LIQUID-LIQUID EXTRACTION

CHAPTER 22

LIQUID-LIQUID EXTRACTION

LIQUID-LIQUID extraction is the term applied to any operation in which a material

dissolved in one liquid phase is transferred to a second liquid phase. The solvent must be
insoluble, or soluble to a limited extent only, in the solution to be extracted.

Liquid-liquid extraction consists of the same basic steps:

1. Intimate mixing or contact of the solvent with the solution to be treated, so as to
transfer the solute from the solution to the solvent.
2. Separation of the liquid solution phase from the liquid solvent phase.

The complete extraction process may involve other operations such as the separation and
recovery of the solvent from the solute and of the solvent. The removal and recovery of
the solvent may be more important in determining the successful application of the
extraction process than the degree of extraction and separation accomplished in the two
basic steps. The separation and recovery of the solvent may be accomplished by various
methods such as distillation or simple heating or cooling to diminish the solubility of the
solute or of the solvent.

Liquid-liquid extraction is widely used for the separation of the components of a solution,
particularly when:
1. The components are relatively nonvolatile.
2. The components have substantially the same volatilities from the mixture.
3. The components are sensitive to the temperatures required for the separation by
distillation.
4. The desired less-volatile component is present in the solution only in relatively small
amounts.

The different distribution of the components of the feed mixture between the two layers
at equilibrium is depended upon to effect the desired separation. The layer containing the
greater concentration of the solvent and the smaller concentration of the feed liquid is
referred to as the "extract" layer. The other layer, containing the greater concentration of
the feed liquid and the smaller concentration of solvent is referred to as the "raffinate"
layer.

The solvent is said to be selective for the component of the feed which is found in greater
ratio to the other components in the extract than in either the raffinate or the original feed.
The solvent is selective for component A if ( x A /x B )F < ( y A / y B )1> ( x A / x B )n .

The residual materials remaining from the extract and raffinate layers after the major part
of the solvent is removed are frequently referred to as the extract and the raffinate,
respectively.
 LIQUID-LIQUID EXTRACTION
The extraction may involve only the physical process of separation by solution, or
chemical reactions between the extracted substances and the solvent or other materials
dissolved in the solvent may take place. Liquid-liquid extraction has been widely used for
the removal of the naphthenic and aromatic constituents from the paraffinic constituents
of lubricating oil stocks by means of a wide variety of solvents and solvent mixtures. A
combination of liquid-liquid extraction with fractional distillation known as "extractive
distillation" has become of increasing industrial importance in recent years for the
separation of close-boiling com pounds and azeotropic mixtures.

EQUIPMENT

All extraction equipment attempts to secure a large contact area between the phases since
the rate of transfer of the distributed component is directly proportional to this area.
Differentiation between the various types of equipment is based on the method employed
for contacting the liquid phases. Mixing the two phases by subdividing and dispersing
one phase forms new surfaces with rapid transfer of the solute across the large contact
area. The ease of mixing depends upon the interfacial tension between the two phases, the
relative densities of the two phases, and the viscosity of each phase. Separation of the two
phases after they have been brought into contact may be accomplished by gravity or, less
frequently, by centrifugal force.

Fig. 303. Diagrammatic cross section of a baffle plate column for liquid-liquid extraction.
 LIQUID-LIQUID EXTRACTION
The equipment used to contact the two phases also acts as the separator, and mixing of
the two phases is undesirable. This method depends on the in creased length of the path
of flow to obtain a large contact area and usually requires less energy consumption than
when the two phases are mixed. The term "wetted-wall" tower is often used for the
vertical type. In both the horizontal and vertical type of equipment the extended contact
area is obtained by having the equipment of sufficient length.

The baffle-plate column (Fig. 303) is a modification of the simple vertical column which
provides an increased contact area without greatly increasing the length of the column.
The lighter liquid flows upward around the baffle and through the free area between the
tray and the inside walls of the column. The heavier liquid flows along the baffle,
overflows over the lip, and then flows downward to the next tray.

If centrifugal force is utilized to prevent mixing of the phases, higher flow rates may be
used. The Podbielniak centrifugal extractor (Fig. 304) is based on this principle.
Mixers include air agitators, mechanical mixers, and flow mixers and are used to mix the
phases in one vessel with the separation accomplished in a separate vessel. Columns may
be of the spray, packed, or plate type and are usually operated with countercurrent flow
of the phases. Separation of the two phases takes place within the column itself and not in
a separate vessel. The heavier liquid phase enters at the top and leaves at the bottom ; the
lighter liquid phase flows upward in the opposite direction.

Fig. 304. Diagram of a centrifugal countercurrent extractor

 LIQUID-LIQUID EXTRACTION

Fig. 305. Schematic diagram indicating methods for the control of the interface level in
columns used for liquid-liquid extraction.

The spray column is the simplest type of equipment and consists of a suitable vessel,
usually cylindrical and considerably longer in length than in diameter, and equipped with
nozzles or distributors for the phase to be dispersed. The continuous phase fills the
vessel, and the dispersed phase flows through the continuous phase. The effectiveness of
the extraction depends upon the subdivision of the dispersed phase into small droplets.
Coalescence of these droplets after they are formed tends to decrease the effectiveness.
Coalescence is favored by a high interfacial tension between the liquid phases and by
high flow rates of the dispersed phase.

The packed column differs from the spray column in that the vessel is partially filled
with suitable packing, either solid or hollow. The packings used have a wide variety of
shapes and sizes. Thin-walled hollow cylinders of the same length as diameter (Raschig
rings) and saddle-shaped units called Berl saddles are frequently used. The performance
of a packed column depends primarily on the large contact area produced by the packing
and less on the subdivision of the dispersed phase. The level of the interface may be
maintained at any point in the column although usually at the top or bottom of the
column.
Figure 305 indicates methods for controlling the level of the interface.

A plate column consists of a series of plates, spaced at regular intervals along the
column. Circular pipes extending above the bottom of the plates are used for the flow of
the continuous phase from plate to plate (Fig 306). If there is a marked difference in the
wetting of the column by the two liquids, successful operation is obtained only if the
nonwetting phase is the dispersed phase.
 LIQUID-LIQUID EXTRACTION

Fig. 306. Perforated plate, or sieve plate, column for liquid-liquid extraction.

The sieve-plate column corresponds, in a sense, to a series of short spray columns

mounted one above the other. The dispersed liquid recombines above the plate and is
then again subdivided and redispersed in passing through the perforations of the next
plate. Since it has been shown that for single drops an appreciable amount (40 to 45 %) of
the total extraction occurs as the drop is formed and before its release from the nozzle,17
it is possible that the reported effectiveness of this type of equipment is due to the
frequent formation of new surfaces at each of the plates.

The bubble-cap plate column, Fig. 327, widely used for liquid-vapor contacting has
been found unsatisfactory for liquid-liquid extraction as ordinarily designed.16 The
higher interfacial tension between two liquids as compared to that between a liquid and a
vapor, and the lower agitation obtained due to higher viscosities when two liquid phases
are contacted, probably account for the poor performance of bubblecap columns when
used for liquid-liquid extraction. The flow rates of the liquid phases in columns used
for liquid-liquid extraction are limited by the fact that after certain limiting flows have
been reached the column will no longer function satisfactorily. This limiting flow is
called the "flooding point" and depends on the flow rates of both the phases.

METHODS OF OPERATION

The same methods of operation that were used for solid-liquid extraction may also be
applied to liquid-liquid extraction, namely,
(1) single contact
(2) simple multiple-contact
(3) countercurrent multiple-contact.
 LIQUID-LIQUID EXTRACTION
Countercurrent multiple-contact operation may be either batch or continuous. Because of
the greater ease in handling liquid phases,continuous operation is more commonly used
in liquid-liquid extraction than in solid-liquid extraction.

Fig. 307. Schematic diagram illustrating countercurrent multiple-contact extraction

with extract reflux, stream L0.

Fig. 308. Schematic diagram illustrating countercurrent multiple-contact extraction with

raffinate reflux, stream V n +1.

The use of "reflux" with countercurrent multiple-contact operation may be

advantageous. When countercurrent multiple-contact extraction without reflux is used,
the maximum concentration of solute that can be obtained in the extract layer, even if an
infinite number of stages is used, is that corresponding to equilibrium with the incoming
feed. This type of operation has been termed "enriching by reflux" or "extract reflux "
(Fig. 307). The feed (stream LF ) enters at an intermediate stage of the system. Fresh
solvent (stream V n +1) enters at stage n, and the raffinate layer (stream Ln) leaves from this
stage. The extract layer (stream Vi) leaves stage 1 and is sent to the solvent removal unit
where solvent is removed from the stream. The resulting material is then divided into two
portions, the reflux (stream Lo) which is returned to stage 1 and the extract product
(stream D).
Reflux may also be provided at the end of the system from which the raffinate layer
leaves. With such an operation, termed "exhausting by reflux" or "raffinate reflux"
(Fig. 308), a portion of the raffinate layer leaving the system is mixed with the incoming
solvent so that the resulting liquid (stream V n +1) is usually saturated with respect to the
major raffinate component. This liquid is then introduced into stage n. The feed (stream
Lo) is introduced at the opposite end of the system (stage 1), and the extract layer leaves
this same stage. The use of raffinate reflux has been said to improve the degree of
removal of solute from the rafnnate.
Both extract and raffinate reflux may be employed simultaneously. However, the use of
reflux is not generally applicable but is limited to certain types of ternary systems as will
be considered under equilibrium relationships.
 LIQUID-LIQUID EXTRACTION

METHODS OF CALCULATION

In the case of liquid-liquid extraction where separate mixing and settling vessels are used,
each combination of a mixing vessel and a settling vessel constitutes a stage which may
or may not be an equilibrium stage, depending on whether or not equilibrium exists
between the two phases leaving the stage.

In the present methods for calculating the number of equilibrium stages required for a
liquid-liquid extraction, it is assumed that only the two liquid phases are present, and the
system consists of three (or more) components, the two (or more) components present in
the original solution, and the solvent used for the extraction. The presence of small
quantities of impurities may be neglected as far as the equilibrium relationships are
concerned. Any single stage operates at a constant temperature.

The calculation of the number of equilibrium stages required for a liquid-liquid extraction
is based on the two principles of
(1) material balances, and
(2) equilibrium relationships.

Material balances
For the total streams and for any individual component may be made as was done for
solid-liquid extraction.

Equilibrium Relationships in Ternary Systems

According to the phase rule there are three degrees of freedom (three independent
variables) for a ternary (three-component) system consisting of two liquid phases at
equilibrium.At any temperature and pressure, therefore, only one degree of freedom
remains.A ternary system composed of components A , B, and C may be regarded as
composed of three binary systems—A and B, B and C, and A and C. The most common
type of ternary-phase diagram is that for which two of the binary systems are completely
miscible liquids and the third binary system is one in which the liquids are only partially
miscible.
 LIQUID-LIQUID EXTRACTION

At 45° C, diphenylhexane and docosane are completely miscible liquids, diphenylhexane

and furfural are completely miscible liquids, and docosane and furfural are partially
miscible liquids.
Any point inside the triangle represents a mixture of all three components. The curve
MPQ , called the solubility curve, separates region I of the triangle representing mixtures
which exist as a single liquid phase under equilibrium conditions, from region II which
represents mixtures of two coexisting liquid phases under equilibrium conditions. Any
straight line such as HI , FG , DE , or MQ joining two points on the solubility curve which
represent the com positions of liquid phases in equilibrium is called a "tie line." Point J
in the two-phase region of the triangle represents the overall composition of a mixture of
two liquid phases which, at equilibrium, will have the compositions indicated by the
intersections of the tie line through point J with the solubility curve (points H and I).
The point corresponding to a tie line of zero length, that is for which the two liquid
phases in equilibrium have the same composition, is called the "critical" or "plait"
point and represented by point P.
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The influence of pressure on the equilibrium liquid phases may usually be neglected
unless high pressures are considered. The effect of temperature usually much more
important as may change the type of phase diagram, increase or decrease the area of the
two-phase region without affecting the type of diagram, or change the slope of the tie
lines. The effect of temperature on the phase diagram for diphenylhexane-docosane-
furfural shown in Fig. 311.

Another type of ternary-phase diagram which not encountered so often that for two
binary systems which have partially miscible liquids and a third binary system in which
the liquids are completely miscible. The phase diagram is illustrated in Fig. 312. In this
case the solubility curve not continuous curve but consists of two branches, MN and QR,
respectively, which extend from the side of the triangle to the hypotenuse. The two-phase
region lies between the two branches, whereas the single-phase regions are outside the
two branches.

This particular diagram is of special interest because it permits the use of extract reflux.
The equilibrium relationships for this system are very sensitive to temperature in the
range from 25° to 45° C. If the temperature is increased to 45° C, the phase diagram
(Fig. 313) is
 LIQUID-LIQUID EXTRACTION

similar to the type first discussed, as the methylcyclopentane and aniline are completely
miscible at this temperature. If a separation is to be effected by liquid-liquid extraction,
the overall composition of the mixture in any stage must lie in the two-phase region of
the phase diagram.

GRAPHICAL METHODS

The graphical method is simply a graphical representation of the material balances and
equilibrium data and is similar to that used for solid-liquid extraction. The representation
of material balances, the concept of addition and difference points, and the general
properties of the triangular diagram are the same in both cases. The main distinction
between the two operations is that the overflow in solid-liquid extraction consists of only
two components whereas in liquid-liquid extraction all three components are usually
present in the overflow. Also, there is no inert material in liquid-liquid extraction.

Nomenclature for liquid-liquid extraction

L－The quantity of one liquid stream, usually that stream consisting primarily of
component C and designated the "raffinate" phase.
V－The quantity of the other liquid stream, usually that stream consisting primarily of
component S and designated the "extract" phase.
x－ Mass fraction in stream L of the component designated by a letter subscript, as x A,
x C , or x S .
y－Mass fraction in stream V of the component designated
by a letter subscript, as y A , y C , or y S .
 LIQUID-LIQUID EXTRACTION
In the diphenylhexane-docosane-furfural system at 45° C (Fig. 310), furfural may be used
as the solvent for the extraction of a solution of diphenyl-hexane and docosane. The
furfural will then be designated as component S. The equilibrium data show that the ratio

Mass of dipℎenylℎexane
Mass of (dipℎenylℎexane +docosane )
is greater in the extract (furfural) phase than in the raffinate (docosane) phase.
Consequently, the furfural is selective for the diphenylhexane. The diphenylhexane will
therefore be designated as component A, and the docosane as component C. The quantity
of the extract phase from any stage will be designated by the symbol V, an appropriate
subscript being used to indicate the stage from which the stream flows. Similarly, L will
represent the quantity of raffinate phase leaving any stage.

CONTINUOUS COUNTERCURRENT MULTIPLE-CONTACT OPERATION

The schematic diagram of a liquid-liquid extraction system using continuous

countercurrent multiple-contact operation may be simplified by omission of the mixer, in
which case V n +1 represents fresh solvent. When the system is operating under steady-state
conditions, the mate rial balances over the whole system are represented by equations
identical to those obtained for solidliquid extraction (equation 241 and 242)

Total material balance:

L0 +V n +1=Ln+ V 1 (241)

Material balance for any component:

L0 x0 +V n+1 y n +1=Ln xn +V 1 y 1 (242)

Material balance for any component A:

L0 ( x A )0 +V n +1 ( y A )n+1=L n ( x A ) n+V 1 ( y A )1 (242.A)

Similarly, the equations defining the quantity and composition of the difference point are
the same.
∆=L0 −V 1=L1 −V 2=⋯
¿ Ln − V n+1 (243)
L0 x0 −V 1 y 1=L1 x 1 −V 2 y 2=⋯
¿ Ln x n −V n +1 y n +1 (244)
L x −V 1 y 1 − V n+1 y n+1
x ∆= 0 0 =⋯
L0 −V 1
L n x n − V n+1 y n+1
¿ (245)
Ln −V n +1