heavy phase
flowing counter currently.

• High shear forces are thus generated

giving high extraction rates.

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