Liquid – Liquid Extraction 1

Liquid – Liquid Extraction

Eckart Müller, Frankfurt a. Main, Germany (Chaps. 1 and 2)
Rosemarie Berger, Ludwigshafen, Germany (Chaps. 3 and 4)
Eckhart Blass, Technische Universität München, München, Germany (Chaps. 1 – 4, Sections 5.1 and 5.2)
Domien Sluyts, Bayer AG, Antwerpen, Belgium (Section 5.3)

1. Fundamentals and Fields of Appli- 3.2.2. Operating Characteristics of Pulsed

cation . . . . . . . . . . . . . . . . . . . . 2 Columns and Columns with Rotating
2. Thermodynamic Fundamentals . . . 4 Internals . . . . . . . . . . . . . . . . . . 25
2.1. Graphic Representation of Phase 3.2.3. Fluid Dynamic Calculation Methods . 28
Equilibria . . . . . . . . . . . . . . . . . 4 3.3. Apparatus Design . . . . . . . . . . . . 30
2.1.1. Triangular Diagrams . . . . . . . . . . . 4 3.3.1. Internals and Operating Conditions . . 30
2.1.2. Other Graphic Representations . . . . 6 3.3.2. Column Diameter . . . . . . . . . . . . . 31
2.2. Measuring Methods of Phase Equi- 3.3.3. Column Height . . . . . . . . . . . . . . 32
libria . . . . . . . . . . . . . . . . . . . . 7 3.4. Criteria for Equipment Selection . . 32
2.3. Empirical Correlations of Phase 4. Phase-Separation Equipment . . . . 36
Equilibria . . . . . . . . . . . . . . . . . 9 4.1. Gravity Settlers without Inserts . . 36
2.4. Selection of Solvent . . . . . . . . . . . 10 4.2. Settlers with Coalescing Aids . . . . 37
2.5. Calculation of Theoretical Stages . 11
5. Liquid – Liquid Extraction Pro-
2.5.1. Selection of Calculation Methods . . . 11
cesses . . . . . . . . . . . . . . . . . . . . 41
2.5.2. Specific Methods . . . . . . . . . . . . . 11
5.1. General . . . . . . . . . . . . . . . . . . 41
2.5.3. Evaluation of Stage-Number Calcula-
5.2. Combined Processes of Extraction
tion for Process Design . . . . . . . . . 13
and Distillation . . . . . . . . . . . . . 43
3. Apparatus . . . . . . . . . . . . . . . . . 15
5.3. Reactive Extraction . . . . . . . . . . . 44
3.1. Survey . . . . . . . . . . . . . . . . . . . 15
3.1.1. Columns without Energy Input . . . . 15 5.3.1. Introduction . . . . . . . . . . . . . . . . 44
3.1.2. Pulsed Columns . . . . . . . . . . . . . . 17 5.3.2. Extraction Mechanism of Different
3.1.3. Columns with Rotating Internals . . . 20 Types of Solvent . . . . . . . . . . . . . 45
3.1.4. Mixer – Settlers . . . . . . . . . . . . . . 21 5.3.3. Uses . . . . . . . . . . . . . . . . . . . . . 48
3.1.5. Centrifugal Extractors . . . . . . . . . . 23 5.3.4. Setting up an Extraction System . . . 49
3.2. Fluid-Dynamic Fundamentals . . . . 24 5.3.5. Diluents and Modifiers . . . . . . . . . 50
3.2.1. Problems and Process Strategy . . . . 24 6. References . . . . . . . . . . . . . . . . . 51

Symbols dp particle diameter, m

2a Pulsing amplitude, m
A key component of the
phase from which the
solute is extracted
B key component of the
phase into which the
solute is extracted
ci constants
C transferred component
di hole or packing diam-
eter, m
d 32 Sauter mean drop di-
ameter, m
D column diameter, m
DR rotor diameter, m
D distribution coefficient
E = K ṁs /ṁF extraction factor
f pulsing frequency, s−1
g acceleration due to
gravity, m/s2
Gi coefficients in empiri-
cal correlations of the
distribution coefficient

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.b03 06
2 Liquid – Liquid Extraction

h compartment height, Dimensionless Groups

m
Ar = d3P gc ∆/ηc2 Archimedes number
H height of column, m
F rR = N 2 DR /g Froude number
HETS height equivalent of a
Rep = vp dp /vd Particle Reynolds
theoretical stage, m

 number
k = yc /x c distribution ratio of
KL = 2c σ 3 / ∆gηc4 Characteristic num-
transferred component
ber of liquid
(in terms of mass frac-
tion)
K = Y C /X C distribution ratio of Subscripts
transferred component
A key component of the phase from which
(in terms of loading)
the solute is extracted
Kp plait point
B key component of the phase into which
mj k mass of component
the solute is extracted
j in phase or flow
C transferred substance (solute)
k ( j = A, B, C; k = F, R,
c continuous phase
S, E), kg
d dispersed phase
mk = mAk + mBk + mCk total mass of phase or
E extract
flow k (k = F, R, S, E),
f flooding
kg
F feed
ṁ mass flow, kg/h
i internals (characteristic size)
ns revolutions of stirrer,
o organic
s−1
p drop (particle)
n number of stages
R raffinate
NTS number of theoretical
S solvent
stages
1 pilot scale
s column cross section,
2 large scale
m
v superficial velocity,
m3 m−2 h−1 or m/s
v = ṁS /ṁF extractant ratio 1. Fundamentals and Fields of
vp individual drop veloc-
ity, m/s
Application
vr slip velocity (Eq. 9),
Liquid – liquid extraction or solvent extraction
m/s
is a separation process which is based on the
xC mass fraction of C in
different distribution of the components to be
A-rich phase
separated between two liquid phases. It depends
X C = x/(1 − x) loading of A-rich
on the mass transfer of the component to be ex-
phase with component
tracted from a first liquid phase to a second one.
C, kg/kg
yC mass fraction of C in
B-rich phase Definitions. The phases form definite con-
Y C = y/(1 − y) loading of B-rich tact areas and cannot or can only to a limited
phase with C, kg/kg extent mix with one another on account of their
properties. The phases are composed of indi-
vidual substances, so-called components, and
Greek symbols flow as liquid streams through the extractor (see
ε holdup, m3 /m3 Fig. 1). Phases are liquid streams that are in equi-
η dynamic viscosity, Pa · s × 10−3 librium with each other.
 density, kg/m3 Generally, more than three components are
σ interfacial tension, N/m × 10−3 involved in an extraction. To make the descrip-
ϕ free area tion of the problem simpler, key components are

defined. The feed to a liquid – liquid extraction
is the solution that contains the components to
be separated. The key component of this liquid
phase (the phase from which the solute is ex-
tracted) is called A, the transferred substance
(the solute) C. The (extraction) solvent is the
liquid added to the process to extract the sub-
stance C from the feed. The solvent can be the
pure component, B, but usually contains small
quantities of C and A, because the solvent is usu-
ally recycled from a recovery system. The sol-
vent phase leaving the extractor is the extract.
The extract contains mainly B and the extracted
component C but also small quantities of A. The
raffinate is the liquid phase left from the feed
after being contacted by the extraction solvent;
it is composed mainly of A, but generally small
quantities of the extracted component C and sol-
vent B.
Comparison with Distillation. Liquid – liq-
uid extraction has similarities with distillation.
In both cases the substances to be separated have
concentration ratios = 1 in the two phases. In the
case of distillation the second phase (the vapor
phase) is formed exclusively from the compo-
nents of the initial (liquid) phase, with extraction
a new substance, the (extraction) solvent, must
be added to form the second (liquid) phase. The
solvent enters into the material balance of the
process and its behavior towards the substances
to be separated is decisive for the separation
process.
Generally, the extracted substance is sepa-
rated from the solvent by distillation and the
solvent B is recycled to the extractor. Sometimes
the selective action of the solvent is used in the
distillation which generates the reflux for the
extraction, e.g., extractive distillation (extrac-
tion of aromatic compounds, see Section 5.2)
or azeotropic distillation (extraction of acetic
acid). In the extraction of metal salts (see Sec-
tion 5.3) the purity is often achieved by adjust-
ing the pH. Extraction is an isothermal process,
normally carried out at ambient temperature and
pressure.
Comparison with Absorption. In both ab-
sorption and extraction solvents are used which
are recycled and thereby take up the required
components selectively and then release them
again. Selection of the most suitable solvents
Liquid – Liquid Extraction 3
therefore plays an important role in the design
of the two separation processes.
Applications of Liquid – Liquid Extrac-
tion. Liquid – liquid extraction is primarily ap-
plied where direct separation methods such as
distillation and crystallization cannot be used or
are too costly. Liquid – liquid extraction is also
employed when the components to be separated
are heat-sensitive (e.g., antibiotics) or relatively
nonvolatile (e.g., mineral salts).
Liquid – liquid extraction is used in industry
for the following purposes:
1) Separation of systems with similar boiling
points (e.g., separation of aromatics from
aliphatic hydrocarbons);
2) separation of highboilers and low concen-
trated solutes from aqueous solutions (e.g.,
phenol);
3) separation of mixtures with high boiling
points (e.g., vitamins);
4) separation of temperature-sensitive com-
pounds (e.g., acrylates, biotechnology);
5) separation of azeotropic mixtures (extrac-
tion of acetic or formic acid from aqueous
media using, e.g., MTBE as solvent);
6) extraction of organic compounds from salt
solutions (e.g., caprolactam);
7) extraction of salts from polymer solutions
(e.g., ketone resins, polyols);
8) extraction of metal salts from low-grade
ores (e.g., copper);
9) extraction of metal salts from wastewater
(e.g., copper);
10) recovery of nuclear fuels (Purex process).
Figure 1. Principles of extraction – streams, phases and
components
Processes applied in the petroleum industry,
in metal-salt extraction and in chemical and bio-
chemical processes are described in Chapter 5.
4 Liquid – Liquid Extraction
Only a general outline is given in this arti-
cle. For further details, the reader is referred to
books [1–7] and the Proceedings of the Inter-
national Solvent Extraction Conference (ISEC)
[8–17]. Data of liquid – liquid equilibria can be
found in [18], [19] and [20].
Figure 2. Triangular diagram for representation of a three-
component system
2. Thermodynamic Fundamentals
A comprehensive treatment of the thermody-
namic fundamentals of phase equilibria is given
elsewhere (→ Absorption; → Distillation and
Rectification).
2.1. Graphic Representation of Phase
Equilibria
2.1.1. Triangular Diagrams
Triangular diagrams (Fig. 2) are used for repre-
senting three-component systems. Every possi-
ble composition of the ternary mixture corre-
sponds to a point in the diagram. Each corner
of the triangle represents a pure component and
its designation is marked at this corner. On the
side opposite to this corner the mass fraction of
this component is zero. The sides of the trian-
gle represent the corresponding two-component
systems. The proportions of the individual com-
ponents in a mixture are obtained as follows:
The mass fraction of each component is given
by lines parallel to the side opposite to the cor-
ner which represents the pure component, from
0 kg/kg at this opposite side to 1 kg/kg at the cor-
ner. The numbering can be placed at the edges
of the triangle, in which case it is advisable to
extend the lines. The numbers can also be in-
serted in the middle of the lines. This makes the
diagram easier to use but some of the numbers
are always skew and inverted. The point P has
the composition 0.5 kg/kg C, 0.2 kg/kg A, and
0.3 kg/kg B.
The following rules apply in the triangular di-
agram: If component C is added to a mixture of
0.8 kg/kg A and 0.2 kg/kg B, represented by the
point D, then the composition of the new mix-
ture follows the path of the straight line DC. On
this straight line, and on all straight lines which
pass through a corner, the ratio between the two
other components which do not form the corner
is constant.
If a mixture of composition U and one of
composition V are combined then the resulting
mixture lies on the straight connecting line UV.
The composition of the final mixture is obtained
by dividing the connecting line between the two
original mixtures in inverse ratio to the quantities
mixed (lever rule). The mixture M, for example,
comprises three parts U and one part V, and the
mixture G comprises three parts C and two parts
D.
The concentration data obtained from the
triangular diagram (e.g., point G: 0.6 kg/kg C,
0.08 kg/kg B, 0.32 kg/kg A; B : A = 1 : 4) apply
to the total quantity of resulting mixture regard-
less of whether it is homogeneous or separated
into several phases.
As every point in a triangular diagram corre-
sponds to a composition there is no coordinate
free for another reference variable. It is only pos-
sible to plot parameters such as lines of equal
density, boiling points or other physical data,
lines of equal activity coefficients or lines of
phase boundaries.
Only ternary systems with miscibility gaps
are suitable for extractions, and the boundary
line between the liquid single-phase region(s)
and the two-phase region is particularly impor-
tant. This boundary line is called the binodal
curve (Fig. 3). Every point on the binodal curve
(except the plait point in systems with a com-
plete binodal curve, see below) is in equilibrium
with another binodal point. The lines which con-
nect points in equilibrium with one another are
called tie lines. All mixtures which correspond
to a point on the tie line separate into two phases.
The composition of these phases is given by the

Figure 3. Definitions of phase equilibria and mass fractions in a triangular diagram
A) Phase equilibria; B) Mass fractions
end points of the tie lines and their quantities
are given by the lever rule. The equilibrium data
have to be determined experimentally in each in-
dividual case. Lines parallel to the triangle sides
CB and AC respectively, drawn through related
points of equilibrium on both branches of the
binodal curve, produce an auxiliary line, formed
by the intersections of the parallels, and enable
to construct any tie line as demonstrated in Fig-
ure 3 A.
Several types of triangular diagrams are
shown in Figure 4. In every system with a com-
plete binodal curve (closed diagram, Type II in
Fig. 4) the end points of the tie lines draw closer
and closer together until they finally coincide at
the plait point. The plait point on the binodal
curve represents a single phase which does not
split into two phases.
Diagram I is called an open diagram in which
B is not fully miscible with the substance to be
dissolved. The capacity of such a solvent is cor-
respondingly low and its selectivity is usually
high (see Section 2.4).
Liquid – Liquid Extraction 5
In diagram II the substance to be extracted
(C) is totally miscible with both A and B. This
form of extraction diagram is often found in ex-
tractions where solute C and A are present in ap-
proximately the same quantities. If in this case
the concentration of C in the AB-mixture is too
high (higher than the concentration at the plait
point) the system forms only one phase and ex-
traction is not possible.
Diagram III shows a system where C has a
miscibility gap with A. Its concentration in the
B-rich phase is then substantially higher than in
the feed. The diagram is typical for wastewater
extractions.
Diagram IV is an open triangular diagram in
which three liquid phases are formed in the mid-
dle concentration range. This behavior is often
found in systems consisting of inorganic salts
in aqueous solutions and organic solvents. The
appearance of a third liquid phase can cause con-
siderable difficulties during metal-salt extrac-
tion (see Section 5.3). The influence of pressure
on the binodal curve and equilibria is negligi-
ble below values of several bar. The influence of
6 Liquid – Liquid Extraction

temperature is strong. The lower the temperature

the more will the triangular diagram normally be
filled by the miscibility gap.

Figure 4. Various types of phase equilibria in ternary sys-

tems
Type I: Open system, miscibility gap between the key com-
ponent of the solvent (B) and solute C
Type II: Closed system, C is completely miscible with the
key component of the feed (A) and the key component of
the extraction solvent (B)
Type III: Open system, miscibility gap between A and C
Type IV: System with formation of three phases

2.1.2. Other Graphic Representations

Liquid two-phase systems comprising three

components can also be plotted on rectangular
coordinates. In many cases these diagrams are
preferred because the measured values can be
adjusted better and the configuration of the cal-
culations is simpler. The most important forms
of representation are shown for three mixtures
in Figures 5, 6, 7. A comprehensive review of
forms of representation is given in [27].
In the equilibrium diagram (Figs. 5, 6, 7 II)
the mass fraction of C in the B-rich phase yC
(ordinate) is plotted as a function of this mass
fraction in the A-rich phase x C (abscissa). This
diagram is analogous to the McCabe – Thiele di-
agram in distillation (→ Distillation and Recti-
fication, Chap. 4.1.1.). It shows the relationship
between equilibrium and operating conditions. Figure 5. Representation of phase relationship of the ternary
system heptane (A), diethylene glycol (B), benzene (C), at
20 ◦ C. All data refers to mass fractions.
I) Triangular diagram; II) Equilibrium diagram; III) Distri-
bution diagram; IV) Selectivity diagram
 Liquid – Liquid Extraction 7

In the example shown in Figures 5, 6, 7 III the

distribution ratios of the extracted components
(benzene, caprolactam or phenol) are plotted as
functions of their mass fractions in the A-rich
phase (curve a) and in the B-rich phase (curve
b). The distribution ratio k indicates how much
better or worse the extracted component is sol-
uble in the B-rich than in the A-rich phase; the
minimal solvent ratio can be evaluated directly
from Figures 5, 6, 7 III. The distribution ratio
therefore is an important criterion for the selec-
tion of a solvent. The mass fraction in the A-rich
phase is easier to visualize as a reference vari-
able. At the feed stage it corresponds approxi-
mately to the initial feed concentration. It gov-
erns the yield at the raffinate outlet. On the other
hand, showing k as a function of yC (curve b) has
the advantage that it permits comparisons with
respect to solvent loading. It is always advisable
to plot both curves because their suitability for
extrapolation and interpolation varies consider-
ably in the different concentration ranges.
In the selectivity diagram (Figs. 5, 6, 7 IV) the
quotient of two distribution ratios is plotted as a
function of the mass fractions of component C
in the A-rich (curve a) and in the B-rich phase
(curve b). The quotient of the distribution ratios
for the extracted component C (yC /x C ) and for
A (yA /x A ) corresponds to the relative volatility
in distillation (see Section 5.1). It is a measure
of the selectivity of a solvent.

2.2. Measuring Methods of Phase

Equilibria

Whenever possible a ternary system is used

as the starting point for measurement of liq-
uid – liquid equilibria. It is first necessary to es-
tablish which of the three possible binary sys-
tems have a miscibility gap and which are com-
pletely miscible. For this purpose it is sufficient
in each case to mix the two substances in ra-
tios of 3 : 1, 1 : 1 and 1 : 3. If no formation of
two liquid phases occurs in any of the cases then
the system is fully miscible and not suitable for
extraction.
Figure 6. Representation of phase relationship of the ternary
system trichloroethylene (A), water (B), caprolactam (C),
at 20 ◦ C. All data refers to mass fractions.
I) Triangular diagram; II) Equilibrium diagram; III) Distri-
bution diagram; IV) Selectivity diagram
8 Liquid – Liquid Extraction
Figure 7. Representation of phase relationship of the ternary
system water (A), butyl acetate (B), phenol (C), at 20 ◦ C.
All data refers to mass fractions.
I) Triangular diagram; II) Equilibrium diagram; III) Distri-
bution diagram; IV) Selectivity diagram
If, for example, A and B are not miscible
while the third, C, is completely miscible with
the two others (closed triangular diagram) then
the binodal curve can be determined as fol-
lows. Equal amounts of A and B are placed in
a controlled-temperature vessel which can be
shaken (e.g., an Erlenmeyer flask in a thermo-
stat) and substance C is added until the mixture
becomes clear. In two further experiments pure
A or B is placed in the vessel and in each case
the second substance is then added until turbid-
ity occurs. Three points have now been obtained
in the triangular diagram and the approximate
shape of the binodal curve is known.
For precise determination of the binodal
curve, mixtures of A and C containing 0.9, 0.8,
0.7 (etc., for as far as appears necessary) kg/kg
A are prepared and titrated with B at constant
temperature. When turbidity is reached titration
is ceased and a small quantity of the original AC
mixture is added until the solution is clear again.
Then a characteristic variable such as refrac-
tive index, density, dielectric constant, freezing
point, boiling point, etc. of this mixture can be
determined. In the same way mixtures of C and
B are titrated with A. This measurement gives
the precise shape of the binodal curve and all the
compositions lying on this curve can be defined
by a physical parameter.
To determine phase equilibrium and there-
with the tie lines, i.e., the points which are in
equilibrium with one another, a mixture from the
two-phase region is placed in a controlled-tem-
perature, shaking cylinder. Equilibrium is estab-
lished by shaking. The phases are allowed to set-
tle and are separated by draining off into differ-
ent vessels. Then their quantities are determined
and the physical variable measured during deter-
mination of the binodal curve is then measured
for both phases. This immediately gives the two
tie line points. Furthermore, both phases can also
be analyzed by well known chemical methods,
such as gas or liquid chromatography and titra-
tion. The correctness of the measurement can be
checked by connecting the two tie line points
in the triangular diagram. The connecting line
must pass through the point of the original mix-
ture, and this point must divide the length of the
tie line in inverse ratio to the quantities of the
two phases.

If a system of more than three components
has to be measured then several components are
combined into one group in order to arrive at a
ternary system again. Determination of a binodal
curve would still be possible in such a case but
the two phases into which the test mixture sep-
arates are no longer identical with the mixtures
which were obtained during the determination of
the binodal curve. It is therefore better to allow
the mixture to reach equilibrium conditions in a
controlled-temperature, shaking cylinder, sepa-
rate it and then analyze the phases using some
preplanned method.
The time consuming step in the determination
of equilibria is the preparation of the experiment,
such as purification of the substances, setting up
the calibration curves, etc. Therefore it is sense-
less to restrict the number of measured points
and use interpolation methods. To increase the
accuracy a material balance is set up for each
component and the measured points are adjusted
by drawing the curves from Figures 5, 6, 7.
2.3. Empirical Correlations of Phase
Equilibria
In ternary systems, the use of empirical corre-
lations to represent the binodal curves and dis-
tribution equilibria of component C is of advan-
tage [28]. The mutual solubilities of the liquid
phases are usually determined by a laboratory
turbidity titration. The binodal curve is then de-
termined by extrapolating the measured values
(see Section 2.2). In Type I systems with an open
miscibility gap, the binodal curve can be simply
described by parabolic equations:
x=D +E  xA +F  x2
A
y=D +E  x  2
B +F xB
where x A is the mass fraction of A in the A-rich
phase, x B the mass fraction of B in the B-rich
phase and D , D , E  , E  , F  and F  are coef-
ficients.
In systems with a closed miscibility gap
(Type II), the parabolic equations are only valid
for the lower parts of the curve; they cannot be
used to represent the entire binodal curve. The
best equation for the closed binodal curve is that
proposed by Hlavaty [29]. The correlation is
Liquid – Liquid Extraction 9
derived from a polynomial equation and has the
advantage that the binodal curve ends exactly at
the binary solubility points. Its disadvantage is,
however, that the lower, in practice virtually lin-
ear, regions of the binodal curves are represented
in wave form as a result of the polynomial equa-
tion. The Hlavaty equation should, therefore, be
used with caution.
The equilibrium distribution of solute C in
the A- and B-rich phases is generally determined
independently from the binodal curve by means
of laboratory experiments. The mass fraction x C
and yC of the two phases in thermodynamic equi-
librium are thus obtained and determine the po-
sitions of the end points of the tie lines on the
binodal curves (see Section 2.2). Equations for
correlating and interpolating the end point of the
tie lines are described in the literature, they are
primarily exponential equations such as those
proposed by Othmer and Tobias, and Hand
[1]. However, all exponential equations gener-
ally fail when the concentration of C is very low.
To allow a more accurate estimation of distri-
bution equilibria and extraction processes at the
low raffinate concentrations that are of industrial
importance, Bender and Block [28] proposed
the following correlation for the distribution ra-
tio K:
K = G1 +G2 xC + G3 x2 3
C +G4 xC
The coefficients Gi must be fitted to the mea-
sured values of the tie lines x and y. Although
the equation does not generally permit extrapo-
lation of the curve above the measured values to
the plait point, the distribution coefficient K can
be obtained accurately up to x and y → 0.
The empirical correlations are simple and
clear. They can be calculated quickly with ap-
propriate computer programs and give an accu-
rate representation of the measured liquid – liq-
uid equilibria. However, these advantages are ac-
companied by several disadvantages. The corre-
lations can only be used with ternary systems
and do not allow extrapolation to higher multi-
component systems. Extensive laboratory work
is required to determine the mutual solubilities
of components A and B as a function of the
concentration of C as well as the equilibrium
distribution of component C. Systematic mea-
surement errors cannot be detected because the
experimental values are empirically correlated.
10 Liquid – Liquid Extraction
2.4. Selection of Solvent
The selection of the most suitable solvent is one
of the hardest problems of the extraction, and
the decision made has a great influence on the
economy of the process. The solvent must fulfill
two basic requirements:
1) it must have a miscibility gap with the A-rich
phase, and
2) it must be a better solvent for component C
than for A.
A great number of methods have been recom-
mended for discovering suitable solvents [30],
[31]. The more empirical strategy of former
times is being replaced more and more by a sys-
tematic research with the aid of data banks [26].
The concept of polarity is used for characteriz-
ing suitable parameters [32].
The greater the difference in polarity between
two liquids, the greater is the probability that
they have a miscibility gap. The substance to be
extracted will have a higher concentration in the
liquid to which it is closer in polarity.
However, the relationships are not so simple
that only a scale of polarities has to be set up
and the difference in polarity at which misci-
bility gaps occur read off the scale. For exam-
ple, aniline, phenol, and furfural have miscibil-
ity gaps with both water and hexane. Acetone,
ethanol, and dioxan which have a similar polar-
ity are miscible with both water and hexane. The
molecular form and the size of the molecule also
contribute to solvent behavior. The behavior of
solvents towards hydrocarbons has been inves-
tigated particularly intensively [33], [34]. It is
also possible to obtain effects from mixing two
solvents which could not be predicted from the
properties of the mix components [35], [36].
The most important property of a solvent is
its selectivity. This indicates how much better the
solute is dissolved than the A-rich phase. As can
be seen from Figures 5, 6, 7 III the selectivity is
strongly dependent on concentration.
In addition to selectivity the capacity of a sol-
vent is also important. This is defined by the
distribution coefficient of C between the B-rich
and A-rich phases and determines the quantity of
solvent which has to be recycled. When testing
different solvents for a specific extraction task
it is often found that solvents with higher se-
lectivities have lower capacities and vice versa.
The greater the throughput of a plant the more
important the capacity of the solvent is for the
economy of the process. If there are several pos-
sible solvents for a process then their behavior
with respect to selectivity and capacity can be
tested with a gas chromatograph without start-
ing with time-consuming equilibrium measure-
ments [37].
In addition to these basic requirements there
are also other criteria which must be taken
into consideration when selecting a solvent and
which sharply reduce the number of possible
compounds. Most important is the availability of
the solvent in commercial quantities at an eco-
nomically acceptable price. It is then necessary
to find data concerning boiling points, density,
viscosity and – where available – information
about solubility [38], [39].
The boiling point of the solvent is important
because the extracted component is usually sep-
arated from the solvent by distillation and the
boiling point difference determines the reflux
ratio in this distillation. If the solvent boils at
a higher temperature than the solute, this solute
is distilled overhead. If it is necessary to recycle
a great deal of solvent then the solvent has to
be purified by distillation in a subsequent step;
the specific heat which is required for heating
the solvent to its boiling temperature must also
be taken into account. Too great a temperature
difference is then a disadvantage.
The density of the solvent is important for ob-
taining a sufficiently large difference in densities
between the two liquid phases for the separation
process. Chlorinated compounds are suitable if
a solvent with a high density is to be used, and
particularly low-density compounds are found
among the saturated hydrocarbons and ethers.
The thermal stability of the solvent can be
highly significant. The researcher hardly ever
finds the answer to this question in the literature
and is directed to carry out his own measure-
ment. It is necessary to know (1) how much sol-
vent make-up will be needed in the process; (2)
whether a regeneration process for continuous
removal of decomposition products needs to be
installed. Very careful tests must be carried out
to find out whether decomposition products can
contaminate the extract or have a corrosive effect
on the construction materials of the plant. Some-
times the toxicological properties and biological

degradation of a solvent have to be considered
[40].
The viscosity should be as low as possible as
this favors mass transfer and phase separation.
However, this property is less significant than
those mentioned above. If the possible solvents
have been reduced to a manageable number after
testing all the aspects then the individual prop-
erties can be evaluated with a point system to
discover the best solvent.
The surface tension is another important pa-
rameter because it influences the energy demand
necessary to produce a suitable drop dispersion.
High surface tension gives rise to formation of
stable drops and needs a high energy input. A
solvent with a high surface tension decreases the
danger of producing an emulsion. The surface
tension is dependent on the concentration of the
transfer component. Further properties such as
suitability for regeneration, disposability, costs,
combustibility, toxicity and corrosiveness also
have to be taken into account to select a suitable
solvent.
Bound up with solvent selection is the choice
of the dispersed and the continuous phase, re-
spectively. Direction of mass transfer and phase
ratio have to be taken into account. The direc-
tion of mass transfer influences the surface ten-
sion and in this way can promote or hamper the
coalescence of drops. The phase to be dispersed
should be the one which impedes the drop co-
alescence to produce stable drops, and the one
with the higher flow rate to obtain a mass transfer
area as large as possible.
2.5. Calculation of Theoretical Stages
(→ Absorption, Chap. 4.; → Distillation and
Rectification, Chap. 4.)
Two possibilities exist to calculate the mass
transfer performance of extractors. The first one
uses the concept of theoretical stages and is
based on the assumption that concentration equi-
librium is established in every section of an ex-
tractor. This assumption can be fulfilled only in
the mixer – settler with long contact times of the
phases involved. In this concept the total height
of an extraction column is given by the product
of the number of theoretical stages (NTS) and the
height equivalent of a theoretical stage (HETS).
Liquid – Liquid Extraction 11
NTS follows from a material balance in combi-
nation with the distribution equilibrium; HETS
depends on fluid dynamics and mass transfer
in the columns and comprises all real condi-
tions as for instance the conditions of phase mix-
ing. Therefore this concept is preferred only for
rough estimations in practice because it is easy to
handle and sufficient for preparation of labora-
tory experiments. In the following sections, the
method will be presented by aid of equilibrium
diagrams.
The second possibility is a stream concept.
The column height required for a given through-
put and concentration gradient of phases along
the column can be calculated from height in-
tegration of a set of differential equations, de-
rived from a differential material balance and
the local mass transfer between the both phases.
The stream concept supplies the course of con-
centrations along the column and is suitable for
analysis of the dynamic behavior of a column
and for taking into account the drop population
inside the column. It is preferred until now for
scientific investigations, e.g., for stationarily op-
erated pulsed sieve tray columns [45], [47–49],
[51], [62] and for instationarily operated rotating
extractors [65], [68].
2.5.1. Selection of Calculation Methods
The conditions for an applicable method of cal-
culation are set by the problem to be solved, by
whether simplified assumptions are permissible
and by the main influencing variables of an ex-
traction problem. They are, therefore, different.
The following points should be considered when
selecting a method of calculation:
1) Do changes in mass flows have to be consid-
ered?
2) Is the distribution ratio constant?
3) Is the concentration gradient large or small?
4) Does only one component have to be ex-
tracted, or are there several with different
distribution coefficients?
2.5.2. Specific Methods
Method 1. If the following conditions are
satisfied:
1) the component A and solvent B are virtually
insoluble in each other,
12 Liquid – Liquid Extraction

Figure 8. A) Material balance of a column cross section; B) Corresponding operating diagram

2) the changes in mass flow rates of the extract

and raffinate phase are negligible (e.g., for a
low content of C in the feed)
then the compositions of the phases can be ex-
pressed as loads. If a material balance is made
as shown in Figure 8, the two loads Y c and X c
in a given column cross section can be related as
follows
ṁF

YC −YC,S = · XC −XC,R
ṁs

When plotted on the equilibrium diagram,

this relation gives a straight line, the balance or
operating line. The number of theoretical stages
required to obtain a desired decrease in the con-
centration of C from X C, F to X C, R can be de-
termined graphically by constructing a series of
steps as shown in Figure 9. The result of the use
of the steps often means that the load obtained
from C in the raffinate (X C, R ) does not corre-
spond to the required load (X CR, req ).
Figure 8 also shows the position of the bal-
ance line for the minimum extractant ratio V min
Vmin =ṁs,min /ṁF
The desired enrichment of the feed with C us-
ing the minimum amount of extractant ṁs, min
can only be achieved with an infinite number of
stages.
Figure 9. Construction of steps in the operating diagram to
obtain the number of theoretical stages (NTS)
Method 2. Figure 10 shows the equilib-
rium diagram for the system toluene – ethylene
glycol – water as a double logarithmic plot. This
type of plot is useful if the distribution ratio
varies considerably, despite low loading, and the
concentration range considerably exceeds the
desired raffinate purity. In this case the operating
line is at an angle of 45◦ .
 

 ṁF

log YC −YC,S = log +log XC −XC,R
ṁS

Figure 10. Determination of the number of stages for a vari-
able distribution ratio and a high degree of depletion
The position of the straight lines is deter-
mined by the extractant ratio V . The number of
required theoretical stages can be determined by
constructing a series of steps.
Method 3. If the distribution ratio K is a con-
stant, further simplification is possible; in anal-
ogy with the Colburn equation (→ Absorption,
Chap. 4.2.), the number of theoretical stages
NTS can be calculated:
 X 
Y
log 1+ (E −1) X C,F + XC,S
C,R C,R
NTS = −1
logE
where the extraction factor E is given by
E =K ·ṁs /ṁF
If NTS is known and the degree of depletion
X C, R /X C, F is desired, the following equation is
obtained:
 
YC,S
XC,R (E −1) 1+ XC,F
= P and the individual stage raffinates in the pro-
XC,F E (NTS+1) −1
This equation can only be solved iteratively; a
graphical solution is shown in Figure 11.
Method 4. If none of the above-mentioned
conditions is satisfied, and the extraction prob-
lem can be limited to consideration of the three
key components, the calculation can be carried
out with the aid of the triangular mass fraction
diagram. This method is based on the mixing
rules described in Section 2.1.1.
Liquid – Liquid Extraction 13
The specified compositions of the feed F
and solvent S streams are plotted on the phase
equilibrium diagram for the ternary mixture
(Fig. 12). For material balance of the feed and
product streams, the column can be assumed to
be a simple mixing vessel. The composition M
of the mixture lies on the tie line FS; the posi-
tion of M on the tie line is determined by the
ratio ṁS : ṁF = MF : MS. The compositions of
the raffinate R and extract E streams leaving the
column are obtained from the intercepts of the tie
line with the binodal curve. The raffinate compo-
sition is determined by the desired mass fraction
of C in the raffinate (x C, R ). The composition of
the extract E is given by the point at which the
extended line RM intersects the binodal curve.
The ratio ṁR : ṁE is obtained by applying the
lever rule. The quantities and the compositions
of the incoming and outflowing streams are thus
determined.
The required number of stages in a counter-
current column are obtained by using the pole
point procedure. The procedure can be explained
by imaging a stream P to maintain the material
balance. Mixing of this stream with the raffinate
stream R gives the composition of the solvent
stream S. To maintain the material balance the
extract on the other hand must be composed of
the feed stream F and the imaginary stream P.
The imaginary stream P can thus be regarded as a
common mixing partner for F and R to maintain
the compositions of E and S. The composition of
the imaginary stream P is represented by a point
outside the triangular diagram, the pole point.
The imaginary mass fractions of the three com-
ponents in the pole point can be > 1 or negativ. If
the material balance boundaries for the individ-
ual stages are taken as shown in Figure 13, the
above procedure gives the stage extracts E2 , E3 ,
etc. from the mixture of the imaginary stream
ceeding stages R1 , R2 , etc. The composition of
the raffinates R1 , R2 , etc. are linked to the corre-
sponding extracts E1 , E2 , etc. via the distribution
ratios (tie lines).
2.5.3. Evaluation of Stage-Number
Calculation for Process Design
In order to determine the operating conditions
and the dimensions of the equipment used for
14 Liquid – Liquid Extraction

Figure 11. Dependence of the theoretical number of stages, the degree of depletion, and the yield on the extraction factor E

Figure 12. Pole point construction – balance diagram


Figure 13. Pole point construction – operating diagram
extraction, the results of several stage-number
calculations must be plotted in a diagram show-
ing the relationship between the solvent circula-
tion, the number of stages, and the residual con-
tent of solute in the raffinate. Such a diagram
is shown in Figure 14 for mixture II (see also
Fig. 6). It represents the extraction of a 10 % so-
lution of caprolactam in trichloroethylene with
water as the extraction solvent. The favorable
operating region is usually located in the region
which shows the most pronounced curvature.
Other variables (e.g., the effect of temperature
and the residual loading of the solvent with so-
lute) may have to be taken into consideration.
3. Apparatus
3.1. Survey
Extraction apparatus can be classified into coun-
tercurrent columns, centrifugal extractors, and
mixer – settlers. All industrial equipment de-
signs use the principle to disperse one of the
two liquids into the other in order to enlarge the
contact area for mass transfer and to influence
the drop generation by energy input such as mix-
ing or pulsing. After the resulting droplets have
been contacted with the continuous phase long
enough to allow the extractable component(s) to
migrate to the dispersed phase, both liquids have
to be separated again. Densities will define the
flow directions of the phases: The heavier liquid
flows from top to bottom, the lighter one from
Liquid – Liquid Extraction 15
bottom to top. Accordingly, the fluids have to
be transported to the apparatus and removed by
pumps.
In the following chapter, a few typical de-
signs have been selected from the large number
of equipment designs actually used in industry.
A more detailed treatment can be found in liter-
ature, especially in [5] and [6].
3.1.1. Columns without Energy Input
The simplest extractor is the spray column
(Fig. 15 A). The spray column achieves only
very small numbers of separation stages and
is rarely used nowadays. If the column of Fig-
ure 15 A is filled mainly with the heavier liquid,
the lighter liquid breaks at the feeding point into
drops that rise in the continuous liquid. Drops
reaching the interface are kept at this position by
controlling the bottom discharge (LIC). There,
they will then gradually coalesce and form a con-
tinuous layer floating on top of the continuous
liquid.
The reverse procedure is possible as well, as
shown in Figure 15 B. Here, the distributor is lo-
cated at the top and the water interface, called
the principle interface, is controlled at the bot-
tom of the column by filling it mainly with the
lighter liquid. In this case, the heavier liquid is
the dispersed one, broken into droplets descend-
ing in the lighter liquid. The principle interface
can be adjusted at any height (between top and
16 Liquid – Liquid Extraction

Figure 14. Extraction of caprolactam from a 10 wt % solution in trichloroethylene with water as solvent

Figure 15. Columns without energy input (LIC = level indicating controller)
A) Spray column (light phase dispersed); B) Packed column (heavy phase dispersed); C) Sieve plate column (light phase
dispersed)

bottom) of the column as needed, thus the heav-
ier liquid being dispersed above and the lighter
liquid below the principle interface.
Countercurrent columns are equipped with
settling zones at the top and the bottom, with
coalescing aids provided if necessary. The liq-
uids should never be fed into the column in these
settling zones because this would cause hydro-
dynamic instability of the column thus reduc-
ing the operational performance. The dispersed
liquid often cannot be selected from theoretical
considerations, but only by aid of experiments
in a pilot column using the real material system.
Packed columns (structured and unstruc-
tured) and sieve plate columns have
been adopted from distillation technology
(→ Distillation and Rectification, Chap. 8.).
In packed columns drop formation occurs on
entry of the dispersed phase in the packed bed
(Fig. 15 B). The drops rise through the packed
bed without significant further dispersion. How-
ever, mass transfer takes place mainly during
the formation of a new interfacial area. This
explains the low efficiency of packed columns
[6, Chap. 8].
In a sieve plate column with downcomers, as
shown in Figure 15 C, the lighter dispersed phase
coalesces beneath each plate to give a continuous
layer. Its buoyancy presses the liquid through the
holes of the sieve plates, producing jets which
disintegrate into drops. The continuous liquid
flows through the downcomers from stage to
stage and then across the plates. In the case of
low interfacial tension the layers of coalesced
phase are too small for a symmetrical operation
of the plates. Then it is advantageous to use dual
flow plates without downcomers [57].
Sieve plate columns have the advantage over
packed columns that new drops are formed at
each tray. However, the drop load of the plate
is often irregularly distributed, especially if the
column diameter is large (more than 1 m). This is
the reason why sieve plate columns can reach ef-
ficiencies of 10 – 15 % only in rare favored cases.
Moreover, since columns are generally built with
a plate spacing of 0.3 m, even simple separations
require considerable overall heights.
Mass transfer between the two liquids can be
substantially improved by application of addi-
tional mechanical energy in form of superim-
posed agitation or pulsation, resulting in higher
Liquid – Liquid Extraction 17
turbulence near the drops and enlarged mass
transfer area due to smaller drop sizes.
3.1.2. Pulsed Columns
The simplest design of pulsed column is the
pulsed sieve plate column (Fig. 16 A). A piston
pump with an electrical or an air-pressure drive
causes the entire liquid content of the column
to vibrate. Both phases are alternately forced
through the holes in the rhythm of the pulsa-
tion. The downcomers used in the conventional
sieve plate column are thus superfluous. The dis-
persed phase does not coalesce above or below
the plates to give a continuous layer. The pul-
sation shock flings the drops off the plate faster
than would be possible as a result of only the den-
sity difference. This leads to a fine, uniform drop
distribution and hence enlarges the mass trans-
fer area. Applications are limited by the physi-
cal properties of the substances concerned and
high throughputs. Systems which emulsify eas-
ily cannot be processed in pulsed columns just as
sticky and greasy liquids. For very large through-
puts (column diameter > 0.6 m), the pulsed vol-
ume and pulsing power become very high; how-
ever, pulsing units for large column diameters
have been developed.
The separation effect of the column de-
creases with increasing diameter, this has not
yet been fully investigated. The plate spacing is
50 – 100 mm. Larger plate spacings favor back-
mixing and hence reduce the efficiency of the
column. Smaller plate spacings lead to a strong
decrease of the throughput. Sieve plates have
cylindrical holes and a triangular pitch. The re-
lationship between the fractional free area ϕ, the
hole diameter d i and the pitch p is given by
ϕ = πd2i / 12p2
For usual liquid – liquid systems sieve plates
with hole diameters from 2 to 4 mm resulting in
free areas of 23 to 40 % are recommended [6,
Chap. 10], the lower value of 23 % is used for
high and the higher value of 40 % for low in-
terfacial tensions. Free areas less than 20 % are
used for liquids with higher viscosities [58].
The plate material has a pronounced influ-
ence on drop formation and hence on the sep-
aration efficiency. The plate material and phase
selection must be matched in such a way that the
18 Liquid – Liquid Extraction
Figure 16. Pulsed and reciprocating-plate columns (Light phase dispersed)
A) Pulsed sieve-plate column; B) Reciprocating-plate column (Karr)
plates are wetted by the continuous phase but not
by the dispersed phase, because this would lead
to strong coalescence effects. If, for example,
an aqueous phase is to be dispersed into drops,
metal trays are unsuitable, but plastic plates are
satisfactory. The sharp edged side of the sieve
plate, which is due to manufacturing, should ex-
actly face the flow direction of the dispersed liq-
uid so that drops will shear at the edges of the
holes. Gaps between the sieve plate edge and the
column wall should be avoided by precise con-
struction or by applying edge-sealing elements
made of materials which are wetted by the con-
tinuous liquid.
In most cases, piston pumps or diaphragm
pumps are used as the pulsators. The pulsing
frequencies are between 30 and 150 min−1 , with
pulsing amplitudes from 5 – 15 mm (relative to
the column cross section). (Pulsing amplitude
is defined as the distance between upper and
lower center of the pulsing motion in the ac-
tive part of the column.) The dispersed phase
has to be fed into the column via a distribu-
tor. The mean drop diameter of the predispersed
swarm should be larger than the mean drop size
in the active part of the column, otherwise the
hydrodynamics of the column would mainly be
affected by the distributor. The holes in the dis-
tributor should be very sharp-edged to avoid very
fine drops. Even in packed columns, the sepa-
ration effect can be substantially improved by
pulsing of the continuous phase, at the expense
of a reduced throughput. The increased perfor-
mance results from greater shear forces caus-
ing a reduction in drop size and an increase in
interfacial area [6, Chap. 8]. As in distillation
columns, the phenomenon of maldistribution in
randomly packed columns of larger diameter
can be overcome by use of structured packings.
These packings lead to a good cross-sectional
mixing and have a higher capacity, typically a
total flow rate of both phases of approximately
100 m3 m−2 h−1 compared to 30 m3 m−2 h−1 for
a randomly packed column. Structured packings
are particularly suitable for low interfacial ten-
sion systems or for small density differences;
separation efficiency is nearly independent of
scale-up. Hydrodynamics and mass transfer per-
formance are well investigated [6, Chap. 8], [59].
Pulsing Units. The use of pulsed columns is
currently limited to small and medium through-
puts. The column diameter is limited by the puls-
ing unit. For very large throughputs, the pulsed
volume becomes so large that the use of a piston
pump as the pulsing unit causes difficulties. Con-
sequently, pulsing units have been developed
which operate without a piston pump. The pul-
sator developed by Misek (Fig. 17) is based on
 Liquid – Liquid Extraction 19

a centrifugal pump. The pump (e) is connected

on both the suction side and the delivery side to
pressure vessels which are alternately connected
to the column by means of a rotating valve (c).
With the valve setting shown in Figure 17 A,
the pump delivers the liquid into the column via
the discharge drum (b), taking the rate delivered
from the suction drum (a). After changeover of
the valve (Fig. 17 B), the pump delivers from the
column via vessel (a) into drum (b). The pump
thus always delivers continuously in one direc-
tion. Reversal of the direction of flow in the pulse
line is effected by the change-over valve (c) in
accordance with the pulse frequency. A pulsator
based on this principle has been developed by
Bronswerk/DSM (Fig. 17 C), and is now in op-
eration for columns with a maximum diameter
of 2.7 m.
For large pulsed volumes, the hydraulic pul-
sator from Wepuko [60] is also suitable (Fig. 18).
It is flanged directly to the lower bottom of the
column end and acts in the direction of the col-
umn axis. The pulsing piston is connected via a
common piston rod to a working piston, the hy-
draulic drive of the piston is a rapidly reversible
radial piston pump.

Reciprocating-Plate Columns. In another

approach for solving the problem of large
throughputs, the plates, and not the liquid, are
made to reciprocate, so that the pulsing pump
is eliminated. This principle led to the develop-
ment of the reciprocating-plate column which
can be regarded as the converse of the pulsed
sieve plate column. In the pulsed sieve plate col-
umn, the trays are fixed and the entire liquid
content of the column is caused to vibrate; in
the reciprocating-plate column, the plates are
moved. In both cases, the liquid undergoes an
oscillating motion relative to the plate.
In the Karr column (Fig. 16 B), sieve plates
with a free area of about 60 %, a 10 – 15 mm
hole diameter, and a 25 –50 mm plate spacing,
are mounted on a central shaft. The complete
pack is moved up and down, driven by an ec-
center.
Figure 17. Pulsator with rotating valve
A) Principle diagram of compression stroke; B) Principle di-
agram of suction stroke; C) Technical design (Bronswerk)
a) Suction drum; b) Discharge drum; c) Rotating valve;
d) Column; e) Centrifugal pump
The relatively large free area of reciprocat-
ing plate columns allows much greater through-
puts than conventional pulsed columns. How-
ever, recent investigations showed that pulsed
sieve plate columns can be equipped with larger
free areas, too. Both types of pulsed columns
show very similar performances and operational
behavior if they are equipped with the same free
areas [61]. Research on the established types of
pulsed columns has been very intensive since the
1970s.
20 Liquid – Liquid Extraction
Figure 18. Hydraulic pulsator
a) Pulsing piston; b) Working piston; c) Rinsing; d) Hy-
draulic aggregate with radial piston pump
Figure 19. Rotating disk contactor (RDC)
a) Rotating disk; b) Stator ring
3.1.3. Columns with Rotating Internals
Rotating Disk Contactor (RDC). In the
RDC (Fig. 19 A), stator rings are mounted at
close intervals. Disks are fitted between the rings
to a rotating shaft. The rotating disks fling the
drops of the dispersed phase off centrifugally,
onto the stator rings where they are braked and
deflected. The drop distribution is excellent and
can reach the emulsification limit as the rota-
tional speed increases.
The RDC has a relatively simple construction
with a large free cross-sectional area. On the one
hand, it reaches large throughputs, on the other
hand it favors backmixing of phases causing a
decrease of efficiency. A large range of through-
puts is possible without remarkable decrease of
efficiency. The loading limit is generally lower
than in pulsed columns. The RDC is unsuitable
for mixtures which tend to form emulsions and
for products containing dirt. The separation ef-
ficiency decreases sharply with increasing di-
ameter. Nevertheless, successful RDCs of up
to 3500 mm in diameter have been constructed.
They are thus suitable for greater throughputs
than pulsed columns and are preferably used to
operate with large product flows when the de-
mands on separation performance are only low
as for instance in the oil industry or in wastewa-
ter treatment [42].
As in pulsed columns, the wetting behavior
also influences drop formation in the RDC, and
should therefore be taken into account when se-
lecting a material for the column internals.
Kühni Extractor. The Kühni extractor
(Fig. 20 A) uses a turbine as the mixing ele-
ment. Perforated partition disks separate the
extraction stages and reduce backmixing.
This apparatus is also used for performing
reactions between two liquid phases; the resi-
dence time can be adjusted via the free area of
the perforated disk.
QVF-Extractor. The QVF extractor RZE
(Fig. 20 B) uses blade stirrer as mixing elements.
The partition disks have meander-formed metal
stripes at the inner circumference to reduce the
phase dispersion by channeling of both phases.
The operational behavior is similar to that of the
Kühni extractor (see Fig. 20 A).

Figure 20. Columns with rotating internals
A) Kühni extractor; B) QVF extractor
Graesser Contactor. The Graesser contac-
tor (Fig. 21) is another type of rotating equip-
ment. Here, not only the internals but the entire
apparatus rotate. Internal half-tubes are fitted as
scooping elements in a horizontal rotating cylin-
der. Due to the rotation, the half-tubes transport
part of the heavy phase into the overlying light
phase, and vice versa. To reduce backmixing,
the extractor length is divided into chambers by
partition disks. Because of its low dispersing ef-
fect, this equipment is particularly suitable for
systems which tend to emulsify. The throughput
is low compared with other extractors.
Figure 21. Graesser contactor
Liquid – Liquid Extraction 21
3.1.4. Mixer – Settlers
Mixer – settlers consist of single or several
stages in series (Fig. 22 A), each stage consist-
ing of a stirred vessel and a settling vessel
(Fig. 22 B). Various arrangements are possible
such as cocurrent, countercurrent, or crosswise
flow of phases. The mixer – settler is the only ex-
tractor that reaches stage efficiencies of nearly
100 % and is almost insensitive for load fluctu-
ations.
This extractor has the advantage that back-
mixing can be completely precluded due to the
complete phase separation in each stage. As a re-
sult, there are no transfer problems in scale-up.
The favorable efficiency is almost completely re-
tained even for large throughputs. Any number
of separation stages can be built, and, moreover,
throughput does not appear to be limited. These
advantages account for the widespread use of
mixer – settlers in industrial processes for many
decades. However, early mixer – settler equip-
ment was very complex. Each separation stage
consisted of a stirred vessel and a settling vessel.
The two phases had to be pumped between the
individual stages. Each settler needed an inter-
face level control. The horizontal arrangement
resulted in a large area requirement.
In an effort to overcome these disadvantages
of the mixer – settler batteries without foregoing
any of their advantages, a number of different de-
signs were developed. Mixer – settlers are used
22 Liquid – Liquid Extraction

Figure 22. Principle of a mixer – settler

A) Flow Sheet; B) Arrangement

in two different areas. Industrial-scale equip-

ment is used to obtain extremely high through-
puts when a small number of stages is needed,
e.g., in the extraction of metal salts. Laboratory-
scale devices are employed in process develop-
ment to check the number of calculated stages
as a function of the ratio solvent.
Large-scale mixer – settlers were originally
developed to extract copper from dilute aque-
ous solutions. The basic design is a box-type
mixer – settler according to Denver (Fig. 23).
The mixing and separating zones are combined
in a single unit and are separated by an over-
flow weir for the light phase and an underflow
slit for the heavy phase. The individual stages
are arranged so that the outlet of the settler also
acts as the inlet of the mixer. The agitator has
two functions, it disperses and conveys the liq-
uid phases. These functions may conflict with Figure 23. Box-type mixer – settler (Denver)
one another. The rate of rotation necessary to A) Side view; B) Ground plain
overcome the conveying height may be too high
when unstable systems must be dispersed, caus- A further development of the Davy McKee
ing problems in phase separation, e.g., a high mixer – settler has been described [43]. Each
degree of entrainment. Mixing pumps with low stage consists solely of a vessel in which mixing
shearing forces, and thus a low mixing intensity, and separation occur. The product inlet and the
have been developed to avoid these difficulties. agitator are located in the middle and create a
Examples are the Pumpmix impeller used with dispersion zone. The light phase separates out at
the Davy McKee mixer – settler (Fig. 24 A) and the top and the heavy phase at the bottom.
the IMI turbine pump-mix unit (Fig. 24 B). In the Lurgi tower extractor, the battery of
adjacent settlers is replaced by a space-saving

Figure 24. Industrial mixer – settlers
A) Davy McKee mixer – settler; B) IMI turbine pump-mix unit (cross section A – B – C – D shown in the lower part); C) Lurgi
tower extractor
tower design in which the settlers are arranged
on top of each other. External centrifugal pumps
are used for mixing (Fig. 24 C). Like all mixer –
settlers, this device is suitable for very large
throughputs provided that the liquid system can
withstand the high energy input of the mixing
pump. Backmixing to a certain degree is un-
avoidable since the stages have hydrodynamic
connections.
Multistage mixer – settlers are a valuable aid
in process development on a laboratory scale.
They can be integrated in “mini plants”; at this
stage of development no decision should be
made which type of equipment is suitable for
the large-scale plant. Several examples of lab-
oratory mixer – settlers are shown in Figure 25.
3.1.5. Centrifugal Extractors
Centrifugal extractors are used when the density
difference between the two phases is insufficient
to produce a countercurrent under gravity. The
best known of these devices is the Podbielniak
centrifugal extractor (Fig. 26 A), in which cylin-
drical perforated sheets are concentrically ar-
Liquid – Liquid Extraction 23
ranged as a compact rotor on a high-speed shaft.
The heavy phase is fed in via the shaft and moves
outwards due to the centrifugal force. The light
phase moves in the opposite direction. Similar
to columns, either the light phase or the heavy
phase can be dispersed into drops, as desired. If
the light phase is to be dispersed, the main inter-
face must be located near the shaft. Depending
on the system the number of stages which can
be combined in one unit is limited to 3 to 4 the-
oretical stages.
The Robatel centrifugal extractor is based on
a totally different principle and allows greater
numbers of stages (Fig. 26 B). Disks serving as
the mixing element are centered on a vertical sta-
tor. The housing is divided by annular disks into
a number of stages and rotates around the central
shaft. Each stage consists of a mixing chamber
and a settling chamber. The disks each dip into
the mixing chamber. An extensive review on op-
eration and calculation of centrifugal extractors
is given in [6, Chap. 14].
Centrifuges are more complex than columns,
their investment and maintenance costs are cor-
respondingly high. They can therefore only
stand comparison with columns in cases where
24 Liquid – Liquid Extraction
Figure 25. Laboratory mixer – settlers
A) Normag mixer – settler; B) Schott/QVF mixer – settler
they have advantages which no column can
provide. Phase separation is possible even in
systems having a density difference as low as
15 kg/m3 . Systems with large differences in vis-
cosity can be processed, since the high shear
forces effect intensive mixing.
As a result of its compact design, the centrifu-
gal extractor is a space-saving apparatus with an
extremely small operating volume and a short
residence time. These advantages can be desir-
able if expensive solvents or substances of lim-
ited stability are used. The steady state is reached
soon after starting. This extractor is therefore
suitable for batchwise operation and frequent
changes of products. Extraction under pressures
of up to 5 MPa is possible.
3.2. Fluid-Dynamic Fundamentals
A comprehensive treatment of fluid-dynamic
fundamentals is given elsewhere (→ Fluid Me-
chanics).
3.2.1. Problems and Process Strategy
In Section 2.5, it was shown how the number of
theoretical stages and the flow diagram of the
unit operation “extraction” are calculated on the
basis of equilibria. The selection and design of
apparatus are based on fluid dynamics and are
not carried out until the thermodynamic design
is completed. At present, model experiments are
still necessary for the design of extraction appa-
ratus. For this reason, a knowledge of the op-
erating characteristics of the various types of
apparatus is of great interest so that the num-
ber of experiments can be substantially reduced,
and preselection and preliminary sizing can be
carried out at a relatively early stage of process
development.
The fluid-dynamic design of an apparatus is
divided into the following areas:
1) Selection of suitable internals with respect to
material of construction, shape, and size.
2) Determination of the operating conditions
with respect to phase selection, pulsing, and
loading.
3) Sizing of the column diameter in accordance
with the required throughputs of feed and
solvent.
4) Sizing of the column height in accordance
with the actual separation problem.
However, these four problems cannot be con-
sidered in isolation. Thus, both the internals and
the operating conditions affect (1) the loading
limit and hence the column diameter and (2) the
separation efficiency and thus the column height.
Measures for increasing the loading limit have

an adverse effect on the separation efficiency,
and vice versa.
Figure 26. Centrifugal extractors
A) Podbielniak extractor; B) Robatel four-stage countercur-
rent extractor
The sizing of the column diameter depends
on the flooding point, i.e., the maximum load-
ing limit at which a column can be operated. On
flooding, accumulation of the dispersed phase
occurs at individual points within the column
and blocks countercurrent flow. Consequently,
the light phase appears in the discharge of the
heavy phase, and vice versa. This phenomenon
is detectable by holdup measurements. On flood-
ing, the holdup increases continuously and indi-
cates an unstable operating state.
Liquid – Liquid Extraction 25
The flooding limit depends on the drop size.
Small drops rise less rapidly than large drops
and therefore cause a greater holdup. The more
energy is supplied to the system – either by puls-
ing or by rotating internals – the smaller are the
drops, so that the flooding limit decreases.
Internals also effect dispersing. The smaller
their open area, the more the flooding limit de-
creases.
The sizing of the column height is determined
by the mass transfer, which is described by the
well-known mass-transfer equation: the rate of
mass transferred is equal to the product of the
mass-transfer coefficient, the mass-transfer area
and the concentration difference between the
two phases. A great progress in scientific re-
search has been achieved as regards measure-
ment and calculation of the quantities of influ-
ence on mass transfer (see for instance [6], [45–
49], [51], [62–65], [68]. But in practice, the var-
ious influences on mass transfer are best sum-
marized in the expression “ height equivalent of
a theoretical stage” (HETS), as a measure for
the separation efficiency of the column, as men-
tioned in Section 2.5.
Measurements in pilot-plant columns will be
used below to demonstrate the way in which var-
ious parameters affect the loading limit and sepa-
ration efficiency. The test systems recommended
by the European Federation of Chemical Engi-
neering (EFCE) are used for this demonstration
[44].
3.2.2. Operating Characteristics of Pulsed
Columns and Columns with Rotating
Internals
Loading Limit. Figure 27 shows the load-
ing limit v C + vD as a function of the pulsing
frequency for plates of small free area ϕ for
the toluene – water system, i.e., for high inter-
facial tension. vc and v d are the volume flows of
continuous (c) and dispersed (d) phase related
to the total cross-sectional area of the column,
the so-called superficial velocities. This flood-
ing point curve starts at the origin of the co-
ordinates; in other words, without pulsing, no
throughput is possible. With increasing pulsing,
the throughput also rises up to a maximum. This
part of the curve is called the lower flooding
limit; here, pulsing has mainly a transport func-
26 Liquid – Liquid Extraction
tion. With increasing frequency, however, the
dispersing function predominates, the drops be-
come smaller and the loading limit falls. The
interesting region in practice is that in which
dispersing predominates.
Figure 27. Loading limit as a function of the pulsing fre-
quency at different free area for toluene – water [50]
a = 6 mm; vd /vc = 1
 ϕ = 0.60; d = 6.5 mm

ϕ = 0.40; d = 4.0 mm
◦ ϕ = 0.23; d = 2.5 mm
As is to be expected, the loading limit rises
with increasing free area over the entire pulsing
range, but the position of the maximum remains
unchanged. At the largest free area of ϕ = 0.6,
a modest throughput is possible even without
pulsing.
Figure 28. Loading limit as a function of pulsation
frequency at different interfacial tension [50]: ϕ = 0.23;
v d /vc = 1
a) Butanol – water: σ = 1.8 mN/m; b) Butyl acetate – water:
σ = 13.5 mN/m; c) Toluene – water: σ = 36.1 mN/m
The effect of the geometry of the internals can
also be shown for pulsed packed columns. There
is no lower loading limit. At frequency f = 0, i.e.,
the unpulsed column, the loading limit has its
maximum value, and decreases with increasing
frequency [53].
Of all the physical properties, the interfacial
tension has the greatest effect on the fluid dy-
namics of an extraction column. Figure 28 shows
a comparison of three test systems with different
interfacial tensions. As can be seen, the through-
put optimum is shifted to higher pulsing frequen-
cies with increased surface tension, i.e., high sur-
face tensions need a high energy supply.
In addition to the physical properties, the
phase ratio is another parameter determined by
the process. Decisions can only be made as to
which of the two phases is to be dispersed (the
organic or the aqueous phase) and whether in the
greater or smaller quantity. Figure 29 shows the
effect of the parameter vd /v c [52]. As the phase
ratio increases, the throughput decreases.
Figure 29. Relative loading of a pulsed sieve plate column
as a function of flow ratio [52]
◦ Toluene – water;
MIBK – water;  Butyl
acetate – water;  n-Butanol – water
A further parameter affecting the loading
limit and separation efficiency is the direction
of the mass transfer. Curve b in Figure 30 A
shows the flooding point curve of the pure two-
component mixture toluene – water, where no
mass transfer takes place [54]. Curve a for mass
transfer from the dispersed organic phase to
the continuous aqueous phase lies substantially
higher by comparison. The reason for this is
an increased tendency to coalescence and hence
formation of larger drops. In the converse case
(mass transfer from the continuous to the dis-
persed phase), the interfacial tension and hence
the drop size are reduced by the component

being transferred, leading to a lowering of the
flooding point [53], [55]. The effect of the di-
rection of mass transfer on the drop size also
causes differences in the separation efficiency.
In the case of mass transfer from the continu-
ous phase to the dispersed phase (into the drop),
smaller HETS values result, i.e., better separa-
tion efficiency is obtained (Fig. 30 B).
Figure 30. Influence of mass transfer on loading limit and
separation efficiency for the toluene – acetone – water sys-
tem (ϕ = 0.60)
 Mass transfer from the disperse to the continuous phase;

System without mass transfer; ◦ Mass transfer from the
continuous to the disperse phase
Pilhofer [56] has shown that the loading
limit of extraction columns depends only on the
drop size. Accordingly, high loading limits can
be obtained only with relatively large drops.
Separation Efficiency. However to obtain a
high separation efficiency a large mass transfer
area, i.e., the greatest possible holdup of dis-
persed phase, is required. The holdup rises with
decreasing drop size. Any input of energy has the
purpose of producing the optimal drop disper-
sion. The interrelation of separation efficiency
and pulsing can be demonstrated by measure-
Liquid – Liquid Extraction 27
ments on the toluene – water – acetone system,
which has a high interfacial tension [41]. Fig-
ure 31 shows the measured height of a theoret-
ical stage (HETS) for this system as a function
of the pulsation frequency, for the three different
plate types (curves a – c). In all cases, the HETS
decreases as expected with increasing pulsing
intensity, i.e., pulsing enhances the separation
efficiency. The curves show an important influ-
ence of the plate geometry: with increasing free
area, the separation efficiency decreases sharply.
Figure 31. Separation efficiency measured as a function of
interfacial tension [41]
a) – c) Toluene – water – acetone;
d) Butanol – water – succinic acid
+ ϕ = 0.60; ◦ ϕ = 0.40;  ϕ = 0.23
The butanol – succinic acid – water system
shows very favorable HETS values because of its
extremely low interfacial tension (curve d). The
effect of free area is negligible. This means that,
for systems of low interfacial tension, the free
area can be increased in favor of higher through-
puts, without a significant loss in separation ef-
ficiency.
A comparison of these two systems clearly
shows the pronounced influence of the interfa-
cial tension on separation efficiency. This fluid-
dynamic aspect should also be taken into ac-
count when selecting solvents for extraction pro-
cesses. Hitherto, this selection has been made al-
most exclusively under thermodynamic criteria.
28 Liquid – Liquid Extraction

The relationship between plate geometry, in-
terfacial tension, and separation efficiency, as
described here for a pulsed sieve plate column,
qualitatively applies also to reciprocating-plate
columns and pulsed packed columns. Generally
speaking, in systems with a high interfacial ten-
sion, particular attention must be paid to the
choice of the internals, a higher energy input is
also necessary.
3.2.3. Fluid Dynamic Calculation Methods
The calculation methods for determining the
loading limit can be classified in two categories.
The first category consists of empirical correla-
tions which are based on physical and geometri-
cal data, and energy input. The second category
is based on fluid-dynamic models and presup-
poses knowledge of the drop size. Both method
classes are applicable only to two-component
systems and thus neglect the effect of mass trans-
fer, as shown in Figure 30. The effects of wet-
ting and of drop coalescence are likewise dis-
regarded. Moreover, the empirical correlations
in particular are frequently restricted to certain
geometries and cannot be extrapolated to other
designs, they can therefore only be used to ob-
tain an approximate estimate. For final equip-
ment sizing, an experimental determination of
the loading limit in the particular type of equip-
ment with the original process streams is abso-
lutely necessary.
Packed Column. Unpulsed packed columns
have no industrial significance any longer. A re-
view on empirical equations to calculate holdup,
drop size, flooding, mass transfer, and axial dis-
persion is given in [6, Chap. 8]. Performance
can be improved by mechanical pulsation of the
continuous phase at the expense of a reduced
throughput. For a rough estimate, pulsing within
reasonable ranges may be assumed to cause the
load limits to fall by 20 – 30 % as compared with
the unpulsed column. Still, no equations for cal-
culation are known.
surface tensions and density differences than
toluene – water and to dual flow plates. For cal-
culation see [69].
Sieve Plate and Rotating Columns. Spe-
cial empirical equations are given in the lit-
erature for each type of extraction columns in
order to calculate the flooding condition, so,
e.g., for sieve plate columns in [66] and [67], for
pulsed sieve plate columns in various chapters
of [6], for rotating columns in [6] and [5]. How-
ever, since important effects are disregarded
as mentioned before, here it will be sufficient
to introduce a rough method based on a fluid
dynamic model [66]. The model, originally de-
veloped for unpulsed sieve tray columns, proved
to be applicable to all types of columns. It is as-
sumed that the liquids occupy a share of the
cross-section according to their holdup ε and
flow toward each other as layers. If their super-
ficial velocity v, i.e. their volumetric flow rate V
related to the complete column cross section S,
is
Vc Vd
vc = ; vd = (1)
S S
they have an effective velocity vc /(1 − εd ) or
v d /εd . That yields the relative velocity vr , also
called slip velocity, between the two liquids
vd vc
vr = + (2)
εd 1 − εd
Either vr or εd can be calculated from Equa-
tion (2) if one or more relationships between the
two terms are known. In [45] a simple empirical
equation is given to calculate vr
vr
= (1 − εd )k (3a)
vp
k = 4.6 − 0.13 lnAr (3b)
7
when 1 < Ar < 10 and 2.5 < k < 4.6
vP is the individual drop velocity given by
[66]
for circulating drops
 
0.15 −0.1435
Rep = KL Ar0.523 KL − 0.75 (4a)

Sieve Plate Column. The conventional if

sieve plate column has been investigated by 1.83 K 0.275 <Ar< 3.94 K 0.275
L L
Pilhofer [66] for toluene – water systems.
Hirschmann [69] expanded the investigations
of Pilhofer to liquid systems with lower for oscillating drops
 Liquid – Liquid Extraction 29
 
0.15
Rep = KL 4.18Ar0.218 KL−0.00773 − 0.75 (4b)
for flooding point diagrams according to Fig-
ure 32. Ordinate and abscissa contain the su-
if perficial velocities v d and vc , i.e., the phase
flow rates, modified by physical data groups to
0.275 a dimensionless form. The diagram shows the
Ar > 372.9KL (4c)
calculated flooding curves of circulating drops
The dimensionless numbers are defined as fol- as solid lines with the parameter Ar. Dashed
lows: lines of constant phase ratio vd /v c and the to-
particle Reynolds number tal throughput as the sum of v d and vc are also
vp dp shown.
Rep = (5)
νd

Archimedes number
d3p gc ∆
Ar = (6)
ηc2

characteristic number of liquid

2c σ 3
KL = (7)
∆gηc4

density difference

∆ = |c − d | (8)

Mathematical formulation implies the fact that

an increase of the flow rate at flooding cannot
Figure 32. General loading diagram [52], [56]
increase the drop holdup:
dvd
It can be seen from Equation (4b) that ReP is
=0 (9a) approximately proportional to Ar 0.3 and there-
dεd
fore to d P . That means that the drop velocity vP
when vc = constant, is nearly independent of drop diameter d P in the
region of oscillating drops. Therefore Figure 32
dvc
=0 (9b) can be used also for oscillating drops if Ar is
dεd
replaced by K L using Equation 4c. Otherwise
when vd = constant. the diagram is valid for a certain K L value in the
With Equation (2) for the slip velocity vr the region of circulating drops, in case of Figure 32,
equations for calculating the superficial veloci- K L = 1011 .
ties v c , vd at the flooding point are obtained in a The dependence of drop diameter d P upon
dimensionless form: parameters of influence must be known in or-
 1/3 der to use Figure 32 and to calculate flooding
c curves. Many scientific investigations on drop
vc = Ar−1/3 (1 − εd )2 (Rer +
∆vc g disintegration in various extractors are found in
 the literature, but often without considering the
εd dRer
(10a) influence of mass transfer and the interaction of
dεd
 1/3 dispersing and coalescence. Furthermore, par-
c ticularly for higher interfacial tension systems
vd = Ar−1/3 ε2d (Rer −
∆vc g a considerable height of column is required to
 reach a steady-state drop size, and this height
dRer
(1 − εd ) (10b) varies with liquid system and inlet arrangement
dεd
for the dispersed phase. Since population bal-
Equations (10a) and (10b) together with Equa- ances are not used in this introductory article,
tion (3) for v r and Equation (4) are the basis
30 Liquid – Liquid Extraction

the concept of mean drop sizes is applied – nor- The values of the constant C 1 are 9.81 × 10−2
mally reported as the Sauter mean or surface for no mass transfer and c → d transfer and 0.31
percentage mean drop size – defined by for d → c transfer. The stage number nS , which

varies from 2 to 17 in the present set of data,
npi d3pi
d32 =

i
(11)
shows a rather weak effect on drop size. Equa-
npi d2pi tion (14) predicts the drop diameter with an av-
i
erage absolute value and relative deviation of
where npi represent the numbers of drops of the 17.6 %.
class i of diameter d pi .
Finally, discussion will be restricted to em- 3.3. Apparatus Design
pirical equations by Kumar and Hartland [6,
Chap. 17] which give the best fit to experimental Extraction apparatus can be approximatively
data and have the broadest range of validity: designed purely by calculation using fluid-
Pulsed sieve tray and reciprocating extractor dynamic models [49], [70]. For reliable design,
 0.10 however, pilot-scale tests are indispensable. If
d32 h
 = C1 e0.74 · possible, the test should be carried out with the
σ 0.05m
∆g
  original operating mixture in the type of appara-
af ∆1/4 tus which is also envisaged for the large-scale
· exp −3.00 1/4 +
gσ 1/4 unit. Desirably, the geometry of the internals
should be the same in the pilot-scale and indus-

af ∆1/4 trial apparatus. However, this condition cannot
exp −28.65 1/4 (12) always be satisfied. Generally, a column diame-
gσ 1/4
ter of at least 60 – 80 mm is necessary for design
The best values of the parameter C 1 are 1.51, tests. Tests in smaller columns cannot be used
1.36, and 2.01 for no mass transfer, c → d, and as the basis for equipment sizing (for criteria
d → c direction of transfer, respectively. The on equipment selection, see Section 3.4). The
product a · f is considered as the agitation vari- number of tests can, however, be substantially
able in the equation, since the fit could not be reduced if knowledge of the operating charac-
improved if a and f were treated separately. The teristics is utilized.
average absolute value of the relative deviation The physical data and the phase ratio are de-
in the predicted values of d 32 from the experi- termined by the process used, the following pa-
mental points is 16.3 %. rameters are available for optimization: pulsing
Rotating disk extractors or rotation, geometry of the internals, material
  −0.12
d32 C1 ηc of the internals, and phase selection, i.e., the di-
= √ √
DR 0.07 + F rR σc DR rection of mass transfer. Energy input and the
 0.16 2 −0.59 geometry of the internals are selected on the ba-
d DR c g
· sis of the physical data.
c σ
 0.25  0.46
h D
(13)
DC DR 3.3.1. Internals and Operating Conditions
The optimized values of C 1 are 0.63, 0.53, and
0.74 for no mass transfer, c → d and d → c di- The following guidelines apply for the selection
rections of transfer, respectively. The effect of of the free area in pulsed columns. An increase
holdup is ignored due to lack of data. Equation in the free area is recommended in systems with
(13) predicts the drop size with an average ab- a low interfacial tension where it leads to a great
solute value of the relative deviation of 23 %. reduction in the column volume. At moderate
Kühni columns interfacial tension, the column diameter can be
d32
reduced by a greater free area, but at the expense
= C1 e0.37 n−0.11
S [0.14 + exp (−18.73F rR )] · of the column height. In the case of extremely
DR
 −0.20 2 −0.24
ηc DR c g
· √ (14)
σc DR σ
 Liquid – Liquid Extraction 31

Figure 33. Selection of phases and plate materials

high interfacial tension, there is no point in in- this expression is equivalent to a minimum col-
creasing the free area. umn volume. Figure 34 shows that optimum
The material of the internals should be se- pulsing is obtained between the maximum of
lected so that the continuous phase, but not the the flooding point curve and the minimum of
dispersed phase, wets the plates. As a rule of the HETS curve. An analogous procedure is
thumb, metal plates can be used when the or- used for rotary agitated columns. The design
ganic phase is dispersed; if the aqueous phase point for industrial-scale columns is chosen to
is dispersed, the internals should be of plastic, be 75 – 80 % of the load limit. The operating
both in pulsed columns and in rotary-agitated point with respect to load and pulsing (rotation)
columns. is fixed by this procedure.
In deciding which phase should be dispersed,
the direction of mass transfer must be taken into 3.3.2. Column Diameter
account. In accordance with Figure 30, mass
transfer should be from the continuous phase Assuming the same column geometry, the spe-
to the dispersed phase, if possible. In the final cific throughput of the test column is adopted for
phase selection, however, fluid-dynamic consid- the large-scale column.
erations frequently conflict with operating and (vc + vd )2 = (vc + vd )1
safety requirements. The position of the inter-
face in the column determines the phase which with
is dispersed. Figure 33 summarizes the possible (vc + vd )1 = 0.75· (vc + vd )1max
combinations.
The separation efficiency determines the col- Index 1 = pilot scale
umn height and the load limit determines the col- Index 2 = large scale
umn diameter. For optimization, the two param- This gives the column diameter:
eters are related by the ratio θ = HETS/(v c + vd )   

which can be used to optimize the column in-  4 ṁF + ṁS
 F S 2
ternals and energy input. A minimum value of D2 =
π· (vc + vd )2
32 Liquid – Liquid Extraction
Figure 34. Optimization of pulsation
3.3.3. Column Height
The separation efficiency of all columns de-
creases with increasing column diameter, be-
cause the residence time distributions of the
phases increase. Therefore values of the height
of a theoretical stage, measured for a laboratory
column, need to be corrected by empirical scale-
up equations to be applicable for industrial-scale
columns. However, scientific investigations of
this problem are rather poor and mainly empiri-
cal knowledge of industrial engineers exists. The
different chapters of [5] list formulae from ex-
perience with countercurrent extractors as de-
scribed here, including
Pulsed sieve tray columns [71]
HETS2
=exp [1.64 (D2 − D1 )] (15)
HETS1
(in Equation 15 the factor 1.64, given by Thorn-
ton, is only valid for small columns. Figure 35
shows an empirical dependence of the Thornton
factor from the column diameter published by
Reissinger [49])
Reciprocating columns [72]
 0.38
HETS2 D2
= (16)
HETS1 D1
When the plate geometry and amplitude of
the vibration are left unchanged in the large-
scale column, the frequency should be reduced,
according to:
 0.14
f2 D1
=
f1 D2
The following applies to stirred columns [73]:
 0.33
HETS2 D2
=
HETS1 D1
Figure 35. Dependence of Thornton factor on column di-
ameter
3.4. Criteria for Equipment Selection
For a given separation problem, equipment is
selected essentially according to three criteria:
physical properties, required number of separa-
tion stages, and throughput. Further operating
aspects are frequently important, for example,
flexibility regarding load variations or product
quality, sensitivity to small amounts of solids,
suitability for batch operation.
The physical properties of interest in extrac-
tion are the density difference between the two

Figure 36. Comparison of the number of theoretical stages NTS in dependence of total load for Kühni, QVF, Karr and pulsed
sieve plate extractors (PSE) [64] (system butyl acetate – water – acetone, phase ratio vd /vc ≈ 1.12, measurements of various
authors cited in [64])
phases, their viscosity, and interfacial tension.
These three parameters affect dispersibility and
phase separation behavior.
High density difference, viscosity, and inter-
facial tension make dispersing more difficult;
systems with such physical properties require a
higher dissipation of energy than in the converse
case. Phase separation is favored by a high den-
sity difference and interfacial tension, whereas
a high viscosity makes phase separation more
difficult.
The lower limit for the density difference can
be taken to be 50 kg/m3 . Mixtures with higher
density differences can generally be processed in
columns and mixer – settlers. If the density dif-
ference is smaller, a centrifugal extractor must
be used.
A low interfacial tension leads to phase sep-
aration problems. In industrial units, approxi-
mately σ = 1 – 2 mN/m can be taken as the lower
limit. Therefore, mixer – settlers can certainly
not be used for mixtures of relatively low interfa-
cial tension; because of the shear field generated,
centrifugal extractors also have a dispersing ef-
fect which should not be underestimated. In such
cases, the energy input must be very carefully
controlled. Rotary-agitated columns and pulsed
columns can be used, in which the energy input
Liquid – Liquid Extraction 33
can be adapted to the physical properties by the
speed of rotation or the pulse frequency.
The selection of equipment is also affected by
the number of theoretical stages (NTS) required
for a given separation problem. Only small num-
bers of theoretical stages can be achieved in
columns without energy input, because of their
poor separation efficiency. Pulsed columns and
rotary agitated columns give higher numbers
of separation stages. They are limited by the
pulsing units or by the lengths of the contin-
uous shaft. In centrifugal extractors, the Ro-
batel design provides more separation stages
than, for example, the Podbielniak extractor.
Mixer – settlers are constructed in modules so
that there is virtually no limit to the number of
separation stages.
A first estimate of the maximum possible
throughputs in the individual extractor types can
be obtained by considering the largest diameters
(Dmax ) which have hitherto been installed:
Dmax , m
Reciprocating-plate column 1.5
Pulsed column 2.7
Kühni extractor 2.5
QVF extractor 2.8
Rotating Disk Extractor 3.0
Mixer – settler tower 8.0
34 Liquid – Liquid Extraction
Figure 37. Comparison of efficiency versus load of packed columns with and without pulsing and pulsed sieve tray extractors
a · f = pulsation intensity, Bf = flooding load, ϕ = relative free area
Accordingly, the highest throughputs can
clearly be achieved with the mixer – settler. In
pulsed columns, the diameter is limited by the
pulsing unit. In rotation columns, the separation
efficiency at large diameters is no longer satis-
factory. However, informations about maximal
cross-sectional loads which are necessary to ob-
tain definitive throughput data of a type of ex-
tractor are not given in the list.
The literature contains some publications
which recommend criteria for the selection of
the best apparatus. However, most of these rec-
ommendations are only qualitative, and some are
even contradictory; no studies of apparatus have
so far allowed an objective comparison. Only the
standardization of test systems for extraction has
allowed fluid-dynamic studies to be carried out
under comparable conditions [44]. The follow-
ing systems have been recommended:
Toluene – water – acetone
Butyl acetate – water – acetone
Butanol – water – succinic acid
These systems provide an objective basis for
comparison of equipment. Nevertheless, investi-
gations by different authors are not always mu-
tually comparable with respect to the absolute
HETS values. Evidently, the column length and
the phase ratio have an unexpectedly large effect.
For the toluene system, Pilhofer compared
the different operating characteristics of vari-
ous groups of equipment. Analogous studies on
the liquid system butyl acetate – water – acetone
were carried out by Goldmann [64]. Figure 36
shows a diagram of Goldmann with the number
of theoretical stages NTS per meter of column
height, as a function of the load. The figure con-
tains data for QVF and Kühni columns – the lat-
ter with five different free areas of the perforated
partition disks – and for pulsed sieve plate ex-
tractors (PSE) with five different free areas ϕ and
one reciprocating column (Karr). The rotary agi-
tated columns of QVC and Kühni with the small-
est free areas ϕ clearly achieve the highest NTS
values, but allow only low loads. Also, the other
Kühni columns show higher NTS values than the

pulsed columns but smaller ranges of load. Gen-
erally speaking, all measures which improve the
separation efficiency reduce the load capacity.
A comparison between pulsed sieve trays
and structured packings with the test system
toluene – water – acetone was published [74].
Figure 37 shows the diagram with the extractor
efficiency in dependence on the load. It is obvi-
ous that structured packings have the broadest
range of load capacity and reach the same or
higher efficiencies as pulsed sieve trays. From
the results for two structured packings without
pulsation the positive influence of pulsing can
clearly be seen: The pulsed unstructured pack-
ing, Pall rings 15 × 15 mm, has a clearly smaller
load range.
In Figure 38, the range of loads is compared
for sieve trays and structured packings with pul-
sation [75]. According to that, packed columns
have significant advantages. As shown in [75],
the investment costs of pulsed structured packed
columns are 30 % lower than the ones of pulsed
sieve tray columns and 40 to 50 % lower than
pulsed unstructured packed columns.
Figure 38. Range of load of pulsed structured packed
columns in comparison to pulsed sieve tray columns in de-
pendence of the mass density difference for aqueous systems
and systems similar to water
In [76] a systematic study on extractor selec-
tion is given.
Adaptation of the Column Geometry to
the Separation Problem. In the early days of
extraction, various types of apparatus were re-
stricted to clearly defined geometries and were
thus sharply distinguished from one another. Re-
cent apparatus developments allow adaptation
Liquid – Liquid Extraction 35
of the column geometry to physical data, both
for pulsed columns and rotary-agitated columns.
The boundaries are thus no longer distinct and
a general fluid-dynamic description of related
types of apparatus is feasible. The optimization
of operating conditions and the geometry of the
internals is as equally important as the selection
of a suitable type of apparatus.
In practice the final selection of equipment
is often based on product-specific conditions or
plant requirements which include sensitivity to
solids, tendency of the product to polymerize,
and safety aspects, for example with regard to
solvent holdup.
Untypical Operating Conditions. Usually
extractors operate with nearly the same vol-
ume flow for both liquids and for liquids with
viscosities similar to that of water. Therefore,
the equations given before are only valid for
such conditions. Some approaches for untypical
operating conditions are given below.
Rauscher [62] investigated pulsed sieve tray
extractors with phase ratios between 0.06 and 10
and the liquid system n-butyl acetate (o) – water
(d) – methyl isopropyl ketone (MIPK), which
enriches MIPK in equilibrium preferable in the
organic phase. He confirmed the experience that
the separation efficiency declines for phase ra-
tios unequal 1 and found the following causes:
By dispersion of the smaller volume flow (phase
ratio  1), stronger backmixing of droplets by
the continuous phase will occur, leading to a
broader drop size distribution. By dispersion of
the larger volume flow (phase ratio  1), the
wake behind the drops causes remarkable back-
mixing of continuous phase. These phenomena
have to be taken into account by an adequate
calculation via drop population balances.
G. Wagner [58] investigated the fluid dy-
namics of pulsed sieve tray and Kühni rotating
extractors using liquid systems with viscosities
up to 50 mPa · s, mixed from paraffin oil and
n-hexane as organic phase and of glycerol and
water as aqueous phase. I. Wagner [77] con-
tinued the work with mass transfer investiga-
tions using the system tridecanol as drop phase
(η = 42 mPa · s), water, and propanol. The exper-
iments showed that the mean Sauter drop di-
ameter increases with increasing drop viscosity;
holdup is decreased, while the flooding curve
is shifted to higher throughputs. In case the
36 Liquid – Liquid Extraction
continuous phase is the more viscous one, the
drop swarm contains a larger fraction of small
droplets causing increased droplet entrainment
by the continuous phase. In stirred columns, the
drop size can be influenced in a broader range
than in pulsed columns; yet, more energy will be
required for a certain drop dispersion. Intensive
stirrers as in Kühni and QVF extractors should
be preferred to stirrers in RDC extractors.
In the case of a more viscous continuous
phase, the drop dispersion is nearly independent
of drop viscosity and is hardly influenced by the
rotating or pulsating internals. Here, lower in-
tensity dispersers are preferable, such as RDC
extractors.
The mass transfer to drops is distinctly de-
creased by increasing drop viscosity, developing
towards the state of transfer to rigid spheres, and
depends on the contact time. It can be improved
by suitable internals and by supply of energy.
4. Phase-Separation Equipment
4.1. Gravity Settlers without Inserts
Each extraction stage consists of two steps: (1)
dispersing and (2) phase separation by coales-
cence of drops, thus generating a homogeneous
layer of drop phase. Figure 39 A shows a vertical
settler at the top of a column for the case that the
drop phase has a lower density than the contin-
uous phase. The drops rise against the sinking
continuous liquid and are blocked by the upper
level of the continuous phase, which is the prin-
cipal interface. There, coalescence of the dis-
persed phase will occur both between adjacent
drops and at the principal interface. The coa-
lesced drop phase leaves the extractor at the top
of the column.
In a horizontal settler, as shown in Fig-
ure 39 B, both phases flow in the same direction.
Drops of lighter dispersed phase rise to the inter-
face where they coalesce to form a homogeneous
layer. In the lower part of the settler a layer of
the continuous phase remains, growing in flow
direction due to decreasing drop numbers. The
wedge-shaped zone of dispersion should end be-
fore the placement of phase outlets.
As the accumulation of impurities in tech-
nical liquid systems changes important proper-
ties such as viscosity and surface tension, an ex-
clusively theoretical modeling, as developed by
many authors (see for instance [80]), is insuffi-
cient. However, the length of a horizontal settler
can be estimated by a combined procedure of
calculations and simple and cheap batch settling
experiments [79]. The calculation is based on
a model of the physical processes in a settler,
while experiments supply one empirical param-
eter to include surface phenomena that could not
be modeled so far (see Figs. 40 and 41).
A glass cylinder as shown in Figure 40 A,
filled with about 1 L of the original liquid – liq-
uid system, is vigorously shaken for 1/2 to
1 min. After placing it in an upright position, the
heights of sedimentation and coalescence fronts
are measured in dependence of time as shown
in Figure 40 B for drops being lighter than the
continuous phase. The drops are banked up in
a dense layer if sedimentation is faster than the
drop coalescence. The curves of sedimentation
and coalescence meet each other at time t e when
all drops are coalesced. For a sufficient repro-
ducibility of measurements it should be made
sure that the glass flask is washed with deion-
ized water, that the distribution of drop sizes is
narrow and the temperatures of the liquid – liq-
uid system in the glass cylinder and the continu-
ous settler are equal [78]. Figure 37 C shows the
height H of the wedge-shaped zone between the
curves of sedimentation and coalescence.
The concept of settler dimensioning is shown
in Figure 41. All equations mentioned in the fol-
lowing are given in [79]. Settler dimensioning
starts with evaluation of settling experiments ac-
cording to Figure 41 A. The linear curve of sed-
imentation supplies the velocity of sedimenta-
tion; a model of drop swarm sedimentation sup-
plies the diameter of the starting drop swarm
[66]. The thickness of the dense layer of drops
follows from a balance of sedimenting and co-
alescing drops in time steps. The next stage
is calculation of drop deformation in vertical
steps [80]. This serves to calculate coalescence
times between drops and between drops and
their homophase, the former to determine the
drop growth, the latter to calculate the drop ho-
mophase formed by coalescence [80]. The coa-
lescence model contains a fitting parameter F p
to fit the calculated and measured coalescence
curve in Figure 41 B. This parameter is the link
between the settling experiment and the settler

Figure 39. Vertical (A) and horizontal (B) gravity settlers for drop separation from a continuous liquid
Figure 40. Experiments on batch settling
dimensioning; F p can be used for the settler cal-
culation, given in Figure 41 B.
The settler needs an inlet length L in which
can be calculated by a model equation in depen-
dence on settler diameter, operation parameters,
and the mean drop size at the settler inlet, coming
from the extractor outlet. For calculation of coa-
lescence in the dense drop layer the same equa-
tions that were modeled for the settling experi-
ment can be applied using the fitting parameter
F p derived from these experiments. The result
is the geometry of the wedge of dispersion, i.e.,
its height and length, which has to be taken into
account for dimensioning the settler.
This combined experimental and theoretical
procedure yields good results although the drop
distributions in the settling experiment and the
real settler are not the same. The extensive equa-
tion system needs computer aided solving. A
Liquid – Liquid Extraction 37
computer program is offered by [81]. A simpli-
fied method is given in [79].
4.2. Settlers with Coalescing Aids
Gravity settlers are often equipped with coalesc-
ing aids to fit a settler to special conditions of the
liquid system or of the operational behavior. In-
dustrially proven coalescing aids are inclined or
corrugated plates, fixed beds of small packings,
fiber beds, porous sintered materials, and mem-
branes. In some cases, when the drop sizes to
be settled are smaller than 1 µm or if surfactants
render the settling more difficult, centrifuges [6,
Chap. 8] or electrical fields must be applied [82].
The most important coalescing aids are inclined
packages of plain or corrugated plates and fiber
bed filters.
38 Liquid – Liquid Extraction
Figure 41. Dimensioning a continuous settler [79]
A) Evaluation of settling experiments; B) Fitting of measured and calculated curve
Inclined Plates. Figure 42 shows one possi-
ble arrangement of inclined plates in a horizon-
tal settler. Other plate configurations are possi-
ble. In any case, the feed has to be distributed
by a sieve plate at the settler entry over the
cross-sectional area, filled with inclined plates.
The plates shorten the sedimentation distance of
drops and provide a larger interfacial area for the
coalescence. The drops coalescing at the plates
form trickling films which flow off to the hor-
izontal, principle interface due to a hydrostatic
pressure difference. A plate material wettable by
the drop phase is a prerequisite. Several scien-
tific investigations and experiments with liquid
systems of a wide range of properties were made
during the 1970s and 1980s on the hydrodynam-
ics of inclined films and the coalescence of drops
at the film surface, these are summarized in [83–
86]. The main results are:
1) Thin laminar films should flow on the
plates, because the coalescence of drops is
promoted by the shear stress of film flow
near the plate; the larger the volume flow
of cocurrent continuous phase, the smaller
the film thickness and the better the coales-
cence.
2) The plate should be wettable by the drop
phase (advancing contact angle < 70◦ , re-
ceding contact angle > 15◦ ).
3) The drop swarm has to be distributed
equally over the width of plates.
4) Constructions that can thin the trickling
film increase the settler performance.

5) Short lengths of plates of about 400 mm are
sufficient for coalescence of drops riding on
the film.
6) The width bp of a plate can be calculated
by the empirical equation of the Reynolds
number of trickling film
0.19
Ref ≤ 80KL,d
 
Vd ∆ g sinα
bp = 0.03
(Ref kvd )3/2 ηd
with the liquid number of trickling film
σ 3 d d
KL,d =
gηd4 ∆
where α is the plate inclination, V d,1 = V d /n
the volume flow of dispersed phase on a
plate, and n the number of plates.
7) The optimum of plate inclination is within
the range 10◦ < α < 15◦ .
8) The distance of adjacent plates should not
be smaller than 30 to 40 mm in order not to
disturb film flow and drop coalescence.
9) The trickling film continuously carries sur-
factants to the outflow of a plate and thus
prevents their accumulation. Therefore sur-
factants hardly influence coalescence and
settling performance up to medium flow
rates of drop phase.
10) Under certain conditions, the drop coa-
lescence leaves very small droplets, so-
called secondary drops, due to partial coa-
lescence, which generate a droplet entrain-
ment at the settler exit. Its occurrence is pri-
marily a question of liquids involved, i.e.,
their viscosity ratio [86].
The coalescence time of secondary drops is
significantly higher than that of primary drops,
due to interfacial effects. Settling of secondary
drops requires other coalescers, for instance
membrane coalescers or centrifuges.
Fiber bed filters are built from short fibers
stuffed to rectangular mats or to disks of 15 to
25 mm thickness, held in a suitable support, or
from fiber fleeces as shown in Figure 43.
They have a definite, large voidage of about
95 %, nevertheless they are sensitive to solid dirt
particles in the liquid. The droplets couple to the
fibers while flowing through the fiber bed, suc-
ceeding drops coalesce with them and enlarge
Liquid – Liquid Extraction 39
the size of adhering drops until the liquid flow
pulls them out of the bed due to increasing flow
resistance. A fiber bed is able to enlarge the sizes
of incoming drops at least by one order of mag-
nitude so that they can coalesce in a subsequent
settler with their homophase. Fiber bed filters
are restricted to drop concentrations < 10 vol %
to avoid redispersion.
Rebelein [87], [88] and Magiera [89], [90]
defined heuristic rules for the design of fiber beds
on the basis of careful experiments with a broad
variation of parameters of influence:
1) Fiber materials as glass or stainless steel
with high energetic surfaces provide differ-
ent interaction sites (e.g., hydrogen bonds
and ion – dipole interaction) for the liquid
and improve the fiber bed performance com-
pared to materials with low energetic sur-
faces as for instance teflon. High energetic
surfaces improve the wetting properties of
the fibers.
2) The drop enlargement in a fiber bed de-
creases with increasing flow rate, i.e., with
superficial velocities > 1 cm/s.
3) Small fiber diameters of about 15 µm are fa-
vorable.
4) The bed depth required for coalescence in-
creases with the fiber diameter.
5) The concentration of droplets in the incom-
ing liquid hardly influences the bed perfor-
mance.
6) Best efficiency means a separation of about
95 % of incoming drops.
7) The larger the surface tension of the liq-
uid system, the better the separation perfor-
mance.
8) Smallest drop sizes that can be separated are
about 10 µm.
9) Presence of surfactants and mud and a higher
viscosity of the continuous phase reduce the
separation performance, the viscosity of the
drop phase has no influence within 50 and
5000 mPa · s.
All attempts to calculate the bed performance
in advance via filter coefficients were fruitless
[87–90]. Magiera developed a mathematical
model of physical mechanisms inside a fiber bed
and was able to simulate the bed behavior and
drop enlargement by introduction of two exper-
imental fitting parameters. Therefore, a reliable
dimensioning of fiber beds needs experiments
40 Liquid – Liquid Extraction
Figure 42. Horizontal gravity settler with two inclined packages of plane, parallel plates. The height of principal interface is
best situated, when both phases have the same exit velocity
Figure 43. Combined fiber bed coalescer and gravity settler
with the liquid dispersion which is to be sepa-
rated.
Figure 44. Membrane coalescer [91]
Membrane Coalescence. A new and very
promising method to separate fine droplets down
to 1 µm from emulsions, stabilized by surfac-
tants, was discovered and investigated by Hoff-
mann [91] (Fig. 44).
Membrane coalescers are applicable in a
broad range of volume concentrations down to a
lower concentration limit of the organic phase
(0.1 vol %). A thin, hydrophobic, stretched
membrane, for instance polytetrafluoroethylene
(PTFE), held in place by a support, is perme-
ated by two-phase flow of emulsion. The emul-
sion leaves the membrane as a liquid foam with
large oil domains which will immediately co-
alesce at the principle interface in a succeed-
ing settler. A superficial velocity through the
membrane is possible within the range of 0.1
to 19 cm/s, the pressure drop is comparable with
that in fiber beds. The main advantages are huge
separation performances of about 98 %, in com-
bination with a large range in throughput; the

ability to separate droplets one order of mag-
nitude smaller than in fiber beds; and the in-
sensitivity against hydrophobic surfactants. Hy-
drophilic surfactants are without influence, too,
if their amount is clearly lower than the critical
micelle concentration.
Selection of Appropriate Settler. Most im-
portant and the first step in selection of a settler
is a careful analysis of separation problems [78],
[92]. The flow sheet of the complete process can
give hints on origin and kind of the dispersion
to be separated. Sometimes the preceding steps
could be altered in order to simplify the phase
separation problem. Measurements of properties
of the liquid system and settling experiments in
a glass cylinder show, if and why a phase separa-
tion can be problematic. Drop sizes smaller than
100 µm need suitable coalescing aids which are
supposed to be well wettable by the drop phase.
When the drop settling in a glass cylinder is fast,
but the liquids appear cloudy, this indicates par-
tial coalescence, resulting in very fine drops, so
that a fiber bed or a membrane coalescer will be
necessary.
The presence of solid particles and mud re-
quires filters before the settler. The wetting
behavior of coalescing aids can significantly
change the operation of the process. This should
be accounted for in the procces. The phase ra-
tio can be changed by recycling of one phase to
the settler. By this, the type of dispersion can be
inverted. In case the organic phase has a higher
viscosity than the water phase, an o/w dispersion
separates much better than a w/o dispersion, and
vice versa.
5. Liquid – Liquid Extraction
Processes
5.1. General
The quality of the raffinate in liquid – liquid ex-
traction can be controlled easily by changing the
ratio of solvent to feed and the extraction tem-
perature. The quality of the extract is governed
only by the conditions of feed location and no
direct control is possible.
This is especially true because most extrac-
tions are carried out in a closed system to min-
imize solvent requirements. In such a system, a
Liquid – Liquid Extraction 41
maximum extract purity is obtainable and some
components that should end up in the raffinate
leave with the extract.
Additional steps are, therefore, required to
enhance extract purity and thus raffinate yield.
If the extract is the product desired, improving
extract purity is the most important – in fact,
the only – objective. Different solutions to this
problem are applied in commercial operation.
Change in Temperature. Extract purity can
be increased by cooling the extract from the
main system and adding one more stage (see
Fig. 45 A). In the triangular diagram, this means
that the binodal curve is changed from a to b
(Fig. 45 B).
Because the composition of the first extract
is now inside binodal curve b, it separates in a
settler b in a purer final extract phase and a small
amount of intermediate raffinate phase. The lat-
ter is returned to the main extraction system.
The selectivity of separation in the additional
stage is not very great because the loading of
the first extract phase is rather high and separa-
tion takes place near the plait point. This system
can be used when the main system is operated
at high temperature for other reasons or when
an increase in extract purity and the resultant
increase in raffinate yield are desirable.
Addition of Water. The addition of water at
or below the feed point generally changes the
system from a closed to an open one (see Sec-
tion 2.1.1.). In this way, extract purity can be
increased to the required level. Water is soluble,
at least to some extent, in most polar solvents
and therefore leaves the system with the final
extract phase. In this way, no unwanted influ-
ence is exerted on the main extraction system.
However, because water must be separated
from the solvent by distillation before its rein-
troduction in the main extractor, the heat require-
ments are high. Addition of water is, therefore,
not regarded as a generally attractive solution.
Also, water can only be added when its boiling
point is much lower than those of the solvent and
the feedstock.
Use of a Countersolvent. As shown in Fig-
ure 46, a second solvent can be fed into one end
of the extraction system, on the opposite side of
42 Liquid – Liquid Extraction

Figure 45. Use of cooling stage

A) Process flow scheme: a) Extractor; b) Settler
B) Triangular diagram: a) Binodal curve at higher temperature; b) Binodal curve at lower temperature

the solvent entry point. The feed in this case is
introduced somewhere in the middle of the sys-
tem.
Figure 46. Extractor for separation using a countersolvent
(a) Extractor
The countersolvent should be only slightly
soluble in the solvent and, therefore is generally
similar in chemical structure to the key com-
ponent of the raffinate phase. The boiling point
of the countersolvent should be such that it can
easily be separated by distillation from the sol-
vent as well as from the raffinate and the extract
(i.e., either a much lower or a much higher boil-
ing point). Because the countersolvent does not
contain any raffinate components when it enters,
it can wash out the raffinate components in the
solvent at the feed point.
Additionally, some extract components are
washed back by the countersolvent, thus increas-
ing the load in the top section. In this way, a very
pure final extract can be produced, depending on
the ratio of countersolvent to feed used.
A disadvantage of this system is that the coun-
tersolvent enters the top section. Consequently,
the phase ratio of B-rich to A-rich phase is re-
duced, resulting in a less pure raffinate (this also
means a lower yield of extract). To restore raffi-
nate purity, more B-rich phase must be applied.
Such a system is thus costly and sensitive to
changes in feed composition, solvent-to-feed ra-
tio, and ratio of countersolvent to feed.
Some improvement can be obtained by car-
rying out the extraction in two parts (Fig. 47).
In the first extractor (a), the feed is extracted
with the primary solvent. The intermediate ex-
tract phase is fed to a second extractor (c) and

brought in contact with the countersolvent. The
mixture of countersolvent and intermediate raf-
finate is fed to a column (b) in which the in-
termediate raffinate and the countersolvent are
separated by distillation. The pure intermediate
raffinate is then fed to the first extractor, while
the countersolvent is charged to the second ex-
tractor. In this way, some of the disadvantages
can be overcome.
Figure 47. Use of countersolvent with intermediate recov-
ery
a) First extractor; b) Distillation column; c) Second extrac-
tor
5.2. Combined Processes of Extraction
and Distillation
Azeotropic Distillation. Usually it is neces-
sary to combine extraction and distillation pro-
cesses for recovering the solvent from the ex-
tract phase and also from the raffinate phase, if
the solvent is soluble in the raffinate.
Figure 48 shows as an example the recovery
of acetic acid from an aqueous solution with
methyl tert-butyl ether (MTBE) as solvent. The
system of water and acetic acid is a highly non-
ideal azeotropic mixture that could be separated
by simple distillation. However, for dilute feed
compositions solvent extraction is more advan-
tageous because of the very high energy demand
of a water-rich feed distillation. The triangular
diagram of Figure 48 shows that the binary sys-
Liquid – Liquid Extraction 43
tem of solvent MTBE and water has a heteroge-
neous azeotrope. As a consequence, extraction
has to be combined with azeotropic distillation
as shown in the flow sheet of Figure 48 B. By
extraction in the extractor E extraction feed F
is changed to raffinate R and the solvent L1 to
extract phase F1, which on the other hand is the
feed of distillation column C-1. In C-1 the ex-
tract is split into the bottoms acetic acid B1 and
an acetic acid-free distillate D1 connected by
the main balance line of distillation in the trian-
gle diagram. The acetic acid-free raffinate R is
fed into column C-2 where it is separated into
the bottoms, pure water B2 and water – MTBE
azeotrope D2. Both distillates D1 and D2 lie
in the immiscible region between MTBE and
water. This makes simple decantation (S) of
the condensed phases possible. The solvent-rich
fraction L1 is not further purified since MTBE
as solvent needs not to be pure. So L1 can be
recycled directly to the extractor E, a part of it is
used as reflux for C-1. In column C-2 a mixture
of water and MTBE has been separated into pure
water and MTBE – water azeotrope. Therefore,
L2, the water-rich phase from the settler, can also
be fed into column C-2.
The economy of the hybrid process depends
on a careful optimization of operational and
constructional parameters, besides the careful
selection of the solvent. Recently, mixed inte-
ger nonlinear programming (MINLP) has been
successfully introduced in optimization of such
processes [93], [94]. MINLP can be used as a
process synthesis tool. It is necessary to gen-
erate a so-called superstructure of the hybrid
process which contains a variety of alternative
flow sheets. Then MINLP is able to choose the
best solution for given parameters and also from
competitive unit operations like extractive distil-
lation, processes with more than one solvent or
processes with reextraction for solvent recovery.
Extractive Distillation. Another possibility
to separate azeotropic mixtures is extractive dis-
tillation. A solvent with a much higher boil-
ing point than the feed is fed at the top of a
distillation column to entrain one component
of the distillation feed that enters the column
at the bottom (→ Distillation and Rectification,
Chap. 6.5.). The combined system of liquid – liq-
uid extraction and extractive distillation is ap-
plied in nearly all processes used to manufacture
44 Liquid – Liquid Extraction
very pure light aromatics. N-Formylmorpholine
is a suitable solvent to separate the light aro-
matics benzene and toluene used as feedstock
for the petrochemical industry [95–100]. Due to
the selectivity of N-formylmorpholine (NFM),
extremely high yields of very pure products are
obtained.
Figure 48. Triangular diagram (A) and flow sheet (B) of
a hybrid extraction – distillation process for separation of
water and acetic acid with MTBE as solvent [93]
E = extraction; C-1, C-2 = distillation; S = settling;
H = condenser
A simplified process flow scheme for N-
formylmorpholine extraction is given in Fig-
ure 49. Feed enters the extractor at an appro-
priate point in the bottom half of the column.
The exact location depends on the composition
of the feed and can be optimized for each feed-
stock. Solvent enters at the top of the extrac-
tor at the selected temperature. Because NFM
has a high solvent power, this must often be re-
duced by addition of water. In general, 4 – 10 %
water is sufficient to ensure a low solubility of
saturated hydrocarbons while still maintaining a
high solubility of aromatics. The raffinate phase
leaving the top of the extractor is saturated with
solvent. Washing with water has proved to be
a simple and effective means of recovering dis-
solved solvent. The water – solvent mixture from
this washing operation is charged to the bottom
of the main extractor to increase the water con-
tent of the solvent phase as discussed above.
The solvent – aromatics mixture from the bot-
tom of the extractor still contains some alkanes.
This stream is routed to an extractive distillation
column. In the lower part of this column, satu-
rated hydrocarbons are stripped off, which re-
sults in high-purity aromatics at the bottom. Be-
cause the volatility of alkanes in the presence of
NFM is much higher than that of aromatics, the
need for sharp separation is not very high. At the
top of the extractive distillation column, some
solvent is added. This solvent stream serves to
wash back any aromatics evaporated at the feed
point. The resulting top product, therefore, has a
very low aromatic content and is very effective
as a reflux in the bottom part of the extractor,
washing out the heavier alkanes.
The bottom product of the extractive distilla-
tion column, consisting of solvent and very pure
aromatics, is fed to a distillation column where
the aromatics are evaporated along with water.
The top product of this column is condensed and
fed to a settler. The extracted aromatics are avail-
able as product or can be routed to a distilla-
tion train to separate the individual compounds.
Some of the aromatics are returned to the top of
the distillation column as reflux. In this way, any
ascending solvent vapor is condensed and the top
products are solvent-free. The water layer from
the settler is used for raffinate washing. Some-
times, part of the water is used as reflux instead
of extract. In this combination, ultimate use is
made of the solvent characteristics in both the
extraction and the extractive distillation steps.
5.3. Reactive Extraction
5.3.1. Introduction
If the solvent reacts with the extracted substance
during the extraction, the whole process is called
reactive extraction. This reaction is normally
 Liquid – Liquid Extraction 45

Figure 49. Morpholine solvent process

a) Extractor; b) Washing; c) Extractive distillation column; d) Distillation column; e) Settler

used to alter the properties of inorganic cations tance. The mechanism of this type of reaction
that are to be extracted from an aqueous solu- proceeds most of the time through ion pair for-
tion to make them soluble in the nonpolar or- mation and can best be compared with an anion
ganic solvent. The reaction mechanism can best exchange process.
be compared with a cation exchange process. A third possible mechanism is the solvating
The solvent acts like a liquid ion exchanging the and/or chelating reaction. In a reaction of this
ion to be extracted for protons. type, one or more molecules of water in the hy-
Table 1. Commercial chelating extraction reagents
drate layer of the ions are replaced by the active
solvent. The new complex will be insoluble in
Name Producer Chemical composition water but soluble in the solvent.
LIX 63 Henkel 5,8-diethyl-7-hydroxy-6-dodecanone Generally, the formation of a complex is a
oxime slow reaction. Therefore, in many cases, it is
LIX 64 Henkel 2-hydroxy-5-dodecylbenzophenone oxime not possible to use columns for this type of ex-
LIX 64N Henkel LIX 65N with added LIX 63 (promoter)
LIX 65N Henkel 2-hydroxy-5-nonylbenzophenone oxime traction. In many applications mixer – settler are
LIX 70 Henkel chlorinated LIX 65 N with added LIX 63 used to make the extraction possible.
(promoter) A reactive extraction will need a re-extraction
LIX 71 Henkel mixture of LIX 64 N and LIX 70
LIX 73 Henkel mixture of LIX 64 N and LIX 70
to isolate the extracted substance from the sol-
LIX 34 Henkel 8-(p-dodecylphenyl sulfonamido)quinoline vent. The active solvents used in reactive extrac-
LIX 54 Henkel acetyl-p-dodecyl acetophenone tions are water insoluble compounds. They are
LIX 622 Henkel used undiluted or in solution in an inert solvent.
LIX 6022 Henkel
SME 529 Shell 2-hydroxy-5-nonylacetophenone oxime
SME 530 Shell SME 529 with kinetic modifier
P 17 Acorga phenyl benzyl ketone oxime 5.3.2. Extraction Mechanism of Different
P 50 Acorga substituted salicyl aldoxime Types of Solvent
P 5100 Acorga one part P 50 with equal part nonylphenol
P 5200 Acorga one part P 50 with two parts nonylphenol Classical Complexing and/or Chelating
P 5300 Acorga one part P 50 with three parts nonylphenol
Agents. The active solvents are usually large,
P 5050 Acorga two parts P 50 with one part tridecanol
Kelex 100 Sherex substituted 8-hydroxyquinoline with 10 % polyfunctional molecules. Most of them are de-
isodecanol signed to extract specific cations. Dioximes, hy-
Kelex 120 Sherex similar to Kelex 100 but with 20 % droxyoximes, quinolines, β-diketones, etc., are
isodecanol
rather expensive but widely used solvents to ex-
The use of this process for extraction of an- tract metal ions such as copper and nickel from
ions is far less known but is of the same impor- the aqueous phase.
46 Liquid – Liquid Extraction
Metal complexes are formed in the water
phase in a substance-specific pH range and ex-
tracted into an inert solvent. After extraction
the metal ion is liberated from the complex by
changing the pH, and re-extracted into the water
phase. The complexing/chelating agents are de-
signed such that they are chemically stable, non-
toxic, and insoluble in water to minimize losses.
The liquid ion exchange (LIX) [5] agents used
in the production of copper are typical for this
category.
Henkel, Hoechst, Shell, Sherex, and
Acorga are the largest producers of complex-
ing/chelating extractants (see Table 1).
Phosphoric, Sulfonic, and Carboxylic
Acids. This class of products acts typically as
cation exchangers in solution. The products have
one or more protons that can be exchanged for
metal ions.
Naphthenic acids Versatic acids
Sulfonic acids Phosphoric acids
Thiophosphoric acids Phosphonic acids
The metal salts of these acids are soluble in
most nonpolar solvents and, depending on the
pH of the extraction and the pK a of the acid,
the cation will migrate to the organic phase or
stay in the water phase. The dependence of the
distributions coefficients on pH is shown in Fig-
ure 50.
The different curves give the variation of the
distribution coefficient D in dependence of pH
for different cations. These solvents are not spe-
cific for certain cations, but are very suitable to
concentrate and recuperate trace elements from
effluent streams [109], [110].
The major producers of this type of com-
pounds are Bayer, Hoechst, Daihachi, Shell, and
Albright & Wilson.
Ethers and Thioethers.
R2 O + HX
R2 OH+ + X−
R2 S + HX
R2 SH+ + X−
where HX stands for a strong acid, e.g., H2 SO4
or HCl, and X is the anionic rest of the acid.
Most metal ions that are capable of forming an-
ionic complexes are extractable with ethers and
thioethers. Fe, Au, In, Ga, etc. can be extracted
with these solvents from an aqueous HCl solu-
tion (HCl concentration > 6 M) and re-extracted
from the organic phase with water. Most of these
anionic complexes form strong acids which pro-
tonate with the ether group to form oxonium
(thionium) salts. These salts, however, are sol-
uble in ether or thioether. It is also possible to
extract Cl− from water with (R2 O)2 · H2 SO4 ,
the sulfate ion being replaced by the chloride.
This type of solvent is normally used in undi-
luted form [106].
Ketones extract the same anionic complexes
as ethers, but in most cases at lower acid
concentration. Complexes with weaker acids
can also be extracted. Methyl isobutyl ke-
tone and cyclohexanone are industrially used
in the separation of Nb – Ta as F− complexes
[112] (→ Niobium and Niobium Compounds,
Chap. 4.3.1.) and in the separation of Zr – Hf as
CNS− complexes (→ Zirconium and Zirconium
Compounds, Chap. 1.4.2.) [116]. The solvents
are used in undiluted form. A great disadvan-
tage of this and of the former type of solvents is
that they are not completely insoluble in water.
A distillation is needed to remove the dissolved
solvent from the water phase.
Trialkylphosphine oxides, Trialkylphos-
phinates, -phosphonates, and -phosphates.
R3 PO + HX
R3 POH+ + X−
ROR2 PO + HX
ROR2 POH+ + X−
(RO)2 RPO + HX
(RO)2 RPOH+ + X−
(RO)3 PO + HX
(RO)3 POH+ + X−

Figure 50. Plots of log D vs. pH for extraction of metals
With this type of extractants most metals from
group 3 to group 8 can be extracted, even if only
weak complexes are formed with the solvent.
It is for example possible to extract TiOSO4
[114] from a sulfuric acid solution with dibutyl
butylphosphonate (DBBP) as the solvated com-
plex 2 DBBP · TiOSO4 · H2 SO4 · 5 H2 O. These
organophosphorus solvents are, due to their out-
standing chemical stability and good physical
properties, most widely used in reactive extrac-
tion [107], [108].
Free acids can also be extracted, the basic-
ity of the solvents decreases from phosphine
oxide to trialkylphosphate. The distribution co-
efficients are rather small so that large volumes
of solvent are needed in an extraction process
[104], [105], [111]. These extractants are used
as such or diluted in an inert solvent (petroleum
fraction) with or without modifier. The distribu-
tion coefficients in metal extraction are usually
very high and depend on the acid concentration.
The products are rather expensive.
Bayer, Hoechst, Daihachi, Shell, and Al-
bright & Wilson are the major producers.
Trialkylsulfonium (Selenium, Tellurium),
Tetraalkylammonium, and Tetraalkylphos-
phonium (Arsonium, Stibonium) Salts.
[R4 N+ A− ]Solvent + [B− ]Raffinate

[R4 N+ B− ]Solvent + [A− ]Raffinate
These onium compounds form ions both in
acidic and basic medium. The mechanism of
extraction is practically always anion exchange
[106]. The onium compounds are regenerated in
the same way as anion exchanger resins by re-
extraction with a base. These solvents are used
Liquid – Liquid Extraction 47
Producers are Henkel, Sherex, Hoechst, and
BASF.
Amine and Phosphine Salts.
R3 N + HX −→ R3 NH+ + X−
R3 P + HX −→ R3 PH+ + X−
Primary, secondary, and tertiary amines must
be protonated, thus converted to the ionic form
before they can be used as an ion exchanger.
Thus acids can be extracted with free amines,
metals have to be transformed to the corre-
sponding acids: vanadium can be extracted as
HVO3 , chromium as H2 Cr2 O7 , and manganese
as HMnO4 . Most used are the tertiary amines be-
cause they are chemically inert to most reagents.
In the system trilaurylamine – citric acid a
reversible extraction can be set up, due to the
difference in distribution coefficient at differ-
ent temperatures. At low temperature (20 ◦ C),
the distribution coefficient solvent/raffinate is
> 10. At high temperature (130 ◦ C), the coeffi-
cient for the same system is < 1. Thus, the acid
can be extracted from water at low temperature
and re-extracted with water at high temperature.
Much less accounted for is the fact that these
amines have very different distribution coeffi-
cients for different anions.
[R3 NH+ A− ]Solvent + [B− ]Raffinate

[R3 NH+ B− ]Solvent + [A− ]Raffinate
For trioctylamine in an aromatic solvent the or-
der of extractability is
in the production of Cr, V, Re, Tc, Mo, and W I− Br− > NO−
3 > Cl
−

as a solution in a petroleum fraction. F− > S2 O2− 3− 2−

3 > PO4 > SO4
48 Liquid – Liquid Extraction
This series is dependent on the type of amine,
the diluent, and the temperature and must be de-
termined for any given system [5]. This series
can be enlarged for organic compounds, capa-
ble of forming ion pairs with the amine. Phenols
and substituted phenols can be extracted with
better distribution coefficients than chlorides. In
this series thiophenols and some mercaptans are
situated between bromide and nitrate and all sul-
fonic acids are better extracted than phosphate.
This makes the sulfate salts of amines a very
good choice for new extraction systems.
(R3 N)2 · H2 SO4 (R = octyl) is capable of ex-
tracting Cl− and/or NO− 3 [113] from a mixture
of both anions with SO2− 4 . The value of the dis-
tribution coefficient of the anions is surprisingly
high.
DCl /DSO4 ≈ 100
DNO3 /DSO4 ≈ 400
A disadvantage of these solvents is the fact that
per mole amine one mole of salt is formed af-
ter regeneration. However, most of the time, the
anions to be removed are present in the solu-
tion only as trace impurities, so that this draw-
back is not significant. Another disadvantage
of amines is the poor solubility of ammonium
salts in aliphatic hydrocarbons. To avoid third
phase formation, the use of aromatic solvents
(smell) or aliphatics with modifiers is necessary.
Amines can also act as solvating agents in an
acid medium. Iron, zinc, and uranium salts can
be extracted in this way [106].
5.3.3. Uses
1) A bleed from a (NH4 )2 SO4 crystallization
unit in a caprolactam plant contains 40 %
(NH4 )2 SO4 , 10 % NO− 3 , 50 ppm Cl
−
and
3 – 4 % organic sulfonic acids. The solu-
tion is extracted by trioctylammonium sul-
fate, the added amount is stoichiometric
to [NO− −
3 ] + [Cl ] + [sulfonic acid]. In three
stages > 99 % of the nitrate, 90 % of the
chloride, and 85 % of the sulfonic acids are
extracted by the trioctylamine in solution
(40 %) in Shellsol AB (aromatic hydrocar-
bon). The raffinate is returned to the crystal-
lization plant for (NH4 )2 SO4 recovery. The
re-extract contains 35 % of nitrate, 0.016 %
of chloride, the sulfonic acids, and only
0.1 % of sulfate and is treated separately.
Compared with a conventional stripping, the
use of chemicals in this system is strongly
reduced. 80 % less NaOH is consumed be-
cause the base is only used to liberate the
amine and not to neutralize the NH3 from
(NH4 )2 SO4 [113].
2) Traces of phenol (20 – 200 ppm) and bisphe-
nol (20 – 100 ppm) can be extracted from
the wastewater of a polycarbonate plant to
values < 1 ppm, thus avoiding biological
treatment of the water. The re-extract con-
taining sodium phenolate and bisphenolate
(300 – 500 times more concentrated) can be
returned to the polycarbonate plant. The sol-
vent used is 5 % trioctylamine in Shellsol AB
[117].
3) From a plant for the production of vulcan-
ization accelerators 2-mercaptobenzothiazol
(100 – 300 ppm) and its oxidation products
are completely extracted in two stages and
re-extracted as a 20 – 30 % solution. This
concentrated waste can be easily removed.
The solvent is 20 % trioctylamine in Shell-
sol AB [113].
4) Bromide ions can be extracted selectively
from sea water (concentration in the Dead
Sea ≈ 4 %) with amine hydrochlorides and
concentrated in a re-extraction step, thus
avoiding the energetically unfavorable strip-
ping of sea water. The extraction can be car-
ried out with various types of amines as HCl
or H2 SO4 salt [106].
5) Mg2+ can be removed from a saturated so-
lution of (NH4 )2 SO4 by extraction with the
ammonium salt of diethylhexyl phosphonic
acid (DEHPA) at pH > 5. It can be recovered
by lowering the pH to < 3 [115].
6) Traces of uranium are extracted from phos-
phate ores. The uranium content in these ores
is only 30 – 300 ppm. The reserves of those
ores are so huge that the quantity of uranium
from phosphates many times exceeds that of
uranium found in other uranium ores.
7) Lanthanides and actinides have only recently
become available in higher quantity and high
purity. This was enabled by the development
of the extraction technology (→ Rare Earth
Elements).

8) Worldwide about 40 % of the copper is pro-
duced by reactive extraction. The plants are
an order of magnitude larger then any other
type of solvent extraction presently in oper-
ation (→ Copper, Chap. 5.8.). With an aque-
ous feed of 200 – 3000 m3 /h a whole new
technology had to be developed. Copper can
be extracted after acid or ammoniacal leach-
ing. The aqueous stripping phase is used di-
rectly in the electrowinning of copper. To
avoid the build-up of impurities in the elec-
trolysis of copper, Fe, Zn, and other metals
are removed from this phase by extraction
with other solvents [5], [102], [111].
9) More than 90 % of the world production of
cobalt is performed by reactive extraction.
Separation of Co and Ni can be achieved
from alkaline, neutral, or from acidic media.
Most of the impurities (Sn, Bi, Fe, Pb, Cu,
Cd, and Zn) have to be removed from the so-
lution by precipitation or extraction. From a
medium concentrated aqueous chloride solu-
tion (100 – 200 g/L), Co can be extracted by
amines together with only traces of Ni. After
scrubbing with 4 – 5 M HCl, most of the Ni
is removed from the solvent. The cobalt is
stripped by water.
From neutral or weakly acidic media (pH
4.8 – 5.5) Co can be extracted by the Na+
or NH+ 4 salt of di-2-ethylhexylphosphoric
acid (D2EHPA) (to avoid acidification of the
aqueous solution). Some Ni is co-extracted
and is removed by scrubbing with a Co solu-
tion thus replacing any extracted Ni by Co.
Co is finally stripped by HCl, H2 SO4 , or
HNO3 depending on the use.
The use of monooctyl octylphosphonic acid
(MOOP) to replace D2EHPA [101] permits
the same separation, but at lower pH and with
enhanced distribution constants for Co.
In alkaline solution Co and Ni can be ex-
tracted by LIX agents from ammoniacal so-
lution. Prior to the extraction, cobalt is ox-
idized to the Co3+ state. Nickel is stripped
first with dilute acid, Co remaining in the
solvent. Cobalt is then reduced to the Co2+
state and stripped with diluted acid [5], [102],
[104], [105].
All these examples are used in industry or in
pilot plants. Elaborate process and flow control
Liquid – Liquid Extraction 49
are essential to use this technology in a econom-
ical and meaningful way.
5.3.4. Setting up an Extraction System
A solution R contains three components: acid,
metal A and metal B. Both metals and the acid
are extractable with a solvent S and metal A is
the desired component that is to be obtained in
acid solution. The procedure to set up a new ex-
traction system with these data is typical for any
reactive extraction system [114], [118].
The distribution coefficients are to be mea-
sured at different acid concentrations at a tem-
perature suitable for the extraction. A typical
measurement curve is shown in Figure 51.
Figure 51. Distribution coefficient in dependence on acid
concentration
The diagram shows a poor, practically con-
stant distribution coefficient D for the acid and
an increasing one for both metals A and B at
increasing acid concentration.
This means that the acid extraction is in fact a
normal physical extraction and that both metals
form solvation complexes. At any acid concen-
tration, all three components are extracted to-
gether. The extraction coefficients E are related
in the same way as are the distribution coeffi-
cients,
E = D·S /R.
To extract metal A completely and in a reason-
able number of steps extraction has to be carried
out in zone 4 of Figure 51, the extraction zone.
At the same time, metal B and the acid are only
partially extracted into the solvent. The num-
ber of steps can be calculated with the Kremser
formula. The Kremser formula calculates the ef-
ficiency Z in the extraction



Z = E n+1 − E / E n+1 − 1
50 Liquid – Liquid Extraction
over n stages. For this equation the number of
stages can easily be calculated
n = log {[1/ (1 − Z) · (1 − 1/E)] + 1/E} /logE
To remove metal B from the solvent the solvent
has to be washed with water or acid in such a way
that most of metal A stays in the solvent, while
metal B is washed out as completely as possible.
This is done in zone 3 of Figure 51, the scrubbing
zone. The amount of water to be used is given
again by the distribution coefficients of both acid
and metal B. If too much acid is removed, metal
A will also be washed out. Therefore it is more
adequate to use an acid solution. The concen-
tration of the dilute acid should be such that the
acid solution can only take up the amount of
acid to be removed from the solvent. By scrub-
bing with pure water only a limited amount of
scrubbing fluid can be used because of the low
distribution coefficient of the acid. By adding a
calculated amount of acid the amount of scrub-
bing fluid can be increased and more component
B can be removed without removing component
A. The raffinate, leaving the scrubbing zone con-
tains too much of metal A to be discarded and
is sent back to one of the steps in the extraction.
The number of steps can again be calculated with
the Kremser formula.
In zone 2 of Figure 51, the stripping zone,
metal A is washed out of the solvent with water
or a dilute acid solution. The amount of water is
chosen such as to obtain the desired concentra-
tion of metal A in the re-extract. With the given
distribution coefficient, it is not possible to re-
move metal A completely form the solvent. At
any acid concentration, traces of metal A will
remain in the solvent.
In zone 1 of Figure 51, the washing zone, the
acid and the rest of metal A are washed out of the
solvent. After this step, the solvent is completely
regenerated and can be reused.
General Flow Sheet. Figure 52 shows a
general flow sheet of a reactive extraction sys-
tem.
Solvent Make-Up. Due to the poor distribu-
tion coefficient of the acid several extraction
steps are needed to load the solvent with suffi-
cient acid to make extraction of the metals pos-
sible. In the given example the acid comes from
the initial solution. To avoid losses of metal A,
the solvent must be completely free of A. At
the low acid concentration in the first steps of
the solvent make-up any metal A present in the
solvent will be re-extracted in the raffinate.
Reactive Extraction. If sufficient acid is
present in the solvent, both metals will be ex-
tracted from the feed solution. To limit the num-
ber of steps in the extraction, concentrated acid
is added. The high concentration is necessary for
the metal extraction and in the solvent make-up.
Solvent Scrubbing. To make sure that most of
metal B is washed out from the solvent, the acid
solution containing metal A and acid from the
solvent washing step is used, so that we stay in
the extraction zone for metal A. The second com-
ponent, with a lower distribution coefficient, is
already in its stripping zone and will be washed
out of the solvent. To avoid losses, this stream is
sent back to one of the steps in the extraction.
Solvent Stripping. After scrubbing, the sol-
vent contains only metal A and acid. Using water
or a dilute acid solution, the purified metal A can
now be re-extracted into a water phase.
Solvent Washing. The solvent must be com-
pletely regenerated before it can be recycled to
the solvent make-up. This is done by adding
some supplementary washing steps to the sys-
tem. The amount of water is chosen according
to the requirements in the scrubber and the num-
ber of steps is calculated as a function of that
amount.
5.3.5. Diluents and Modifiers
Diluents are used to reduce the solvent viscosity,
improve phase separation, and most of all, when
properly chosen, to reduce the loss of solvent.
The solubility of tri-n-butyl phosphate (TBP, one
of the most frequently used extractants) in pure
water is 420 mg/L at room temperature; a 50 %
dilution of TBP in n-hexane lowers this solubil-
ity to 175 mg/L. The choice of diluent is very
important. Higher amines are completely solu-
ble in aliphatic diluents. Their salts, however,
are only slightly soluble in the same solvents.
Therefore it is essential to test the solutions in
all steps of the process. If third-phase forma-
tion occurs in one of the steps, the diluent must
be changed or a modifier is to be added. These
modifiers are normally long chain alcohols, mo-
noesters of polyhydric alcohols, or phosphate

Figure 52. General flow sheet of a reactive extraction system
esters. These modifiers may considerably influ-
ence the kinetics of the extraction. Especially in
the extraction of copper the choice of modifier
is very important. The different types of solvent
are sold mixed with a suitable modifier which
greatly enhances the extraction performance of
the solvent.
6. References
1. R. E. Treybal: Liquid Extraction,
McGraw-Hill, New York – Toronto – London
1963.
2. S. Hartland: Counter Current Extraction,
Pergamon Press, Oxford 1970.
3. J. Rydberg, C. Musikas, G. R. Choppin (eds.):
Principles and Practises of Solvent Extraction,
M. Dekker, Inc., New York 1992.
4. C. Hanson: Recent Advances in Liquid – Liquid
Extraction, Pergamon Press, Oxford 1971.
5. T. C. Lo, M. H. I. Baird, C. Hanson (eds.):
Handbook of Solvent Extraction,
Wiley-Interscience, New York 1983.
6. J. D. Godfrey, M. J. Slater (eds.):
Liquid – Liquid Extraction Equipment, J.
Wiley & Sons, New York 1994.
7. J. Wisniak, A. Tamir: Liquid – Liquid
Equilibrium and Extraction. A Literature
source Book. Physical Sciences Data, 7, Part A
1980, Part B 1981, Physical Sciences Data, 23,
Supplement 1 1985, Elsevier, Amsterdam.
8. Proceedings ISEC ’88, Vernadsky Institute of
Geochemistry and Analytical Chemistry of the
USSR Academy of Sciences, 4 vols., NAUKA,
Moscow, 1988.
Liquid – Liquid Extraction 51
9. Proceedings ISEC ’90, Chemical Society of
Japan, Elsevier, New York 1992.
10. Proceedings ISEC 71, The Hague, 2 vols.,
Society of Chemical Industry, London 1971.
11. Proceedings ISEC 74, Lyon, 3 vols., Society of
Chemical Industry, London 1974.
12. Proceedings ISEC 77, Toronto, 2 vols., CIMM
Special Publication, no. 21, Can. Inst. Min.
Met., 1979.
13. Proceedings ISEC 80, Liège, 3 vols., Assocn.
des Ingenieurs sortis de l’Université de Liège,
Liège 1980.
14. Proceedings ISEC 83, Denver AIChE 1983.
15. Proceedings ISEC 86, München, 3 vols.,
DECHEMA, Frankfurt 1986.
16. Proceedings ISEC ’93, Solvent Extraction in
the Process Industries, 2 vols., Elsevier, New
York 1993.
17. Proceedings ISEC ’96, Value Adding Through
Solvent Extraction, 2 vols., The University of
Melbourne, Parkville, Victoria, Australia 1996.
18. J. M. Sorensen, W. Arlt: “Liquid – Liquid
Equilibrium Data Collection,” vol. V, part
1 – 3, DECHEMA Chemistry Data Ser.,
Frankfurt 1979.
19. Landolt-Börnstein: II 2 c, Springer Verlag,
Berlin 1980.
20. O. Madelung: Landolt-Börnstein directory
disk 1.1, Springer-Verlag, Berlin 1994.
21. A. Seidel, F. W. Linke: “Solubilities of
Inorganic and Organic Compounds,” in A. W.
Francis (ed.): Ternary Systems Separating into
Two Liquid Layers, van Norstrand, London
1952.
22. A. W. Francis: Liquid – Liquid Equilibria,
Wiley, New York 1963.
52 Liquid – Liquid Extraction
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