EXTRACTION, LIQUID-LIQUID

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Thornton, J.D.
DOI: 10.1615/AtoZ.e.extraction_liquid-liquid
Liquid-liquid (or solvent) extraction is a countercurrent separation process for isolating
the constituents of a liquid mixture. In its simplest form, this involves the extraction of a
solute from a binary solution by bringing it into contact with a second immiscible solvent
in which the solute is soluble. In practical terms, however, many solutes may be present in
the initial solution and die extracting ‘solvent’ may be a mixture of solvents designed to be
selective for one or more solutes, depending upon their chemical type.

Solvent extraction is an old, established process and together with distillation constitute
the two most important industrial separation procedures. The first commercially-
successful liquid-liquid extraction operation was developed for the petroleum industry in
1909 when Edeleanu’s process was employed for the removal of aromatic hydrocarbons
from kerosene, using liquid sulfur dioxide as solvent. Since then many other processes
have been developed by the petroleum, chemical, metallurgical, nuclear, pharmaceutical
and food processing industries.

Whereas distillation affects a separation by utilizing the differing volatilities of the

components of a mixture, liquid-liquid extraction makes use of the different extent to
which the components can partition into a second immiscible solvent. This property is
frequently characteristic of the chemical type so that entire classes of compounds may be
extracted if desired. The petroleum industry takes advantage of this characteristic of the
process and has used extraction to separate, for example, aromatic hydrocarbons from
paraffin hydrocarbons of the same boiling range using solvents such as liquified sulfur
dioxide, furfural and diethylene glycol. In general, extraction is applied when the
materials to be extracted are heat-sensitive or nonvolatile and when distillation would be
inappropriate because components are close-boiling, have poor relative volatilities or
form azeotropes.

The simplest extraction operation is single-contact batch extraction in which the initial
feed solution is agitated with a suitable solvent, allowed to separate into two phases after
which the solvent containing the extracted solute is decanted. This is analagous to the
laboratory procedure employing a separating funnel. On an industrial scale, the extraction
operation more usually involves more than one extraction stage and is normally carried
out on a continuous basis. The equipment may be comprised of either discrete mixers and
settlers or some form of column contactor in which the feed and solvent phases flow
countercurrently by virtue of the density difference between the phases.

Final settling or phase separation is achieved under gravity at one end of the column by
allowing an adequate settling volume for complete phase disengagement.

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Any one extraction operation gives rise to two product streams: the extracted feed
solution, more usually termed the raffinate phase, and the solvent containing extracted
solute termed the extract phase. This nomenclature is unique to liquid-liquid extraction
processes and will be used from hereon.

Choice of solvents

No single criterion can be used to assess the suitability of a solvent for a particular
application and the final choice is invariably a compromise between competing
requirements. Thus not only should the solvent be selective for the solute being extracted
but it should also possess other desirable features such as low cost, low solubility in the
feed-phase and good recoverability as well as being noncorrosive and noninflammable.
Furthermore, interfacial tension between the two phases should not be so low that
subsequent phase disengagement becomes difficult and the density difference between
the phases should be large enough to maintain countercurrent flow of the phases under
the influence of gravity.

Of these factors, the first to be considered is the selectivity of the solvent, or the ease with
which it extracts the desired solute from the feed stream. This is most readily understood
by considering a simple ternary system consisting of a solution of solute C in a solvent A
(the feed solution) and an extracting solvent B, which is designed to extract C from A. A
simple single-stage extraction is shown on conventional triangular coordinates in Figure
1a. Here, a mixture of A and C of composition F is mixed with a pure solvent B in such
proportions as to give an overall composition M. This lies inside the miscibility curve and
so the mixture will separate into two separate phases, R and E, joined by an equilibrium
tie line RE. If the solvent B is now stripped from each phase, the solvent-free composition
of R is given by D and the solvent-free composition of E by the point G. Both solvent-free
compositions lie, of course, on the side of the triangle AC and it will be seen that the initial
feed solution of composition F has been separated into two solutions D and G, which have
low and high concentrations of C, respectively.

Figure 1. Extraction
of solute C from A
using solvents B and
B'.

If this operation is now repeated using another solvent B' , the corresponding
concentrations may be as shown in Figure 1b. In this instance, the solvent-free
concentrations D and G are closer to the initial feed concentration F, and the separation of
C is not as good as in the first case. It will be noted that the two solvents B and B' are

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associated with equilibrium tie lines of very different slopes, and effects of this nature may
be quantified by defining a solvent selectivity βCA, analogous to relative volatility in
distillation, such that:

Since X/XCA is the partition coefficient of the system, m,

(1)
In most instances, β varies widely with concentrations; and for practical
purposes, a solvent should be selected that gives high values of β in
excess of unity and satisfies the other criteria listed above.

The extraction of aqueous solutions is usually carried out using organic solvents or
mixtures thereof. In recent years, interest has developed in the possibilities of using a
second aqueous phase loaded with a suitable polymer so the extracted solute does not
come into contact with organic solvents. This is of particular interest to the
pharmaceutical and foodstuffs industries [see Verrall (1992) and Hamm (1992) for details
of such aqueous-aqueous systems].

Phase Equilibria

The first step in the design of any extraction process is the determination of the
equilibrium relationships between the feed solution and the proposed solvent. This
enables the suitability of the solvent to be assessed in terms of its selectivity, as well as the
calculation of the numbers of extraction stages required for any set of flow conditions and
degree of separation.

Equilibrium data are usually determined directly in the laboratory since such
measurements are more accurate than values calculated from predictive equations.
Equilibria may be represented graphically on either triangular or rectangular coordinates,
and a full discussion of the determination and representation of liquid-liquid equilibria
has been presented by Treybal (1963). The correlation of equilibrium data is best achieved
in terms of activity coefficients calculated from laboratory equilibrium measurements. A
large number of semi-empirical equations are available for this purpose, but two models
have found wide acceptance: the NRTL and the UNIQUAC equations for nonelectrolytes.
In the absence of experimental data, it is not possible to determine the parameters of
these equations and one must turn to purely predictive models, such as the regular
solution and the UNIFAC models. All these procedures, as well as correlations for
electrolyte solutions, have been discussed in detail by Newsham (1992) and this source
should be consulted for further information.

Contactors

Contactors or extractors are specialized items of equipment designed to bring the feed
and solvent phases together in such a manner that rapid transfer of the solute takes place
from one phase to the other, followed by subsequent phase separation. In practice,
efficient extraction involves four separate requirements:

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 a. The initial dispersion of one phase into the other in the form of droplets.

b. The maintenance of a fine dispersion in order to provide a large interfacial area for
diffusion from one phase to the other.

c. The provision of an adequate holding or retention time for an acceptable level of

diffusion to take place.

d. Final separation of the dispersion into raffinate and extract phases.

Numerous contactors have been described in the literature and the characteristics of the
principal types have been summarized by Pratt and Stevens (1992). These authors also
discussed the selection, design and scale-up of industrially-relevant contactors.

In its simplest form, a contactor merely consists of a stirred tank in series with a settling
chamber through which the two phases flow (Figure 2a). Such arrangements are termed
mixer-settlers and a number of units may be assembled in cascade to give the required
degree of extraction. A typical assembly with countercurrent phase flows is shown in
Figure 2b. Such devices can become uneconomical when a high level of extraction is called
for because of the multiplicity of units employed. Each calls for separate stirrers and
instrumentation for interface control in each settler, and it is more usual to employ some
form of ‘column’ contactor in which only one settling chamber is involved, irrespective of
the degree of extraction required.

Figure 2. Contactor arrangements. (a) Single-stage mixer-settler. (b)

Countercurrent multiple contact using mixer-settlers. (c) Spray column. (d)
Packed column. (e) Rotating disc column. (f) Air-pulsed plate column. (g)
Electrostatic column. (F = feedstream; S = solvent; R = raffinate; E = extract.
The feedstream is assumed to be the heavier phase throughout.)

The simplest column contactor is the spray tower (Figure 2c) in which one phase is
dispersed into the other and overall flows are countercurrent through the column. Such
units are inefficient and are of little interest outside the laboratory. If however some form
of ordered or random packing, such as raschig rings, is introduced into the tower,
extraction efficiency is increased several-fold. Such packed columns (Figure 2d) are an
important item of industrial equipment. The packing not only reduces the gross back-
mixing evident in the spray tower but also serves to establish a controllable droplet size

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distribution, as well as inducing additional turbulence inside and outside the droplets so
diffusion from one phase into the other proceeds more rapidly [Batey and Thornton
(1989)].

In column contactors described so far, energy available for droplet dispersion (and hence,
the interfacial area available for solute transfer) is derived solely from the density
difference between the phases; so the physical properties of the system set a limit to
achievable extraction efficiency. This limitation may be overcome by supplying additional
energy to the contactor and this concept has given rise to a large variety of so-called
mechanical columns. Columns with coaxial rotating members of various designs have
been described in the literature and the so-called rotating disc contactor illustrated in
Figure 2e is a good example. This is basically a spray column with a central rotating shaft
bearing a series of flat discs that rotate between fixed annular baffles. The shear forces set
up produce very small droplets of dispersed phase and a correspondingly large interfacial
area for mass transfer. Whilst such a unit gives good extraction efficiencies, the rotating
shaft involves seals or bearings within the column and is therefore unsuitable for
processing toxic or corrosive liquids.

This limitation relative to corrosive liquids may be overcome if mechanical energy is

introduced in the form of reciprocatory, rather than rotary, motion. Such contactors are
known as pulsed columns, and the reciprocatory motion may be applied either to the
plates in the column or to the process fluids themselves. The latter procedure is now
virtually universal. A typical pulsed column is illustrated in Figure 2f and consists, in
essence, of a column shell fitted with a number of fixed perforated plates or sieve trays.
The pulse may be imparted to the process fluids by attaching a cylinder closed by a
reciprocating piston to the base of the column, or more usually by applying a sinusoidally-
varying air pressure to a vertical standpipe connected to the base of the column (Figure
2f). Such a device is known as an air-pulsed column [Thornton (1954)] and has the
advantage that the process fluids are isolated from the pulsing mechanism by a pocket of
air or inert gas. Such contactors have found wide application in the nuclear reprocessing
industries. Column contents are usually pulsed sinusoidally at a frequency within the
range 1–3 cycles per second and with an amplitude, measured in the column, of 12 mm or
less. The perforated plates typically have a free area of 25% and are drilled with 3 mm
diameter holes on a triangular pitch; the spacing between successive plates is 50 mm.
Such a plate geometry does not allow the dispersed phase droplets to pass through readily
except under the influence of the pulse, and very small droplets giving rise to large
interfacial areas are readily obtained by varying the pulse frequency and/or amplitude.
The extraction efficiency of the unit is therefore easily varied by changing the pulse
characteristics and very high rates of extraction may be obtained with these columns.
From an industrial viewpoint, mixer-settlers, rotating disc and pulsed columns have been
employed successfully in a wide range of situations and extensive performance data are
available in published literature.

Mechanical energy is not the only method of producing small droplets and thereby large
interfacial areas for solute transfer. On the laboratory scale, both sonic and electrical
energy have been employed successfully. Thus a sonic generator in contact with process

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fluids in a spray-type column gives rise to good droplet dispersions and high extraction
rates [Thornton (1953)].

A promising procedure developed in recent years is electrostatic extraction, wherein

electrical energy is employed to effect dispersion of one phase into the other by charging
the dispersed phase entry nozzle to a high potential relative to a secondary electrode
downstream in the column [Thornton and Brown (1966); Stewart and Thornton (1967)].
The droplets formed at the entry nozzle are now very small and carry an electrical charge
so that they are accelerated at high velocity towards the secondary electrode.
Furthermore, since the droplets carry a charge they oscillate rapidly due to the lowered
interfacial tension, and contactors can be designed with very small contact times coupled
with high extraction rates comparable with those usually associated with pulsed-plate
columns. Rapid extraction coupled with low retention times in the contactor are
particularly appropriate to processes in which the solute is of biological origin, or is
otherwise unstable during extraction operation. In practice, such electrostatic contactors
comprise a column equipped with a number of insulated nozzle trays with a potential
gradient between successive trays (Figure 2g). Designs for large-scale units have not yet
been investigated in any detail, but the use of radial nozzle trays for larger diameter
columns has been proposed [Thornton (1989)]. For a general discussion of electrostatic
extraction, see Thornton (1976) and Weatherley (1992).

Factors in contactor design

The design of a column-type contactor basically involves the calculation of two

geometrical parameters, viz., the height of column necessary to give the required degree
of extraction and the diameter to handle the necessary flow rates under prescribed
operating conditions. In the design of stage-wise units, such as mixer-settlers, the
corresponding parameters are power input and residence time of the mixing chamber and
the residence time of the settler necessary for satisfactory phase setting.

The fundamental quantities usually employed to describe the hydrodynamic behavior of

column-type contactors are the phase flow rates, fractional holdup of the dispersed phase
and the characteristic mean velocity of the droplets. If the fractional voidage of the
column is denoted by ε, the quantities are related by the holdup equation:

(1)
The term ( ) on the right hand side of Equation (1) takes into
account the reduction in mean velocity of a multiplicity of
droplets by comparison with the velocity of a single droplet in
infinite media. This so-called hindered rising term can frequently be represented by a
function of holdup (1 – x) so long as the droplet size is small and is independent
of the phase flow rates—conditions frequently met in mechanical contactors. On this
basis, the holdup equation takes the form:

(2)

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A plot of [Vd + (x/1 – x)Vc] versus x(1 – x) is linear with a
slope of and enables characteristic velocity to be
determined from flow rate and holdup measurements.
Progressive increases in either or both phase flow rates finally result in flooding of the
contactor, which is manifested by the appearance of a second interface at the opposite end
of the column to the main interface. This condition corresponds to maximum values of
the flow rates beyond which holdup remains constant, and can be found by differentiating
Equation (2) [Thornton and Pratt (1953)].

(3)
(4)
Eliminating εVo between Equations (3) and (4) and solving
for xf yields

(5)
where L represents the ratio Vdf/Vcf and subscript f
denotes values at the flood point. Thus the phase superficial
velocities at the flood point, together with the associated
dispersed phase holdup, may be determined from Equations (3)– (5) once the value of the
droplet characteristic velocity is known; the latter is readily obtained by plotting
experimental holdup measurements in accordance with Equation (2) and measuring the
slope of the linear plot. By this means flood point data may be obtained from holdup
measurements and vice versa [Thornton and Pratt (1953); Thornton (1956)]. It is
important to note that Equations (2)–(5) are only appropriate for situations where mean
droplet size is small and is constant up to the flood point. Furthermore the
assumption is made that the effective buoyancy force between the phases is proportional
to the difference in densities of the mixture and the dispersed phase (ρm – ρd). By the
mixture law, this is equal to (ρc – ρd)(1 – x), thus accounting for the (1 – x) term on the
right hand side of Equation (2). At higher Reynolds numbers, it is possible, in principle, to
derive equations analogous to Equations (2)–(5) provided that satisfactory equations can
be formulated to describe droplet motion in the column. This is not always possible at
present and numerous semi-empirical expressions have been proposed in lieu of Equation
(2) [Pratt and Stevens (1992)]. It should be noted that Equations (3)–(5) cannot be used
to predict flooding rates in packed columns since droplet coalescence sets in prior to the
flooding point.

Relationships can be established between the Sauter mean droplet size, dvs, and the
characteristic velocity by introducing the concept of column impedance, I. Thus in the
case of a spray tower of height H, let the time taken for a droplet to move through this
distance be t. The terminal velocity of the droplet, U, is then equal to H/t. In a contactor
such as a perforated plate-column, the same size droplets will take longer than time t to
pass through a height H because they will suffer a small but finite delay, Δt, at each plate.
In a column of N plates, the total delay will amount to NΔt and the velocity of the droplets
relative to the continuous phase will be given by H/(t + NΔt). In the limit as holdup tends
to zero, this velocity approaches the characteristic velocity , and taking the ratio of
spray and plate column velocities yields the expression

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(6)
where I is the column impedance and is defined as the fractional
increase in time of passage of a single droplet with respect to an
empty spray column. The terminal velocity U can be written in
terms of mean droplet size and the physical properties of the systems using published
drag coefficient data, thereby establishing the link between droplet size and for a
known value of I via Equation (6). Values of I range from zero to some finite value,
depending upon the characteristics of the contactor and the properties of the system. For
the application of this concept to pulsed plate-columns and the use of laboratory holdup
measurements to characterize the behavior of such contactors, see Batey et al. (1987).

Diffusion of a solute from one liquid phase to another is a complex process governed by
molecular and/or eddy diffusional mechanisms. Mass transfer flux is proportional to the
instantaneous concentration driving force, and the ratio of these quantities is called the
mass transfer coefficient and may be defined in terms of either the continuous or the
dispersed phase driving force. Thus if solute A is transferring from phase c to phase d, the
flux NA is given by:

(7)
In practice, it is not feasible to measure the two interfacial
concentrations cci and cdi in a practical extraction system and
so, since the interfacial concentrations are assumed to be in
equilibrium, diffusion from phase c to d can be considered to be diffusion of solute
through two phases or resistances in series. No resistance will be offered by the interface
itself because the chemical potentials in each phase will be equal. On this basis, the so-
called overall coefficients Ko can be defined:

(8)
where all the concentrations are now known. For a linear
equilibrium curve, the relationships between the individual
phase or film coefficients and the overall coefficients are
readily shown to be [Treybal (1963)]

(9)
(10)
Numerous mathematical models have been proposed for calculating
values of the individual phase coefficients k, but these make
assumptions regarding the hydrodynamic characteristics of the
phase in question [Skelland (1992); Javed (1992)]. Knowledge of
turbulence levels and flow patterns in the vicinity of the interface is still far from complete
and this limits the use of models for predicting k values. Contactor design is therefore
based upon experimental measurements of the mass transfer coefficients, using the actual
type of contactor and extraction system in question.

For a detailed consideration of design procedures for column contactors and mixer-settler
devices, see the comprehensive account by Pratt and Stevens (1992).

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Reference must be made, however, to the complications arising when the Marangoni
Effect or spontaneous interfacial turbulence is present. Many solutes promote intense
turbulence at the interface as they diffuse from one phase to the other [Perez de Ortiz
(1992)]. The level of turbulence cannot be predicted from first principles and the
consequences can only be assessed from extensive pilot plant studies. Thus, for example,
extraction efficiency of countercurrent column contactors is usually expressed in terms of
the height of a transfer unit or HTU [Treybal (1963)]. The overall HTU based upon the
continuous phase driving force is defined as:

(11)
where the specific surface area a is equal to 6 εx/dvs, so that

(12)
Marangoni effects can influence mean droplet size, dvs,
through enhanced interdroplet coalescence rates; the
holdup x, by virtue of a correspondingly increased value of
in Equation (2) and the overall mass transfer coefficient Koc through enhanced
turbulence at the droplet interface [Thornton et al. (1985); Javed et al. (1989)]. Moreover,
values of Koc become time-dependent and decrease as the droplet interface ages. (See
Thornton (1987) for a further discussion of this problem.)

The terms in square brackets with subscript M in Equation (12) are therefore all
dependent upon the level of interfacial turbulence induced by the solute. The extent to
which these quantities are modified by Marangoni phenomena is not yet quantifiable. It is
therefore always desirable to study the characteristics of any proposed extraction system
in the laboratory before proceeding to the design stage.

Industrial extraction operations

Details of relevant process chemistry and extraction operations in the hydrometallurgical,

nuclear, pharmaceutical and food industries are provided by Thornton (1992).

Nomenclature

a Specific interfacial area

c Solute concentration

dvs Sauter mean droplet diameter

H Height of column

(HTU)oc Height of an overall transfer unit based on the continuous phase

I Column impedance defined by Eq. (6)

k Single-phase or film mass transfer coefficient

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Ko Overall mass transfer coefficient

m Equilibrium distribution or partition coefficient

NA Transport flux of solute A

U Droplet terminal velocity in infinite media

V Superficial phase velocity

Droplet characteristic velocity, i.e., mean droplet velocity when Vc = o and Vd→ o

x Fractional holdup of dispersed phase. With subscripts concentration (wt fraction)

βCA Selectivity of solvent for solute C from an A–C solution

ε Fractional voidage of column

p Phase density

Subscripts

c Continuous phase

d Dispersed phase

i At interface

AA A in A-rich solution

AB A in B-rich solution

CA C in A-rich solution

CB C in B-rich solution

Superscript

* At equilibrium

References

1. Batey, W., Thompson, P. J., and Thornton, J. D. (1987) Column impedance and the
hydrodynamic characterization of pulsed plate-columns. Extraction ’87. Instn.
Chem. Engrs. Symposium Series. 103: 133.
2. Batey, W. and Thornton, J. D. (1989) Partial mass transfer coefficients and packing
performance in liquid-liquid extraction. I & EC Research. 28: 1096.
3. Hamm, W. (1992) Science and Practice of Liquid-liquid Extraction (Ed. J. D.
Thornton). Clarendon Press. Oxford. 2, Ch 4.

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 4. Javed, K. H., Thornton, J. D., and Anderson, T. J. (1989) Surface phenomena and
mass transfer rates in liquid-liquid systems. AIChE Journal. 35(7): 1125.
5. Javed, K. H. (1992) Science and Practice of Liquid-liquid Extraction (Ed. J. D.
Thornton). Clarendon Press, Oxford. 1, Ch 4.
6. Newsham, D. M. T. (1992) Ibid. 1, Ch 1.
7. Perez de Ortiz, E. S. (1992) Ibid. 1, Ch 3.
8. Pratt, H. R. C. and Stevens, G. W. (1992) Ibid. 1, Ch 8.
9. Skelland, A. H. P. (1992) Ibid. 1, Ch 2.
10. Stewart, G. and Thornton, J. D. (1967) Charge and velocity characteristics of
electrically charged droplets. Instn. Chem. Engrs. Symposium Series. 26: 29, 37.
11. Thornton, J. D. (1953) Improvements in or relating to columns for liquid-liquid
extraction processes. Brit. Pat. 737, 789 (filed 1953, published 1955).
12. Thornton, J. D. and Pratt, H. R. C. (1953) Flooding rates and mass transfer data for
rotary annular columns. Trans. Instn. Chem. Engrs. 31: 289.
13. Thornton, J. D. (1954) Recent developments in pulsed column techniques. Chem.
Eng. Prop. Symposium Series. 50 (No. 13): 39. See also Thornton, J. D.
Improvements in or relating to liquid-liquid extraction columns. Brit. Pat. 756, 049
(filed 1954, published 1956).
14. Thornton, J. D. (1956) Spray liquid-liquid extraction columns. Prediction of limiting
holdup and flooding rates. Chem. Eng. Sci. 5: 201. DOI: 10.1016/0009-
2509(56)80031-6
15. Thornton, J. D. and Brown, B. A. (1966) Liquid-fluid extraction process. Brit. Pat. 1,
205, 562 (filed 1966, published 1970).
16. Thornton, J. D. (1976) Electrically enhanced liquid-liquid extraction. Birmingham
University Chemical Engineer. 27 (No. l): 6.
17. Thornton, J. D., Anderson, T. J., Javed, K. H., and Achwal, S. K. (1985) Surface
phenomena and mass transfer interactions in liquid-liquid systems. AIChE Journal.
31 (7): 1069. DOI: 10.1002/aic.690310704
18. Thornton, J. D. (1987) Interracial phenomena and mass transfer in liquid-liquid
extraction. Chemistry and Industry (SCI London). 16 March: 193.
19. Thornton, J. D. (1989) Euro. Pat. Specn. 0356030 AZ (filed 1989).
20. Thornton, J. D. (1992) Science and Practice of Liquid-liquid Extraction (Ed. J. D.
Thornton). Clarendon Press, Oxford. 2.
21. Treybal, R. E. (1963) Liquid Extraction. McGraw Hill, NY.
22. Verrall, M. S. (1992) Science and practice of liquid-liquid extraction (Ed. J. D.
Thornton). Clarendon Press, Oxford. 2, Ch 3.
23. Weatherley, L. R. (1992) Ibid. 2, Ch 5.

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