Liquid-Liquid Extraction: Ckart Ller Osemarie Erger Ckhart Lass Omien Luyts Ndreas Fennig

2012 Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim
LiquidLiquid Extraction
ECKART M uLLER, Frankfurt a. Main, Germany
ROSEMARIE BERGER, Ludwigshafen, Germany
ECKHART BLASS, Technische Universitat Munchen, Munchen, Germany
DOMIEN SLUYTS, Bayer AG, Antwerpen, Belgium
ANDREAS PFENNIG, RWTH Aachen University, Aachen, Germany
1. Fundamentals and Fields of Application . . 250
2. Thermodynamic Fundamentals . . . . . . . . . 252
2.1. Graphic Representation of Phase Equilibria 252
2.1.1. Triangular Diagrams . . . . . . . . . . . . . . . . . . 252
2.1.2. Other Graphic Representations . . . . . . . . . . . 254
2.2. Measuring Methods of Phase Equilibria . . 256
2.3. Correlation of Phase Equilibria. . . . . . . . . 257
2.4. Selection of Solvent . . . . . . . . . . . . . . . . . . 257
2.5. Determination of Mass-Transfer
Performance . . . . . . . . . . . . . . . . . . . . . . . 259
2.5.1. Specic Methods for Determining the
Theoretical Number of Stages . . . . . . . . . . . 261
2.5.2. Determining Equipment Behavior Based
on Drop-Population Balances . . . . . . . . . . . . 264
2.5.3. Evaluation of Stage-Number Calculation for
Process Design . . . . . . . . . . . . . . . . . . . . . . 266
3. Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . 267
3.1. Survey . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
3.1.1. Columns without Energy Input. . . . . . . . . . . 267
3.1.2. Pulsed Columns. . . . . . . . . . . . . . . . . . . . . . 268
3.1.3. Columns with Rotating Internals . . . . . . . . . 271
3.1.4. Mixer Settlers. . . . . . . . . . . . . . . . . . . . . . 272
3.1.5. Centrifugal Extractors . . . . . . . . . . . . . . . . . 274
3.2. Fluid-Dynamic Fundamentals . . . . . . . . . . 275
3.2.1. Problems and Process Strategy. . . . . . . . . . . 275
3.2.2. Operating Characteristics of Pulsed Columns
and Columns with Rotating Internals . . . . . . 276
3.2.3. Fluid Dynamic Calculation Methods. . . . . . . 278
3.3. Apparatus Design . . . . . . . . . . . . . . . . . . . 281
3.3.1. Internals and Operating Conditions. . . . . . . . 282
3.3.2. Column Diameter . . . . . . . . . . . . . . . . . . . . 283
3.3.3. Column Height . . . . . . . . . . . . . . . . . . . . . . 283
3.4. Criteria for Equipment Selection. . . . . . . . 284
4. Phase-Separation Equipment. . . . . . . . . . . 288
4.1. Gravity Settlers without Internals . . . . . . . 288
4.2. Settlers with Coalescing Aids. . . . . . . . . . . 289
5. Liquid Liquid Extraction Processes . . . . 294
5.1. General . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
5.2. Combined Processes of Extraction and
Distillation . . . . . . . . . . . . . . . . . . . . . . . . . 295
5.3. Reactive Extraction . . . . . . . . . . . . . . . . . . 297
5.3.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . 297
5.3.2. Extraction Mechanism of Different Types of
Solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
5.3.3. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
5.3.4. Setting up an Extraction System. . . . . . . . . . 302
5.3.5. Diluents and Modiers. . . . . . . . . . . . . . . . . 303
References . . . . . . . . . . . . . . . . . . . . . . . . . .303
Article No : b03_06
Symbols
a: Pulsing amplitude (between top and
bottom dead point of motion), m
A: key component of the phase from
which the solute is extracted
B: key component of the phase into
c
i
: constants
C: transferred component
d
i
: hole or packing diameter, m
d
p
: particle diameter, m
d
32
: Sauter mean drop diameter, m
D: column diameter, m
D
R
: rotor diameter, m
D: distribution coefcient
E =
K m_
s
/m_
F
: extraction factor
f: pulsing frequency, s
1
g: acceleration due to gravity, m/s
2
G
i
: coefcients in empirical correlations
of the distribution coefcient
h: compartment height, m
H: height of column, m
HETS: height equivalent of a theoretical
stage, m
k = y
c
/x
c
: distribution ratio of transferred
component (in terms of mass
fraction)
DOI: 10.1002/14356007.b03_06.pub2
1. Fundamentals and Fields of
Application
Liquid liquid extraction or solvent extraction
is a separation process which is based on the
different distribution of the components to be
separated between two liquid phases. It depends
on the mass transfer of the component to be
extracted froma rst liquid phase to a second one.
Denitions. The phases form denite con-
tact areas and cannot or can only to a limited
extent mix with one another on account of their
properties. The phases are composed of individ-
ual substances, so-called components, and ow
as liquid streams through the extractor (see
Fig. 1).
Generally, more than three components are
involved in an extraction. To make the descrip-
tion of the problem simpler, key components are
dened. 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 substance C
from the feed. The solvent can be the pure
K =
Y
C
/X
C
: distribution ratio of transferred
component (in terms of loading)
K
p
: plait point
m
j k
: mass of component j in phase or ow
k (j = A, B, C; k = F, R, S, E), kg
m
k
= m
Ak
m
Bk
m
Ck
:
total mass of phase or ow k (k = F,
R, S, E), kg
m_: mass ow, kg/h
n
s
: revolutions of stirrer, s
1
n: number of stages
NTS: number of theoretical stages
s: column cross section, m
v: supercial velocity, m
3
m
2
h
1
or
m/s
v =
m_
S
/m_
F
: extractant ratio
v
p
: individual drop velocity, m/s
v
r
: slip velocity (Eq. 9), m/s
x
C
: mass fraction of C in A-rich phase
X
C
=
x/(1 x): loading of A-rich phase with com-
ponent C, kg/kg
y
C
: mass fraction of C in B-rich phase
Y
C
=
y/(1 y): loading of B-rich phase with C, kg/kg
Greek symbols
e: holdup, m
3
/m
3
h: dynamic viscosity, Pa s 10
3
r: density, kg/m
3
s: interfacial tension, N/m 10
3
j: fraction of free area
Dimensionless Groups
Ar = d
3
P
gr
c
Dr=h
2
c
:
Archimedes number
Fr
R
= N
2
D
R
=g:
Froude number
Re
p
= y
p
d
p
=y
d
:
Particle Reynolds number
K
L
= r
2
c
s
3
=(Drgh
4
c
):
Characteristic number of liquid
Subscripts
A: key component of the phase from
B: key component of the phase into
C: transferred substance (solute)
c: continuous phase
d: dispersed phase
E: extract
f: ooding
F: feed
i: internals (characteristic size)
o: organic
p: drop (particle)
R: rafnate
S: solvent
1: pilot scale
2: large scale
250 LiquidLiquid Extraction Vol. 21
component, B, but usually contains small
quantities of C and A, because the solvent is
usually recycled from a recovery system. The
solvent phase leaving the extractor is the extract.
The extract contains mainly B and the extracted
component C but also small quantities of A. The
rafnate 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
solvent B.
Comparison with Distillation. Liquid
liquid 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 newsubstance, 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 separated
fromthe 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 reux for the
extraction, e.g., extractive distillation (extrac-
tion of aromatic compounds, see Section 5.2) or
azeotropic distillation (extraction of acetic ac-
id). In the extraction of metal salts (see Section
5.3) the purity is often achieved by adjusting the
pH. Extraction is an isothermal process, nor-
mally carried out at ambient temperature and
pressure.
Comparison with Absorption. In both
absorption and extraction solvents are used
which are recycled and thereby take up the re-
quired components selectively and then release
them again. Selection of the most suitable
solvents therefore plays an important role in the
design of the two separation processes.
Applications of Liquid Liquid Extrac-
tion. Liquid liquid extraction is primarily
applied 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 high boilers and low-
concentration solutes from aqueous solu-
tions (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).
It is expected that the importance of solvent
extraction will increase as the feedstock of
chemical processes changes from crude oil to
biomass. The components obtained in the rst
processing steps from biomass have more
functional groups and are less volatile than
the key components obtained from crude oil.
Figure 1. Principles of extraction streams, phases and
components
Vol. 21 LiquidLiquid Extraction 251
Thus, it may be economically more attractive
to use extraction with suitable solvents
(including newly proposed extractants like
ionic liquids) than to use distillation at low
pressure.
Processes applied today in the petroleum in-
dustry, in metal-salt extraction, and in chemical
and biochemical processes are described in
Chapter 5.
Only a general outline is given in this article.
For further details, the reader is referred to books
[18] and the Proceedings of the International
Solvent Extraction Conference (ISEC) [921].
Data of liquid liquid equilibria can be found in
[22, 23] and [24].
2. Thermodynamic Fundamentals
A comprehensive treatment of the thermody-
namic fundamentals of phase equilibria is given
elsewhere ( Absorption, 1. Fundamentals;
Distillation, 1. Fundamentals).
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 triangle
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 corner which
represents the pure component, from 0 kg/kg at
this opposite side to 1 kg/kg at the corner. 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 inserted 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 composi-
tion 0.5 kg/kg C, 0.2 kg/kg A, and 0.3 kg/kg B.
Mole fractions can be used instead of mass
fractions if desired, but then must be used
consistently.
The following rules apply in the triangular
diagram: If component Cis 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 newmixture
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 nal 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
possible to plot parameters such as lines of equal
density, boiling points or other physical data,
lines of equal activity coefcients or lines of
phase boundaries.
Figure 2. Triangular diagram for representation of a three-
component system
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 important. This
boundary line is called the binodal curve (Fig. 3).
Every point on the binodal curve (except the plait
point in systems with a complete binodal curve,
see below) is in equilibriumwith another binodal
point. The lines which connect points in equilib-
rium 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 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 individual case. Lines
parallel to the triangle sides CB and AC respec-
tively, drawn through related points of equilibri-
um on both branches of the binodal curve,
produce an auxiliary line, formed by the inter-
sections of the parallels, and enable to construct
any tie line as demonstrated in Figure 3 A.
Several types of triangular diagrams are
shown in Figure 4. In every system with a
complete binodal curve (closed diagram, Type
II in Fig. 4) the end points of the tie lines draw
closer and closer together until they nally coin-
cide 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
correspondingly low and its selectivity is usually
high (see Section 2.4).
In diagramII the substance to be extracted (C)
is totally miscible with both A and B. This form
of extraction diagram is often found in extrac-
tions 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
extraction is not possible.
Diagram III shows a system where C has a
miscibility gap with A. Its concentration in the
Figure 4. Various types of phase equilibria in ternary
systems
Type I: Open system, miscibility gap between the key com-
ponent of the solvent (B) and solute C
Type II: Closed system, Cis 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
Figure 3. Denitions of phase equilibria and mass fractions
in a triangular diagram A) Construction of auxiliary line; B)
Compositions of two phases in equilibrium
B-rich phase is then substantially higher than in
the feed. The diagram is typical for wastewater
extractions.
In some practical applications even a third
phase can occur. This is mainly the case if all
binary subsystems show a miscibility gap or if
additional components are produced in chemical
reactions, e.g., in metal-salt extraction, where it
cancauseconsiderableproblems (seeSection5.3).
The inuence of pressure on the binodal curve
and equilibria is negligible below values of sev-
eral bar. The inuence of temperature is strong.
The lower the temperature the more will the
triangular diagram normally be lled by the
miscibility gap.
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 conguration of the cal-
culations is simpler. The most important forms of
representation are shown for three mixtures in
Figures 57. A comprehensive review of forms
of representation is given in [31].
In the equilibrium diagram (Figs. 57 II)
the mass fraction of C in the B-rich phase y
C
(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
diagramin distillation ( Distillation, 1. Funda-
mentals). It shows the relationship between equi-
librium and operating conditions.
In the example shown in Figures 57 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 howmuch better
or worse the extracted component is soluble in the
B-rich than in the A-rich phase; the minimal
solvent ratio can be evaluated directly from
Figures 57 III. The distribution ratio therefore
is an important criterion for the selection of a
solvent. The mass fraction in the A-rich phase is
easier to visualize as a reference variable. At the
feed stage it corresponds approximately to the
initial feed concentration. It governs the yield at
the rafnate outlet. On the other hand, showing k
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
system water (A), butyl acetate (B), phenol (C), at 20

C. All
data refers to mass fractions.
system trichloroethylene (A), water (B), caprolactam (C), at
20

C. All data refers to mass fractions.
as a function of y
C
(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 considerably in the different
concentration ranges.
In the selectivity diagram (Figs. 57 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 (y
C
/x
C
) and for A
(y
A
/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 systemis used as the
starting point for measurement of liquid liquid
equilibria. It is rst necessary to establish which
of the three possible binary systems have a mis-
cibility gap and which are completely miscible.
For this purpose it is sufcient in each case to mix
the two substances in ratios of 3 : 1, 1 : 1 and 1 : 3.
If no formation of two liquid phases occurs in any
of the cases then the system can be regarded as
fully miscible and not suitable for extraction.
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 follows.
Equal amounts of A and B are placed in a
controlled-temperature vessel which can be
shaken (e.g., an Erlenmeyer ask in a thermo-
stat) and substance C is added until the mixture
becomes clear. In two further experiments pure
Aor Bis placed in the vessel and in each case the
second substance is then added until turbidity
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 refractive
index, density, dielectric constant, freezing
point, boiling point, etc. of this mixture can be
determined. In the same way mixtures of Cand 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 dened
by a physical parameter. These titration methods
do not yield information on which two phases are
in equilibrium, i.e., on the tie lines.
To determine phase equilibriumand therewith
the tie lines, i.e., the points which are in equilib-
rium with one another, a mixture from the two-
phase region is placed in a controlled-tempera-
ture, shaking cylinder. Equilibriumis established
by shaking. The phases are allowed to settle and
are separated by draining off into different ves-
sels. Then their quantities are determined and the
physical variable measured during determination
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 titration. It is
recommended to check the correctness of the
measurement by connecting the two tie-line
points in the triangular diagram. The connecting
line must pass through the point of the original
mixture, and this point must divide the length of
the tie line in inverse ratio to the quantities of the
two phases. Any deviation from this hints at an
error in the measurement.
If a systemof 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 separates
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
suitable method.
The time consuming step in the determina-
tion of equilibria is the preparation of the
experiment, such as purication of the sub-
stances, setting up the calibration curves, etc.
Therefore, it is useless 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 57.
2.3. Correlation of Phase Equilibria
Today a variety of thermodynamic and process
simulation packages allow tting and modeling
of liquidliquid equilibria based on models, e.g.,
NRTL [32] and UNIQUAC [33, 34]. The advan-
tage of these thermodynamic models is that they
can be extended to correlate equilibria for an
arbitrary number of components in the mixture.
Also the resulting correlations for the binodal and
tie lines inherently full conditions of thermody-
namic consistency. The parameters of the models
should be tted preferably to liquidliquid equi-
librium data, since prediction of liquidliquid
equilibrium on the basis of parameters tted to
vaporliquid equilibria data, which are more
readily available, usually leads to strong devia-
tions. For a variety of binary and ternary mixtures
parameters for the above-mentioned models are
available in [22].
In some cases it may be advantageous to use
empirical correlations to represent the binodal
curves and distribution equilibria of component
Cin ternary systems [35]. The mutual solubilities
of the liquid phases are usually determined by a
laboratory turbidity titration. The binodal curve
is then determined 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
/
x
/
A
F
/
x
/2
A
y = D
//
E
//
x
//
B
F
//
x
//2
B
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
coefcients.
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 [36]. The correlation is
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
linear, regions of the binodal curves are repre-
sented in wave form as a result of the polynomial
equation. The Hlavaty equation should, there-
fore, 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 y
C
of the two phases in thermodynamic
equilibrium are thus obtained and determine the
positions 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 generally fail
when the concentration of Cis very low. To allow
a more accurate estimation of distribution equi-
libria and extraction processes at the lowrafnate
concentrations that are of industrial importance,
BENDER and BLOCK [35] proposed the following
correlation for the distribution ratio K:
K = G
1
G
2
x
/
C
G
3
x
/2
C
G
4
x
/3
C
The coefcients G
i
must be tted to the mea-
sured values of the tie lines x and y. Although the
equation does not generally permit extrapolation
of the curve above the measured values to the
plait point, the distribution coefcient 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 liquidliquid
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 multicom-
ponent systems. Extensive laboratory work is
required to determine the mutual solubilities of
components Aand Bas a function of the concen-
tration of Cas well as the equilibriumdistribution
of component C. Systematic measurement errors
cannot be detected because the experimental
values are empirically correlated.
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 inuence on the econ-
omy of the process. The solvent must fulll 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 [37,
38]. The more empirical strategy of former times
is being replaced more and more by systematic
research with the aid of data banks [30]. Addi-
tionally, group-contribution and quantum-chem-
ical methods like UNIFAC and COSMO-RS
allow estimation of the thermodynamic proper-
ties of mixtures, including miscibility and distri-
bution ratio [3943]. It can be foreseen that these
methods will further increase in accuracy in the
future. These methods are suitable for screening
different potential solvents in principle. A rigor-
ous screening today still requires an excessive
amount of computer time.
A simple way to characterize miscibility and
distribution behavior is to apply the concept of
polarity for characterizing the components [44].
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 miscibil-
ity gaps occur read off the scale. For example,
aniline, phenol, and furfural have miscibility
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 formand the size of the molecule
also contribute to solvent behavior. The behav-
ior of solvents towards hydrocarbons has been
investigated particularly intensively [45, 46]. It
is also possible to obtain effects from mixing
two solvents which could not be predicted from
the properties of the mix components [47, 48].
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 57 III the selectivity is
strongly dependent on concentration.
In addition to selectivity the capacity of a
solvent is also important. This is dened by the
distribution coefcient 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 specic extraction task it is
often found that solvents with higher selectivities
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 possible solvents for a
process then their behavior with respect
to selectivity and capacity can be tested with a
gas chromatograph without starting with time-
consuming equilibrium measurements [49].
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 com-
pounds. Most important is the availability of the
solvent in commercial quantities at an economi-
cally acceptable price. In the food and pharma-
ceutical industries additional strong limitations
to the choice of extractant apply, and this leaves
little roomfor adjusting the extractant properties,
e.g., by using mixed extractants. It is also neces-
sary to nd data concerning boiling points, den-
sity, viscosity and where available informa-
tion about solubility [50, 51].
The boiling point of the solvent is important
because the extracted component is usually
separated from the solvent by distillation and
the boiling-point difference determines the
reux 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 puried by distillation in a subsequent
step; the specic 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
obtaining a sufciently large difference in densi-
ties between the two liquid phases for the separa-
tion 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 signicant. The researcher hardly ever
nds the answer to this question in the literature
and is directed to carry out his own measurement.
It is necessary to know (1) how much solvent
make-up will be needed in the process; (2) wheth-
er a regeneration process for continuous removal
of decomposition products needs to be installed.
Very careful tests must be carried out to nd out
whether decomposition products can contaminate
the extract or have a corrosive effect on the
construction materials of the plant. Sometimes
the toxicological properties and biological degra-
dation of a solvent have to be considered [52].
The viscosity should be as low as possible as
this favors mass transfer and phase separation.
However, this property is less signicant than
those mentioned above. If the possible solvents
have been reduced to a manageable number after
testing all the aspects then the individual proper-
ties can be evaluated with a point system to
discover the best solvent.
The surface tension is another important pa-
rameter because it inuences 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.
An attribute of the system which until now
could not be quantitatively linked to these physi-
cal properties is the coalescence behavior. This is
inuenced by essentially all of the individual
properties of the phases mentioned above. Addi-
tionally, it is inuenced by the electrostatics of
the interface [5356], which depend on the mo-
lecular behavior of polar components at the inter-
face and strongly on the behavior of ionic com-
ponents present in the system. Especially ionic
surfactants, which can be contained in the system
as trace impurities, can have a strong inuence.
Understanding the basic concepts behind these
ionic effects [53], [54] allows one to design
systematic ways to adjust coalescence behavior
by, e.g., adding small amounts of salts [57]. In
practical applications these salts are often added
in the belief that this inuences the density dif-
ference, but the quantities are actually toosmall to
have a signicant effect on density. Instead, the
electrostatic behavior of the interface is changed,
which in turn strongly affects coalescence.
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 direction
of mass transfer can promote or hamper the
coalescence of drops by inuencing the local
uid dynamics of two approaching drops [58].
The phase to be dispersed should be the one
which impedes the drop coalescence to produce
stable drops, and the one with the higher owrate
to obtain a mass transfer area as large as possible.
The disperse phase should also be chosen, to-
gether with the material of the internals of the
extraction equipment, in such a way that it does
not wet the internals, since this will lead to
smaller drops and more easily controllable
drop-size distribution [59].
2.5. Determination of Mass-Transfer
Performance ( Absorption, 2. Design
Systems and Equipment, Chap. 2.;
Distillation, 1. Fundamentals,
Chap. 4.)
Three possibilities exist to determine the mass-
transfer performance of extractors.
1. The rst one uses the concept of theoretical
stages and is based on the assumption that
concentration equilibrium is established in
every section of an extractor. This assumption
can be fullled only in the mixer settler
with long contact times of the phases in-
volved. 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). NTS follows from a material bal-
ance in combination with the distribution
equilibrium; HETS depends on uid dynam-
ics and mass transfer in the columns and
comprises all real conditions as for instance
the conditions of phase mixing. Therefore
this concept is preferred only for rough es-
timations in practice because it is easy to
handle and sufcient for preparation of lab-
oratory experiments. In the following sec-
tions, the method will be presented by aid of
equilibrium diagrams.
2. The second possibility is a rate-based concept.
The column height required for a given
throughput and concentration gradient of
phases along the column can be calculated
from height integration of a set of differential
equations, derived froma differential material
balance and the local mass transfer between
the two phases. The rate-based concept can be
applied at two different levels of complexity.
The simplest approach assumes segregated
phases with some specied mass-transfer rate
and an effective interface between the phases.
This leads to the HTU-NTU, concept which
can additionally be supplemented by axial
dispersion leading to the HDU-NTU concept.
In a more detailed approach the differential
equations are written for a characteristic drop
of average size. For this drop sedimentation
and transfer are followed. Both versions of the
rate-based approach supply the course of
concentrations along the column and are suit-
able for analysis of the dynamic behavior of a
column. Drop population inside the column
can be accounted for only in an effective way.
This method has been preferred in the past for
scientic investigations, e.g., for stationarily
operated pulsed sieve tray columns [64,
6668, 70, 81] and for instationarily operated
rotating extractors [84, 87].
3. A third approach, which solves the complete
set of coupled integro-differential equations
of the drop-population balances in an extrac-
tion column, has been developed during the
last few decades. In principle, all effects
acting on the drops are modeled by suitable
approaches. These detailed models are then
combined to give a simulation of the popula-
tion balances taking into account the size
distribution of the drops and their concentra-
tions at any time and at any height in the
column.
All three calculation methods can be based on
correlations or available information from the
literature, e.g., on typical values of HETS, mass-
transfer rates and axial-dispersion coefcients, or
individual drop behavior. Experience shows that
extraction behavior can not be described inde-
pendently of considering the behavior of the
individual extraction systems for at least two
reasons. Mass transfer can be strongly inuenced
by specic effects at the drop interface, i.e.,
instabilities induced by mass transfer itself. This
effect until now could not be predicted quantita-
tively and is hardly understood [88, 89]. Second-
ly, the behavior of extraction systems can be
strongly inuenced by components present only
in small concentrations. Thus trace impurities
can signicantly change the interplay between
the different effects acting at the drop, which are
shown schematically and without claiming to
be complete in Figure 8. As a consequence
applying any of these calculation methods with-
out performing an experiment with the original
extraction system can only lead to a rough
estimate of extractor behavior.
For the two rst methods experiments must
be performed with the entire extraction appara-
tus of exactly the type to be built on the technical
scale or at least at pilot-plant scale. Then, e.g.,
HETS can be determined for the specic extrac-
tion system in combination with the specic
type, e.g., an extraction column with specied
internals. This holds likewise for the second
calculation method, where mass-transfer and
axial-dispersion coefcients must be deter-
mined from the pilot-plant-scale experiments.
Only with the third calculation method is there
a chance to reduce the experimental effort sig-
nicantly, because the behavior of individual
drops enters into the calculations. Thus, experi-
ments must be performed only for single drops in
well-designed measuring cells. These measure-
ments are comparatively fast and require only a
small amount of substance from the original
extraction system. Also, based on the single-drop
behavior, any type of extraction column can be
Figure 8. Schematic representation of interplay between
different effects acting at the drops and in an extraction
column
modeled [90]. This of course requires that the
principal uid dynamics of the specic column
design and the inuence of the swarm behavior
can be characterized sufciently well with exist-
ing models. First results indicate that this can be
achieved with sufcient accuracy. The specics
of the extraction system appear to mainly inu-
ence single-drop behavior, while the interplay
between drops and extraction equipment can be
described independently of this individual
behavior. Basic properties of the system like
densities and viscosities enter into all modeling
approaches.
Thus, selection of the method of calculation to
be applied is determined by the problem to
be solved, by whether simplied assumptions are
permissible, and bythe maininuencing variables
of an extraction problem. The required accuracy
and the effort which is permissible for determin-
ing the necessary parameters, e.g., by column or
laboratory experiments, as well as the modeling,
will inuence the choice of the modeling method.
The following points should also be considered
when selecting a method of calculation:
1. Do changes in mass ows have to be
considered?
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 coefcients?
2.5.1. Specic Methods for Determining
the Theoretical Number of Stages
Method 1. The compositions of the phases
can be expressed as loads if the following con-
ditions are satised:
1. Component A and solvent B are virtually
insoluble in each other,
2. Changes in mass ow rates of the extract and
rafnate phase are negligible (e.g., for a low
content of C in the feed)
If a material balance is made as shown in
Figure 9, the two loads Y
c
and X
c
in a given
column cross section can be related as follows
Y
C
Y
C; S
=
m_
F
m_
s
(X
C
X
C; R
)
Alternatively, the concentrations can be de-
scribed as molar loads. 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 concentration of
C from X
C, F
to X
C, R
can be determined graphi-
cally by constructing a series of steps as shown
in Figure 10. Since in this graphical representa-
tion a theoretical number of stages is deter-
mined, a noninteger number of theoretical
stages may result. From Figure 10 an NTS of
2.5 would be estimated. This theoretical value
then forms the basis for determining the
required size of the extraction equipment. If
Figure 9. A) Material balance of a column cross section;
B) Corresponding operating diagram
mixersettlers are to be used, in which
equilibration can be reached with good accuracy
and thus only integer values of stages can be
realized, the purity of the rafnate after three
stages (X
C, R
) exceeds the required value
(X
CR, req
).
Figure 9 also shows the position of the balance
line for the minimum extractant ratio V
min
V
min
= m_
s; min
=m_
F
The desired enrichment of the feed with C
using the minimum amount of extractant m_
s, min
can only be achieved with an innite number of
stages.
Method 2. Figure 11 shows the equilibrium
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 con-
centration range considerably exceeds the de-
sired rafnate purity. In this case the operating
line is at an angle of 45
.
log(Y
C
Y
C; S
) = log
m_
F
m_
S
_ _
log(X
C
X
C; R
)
The position of the straight lines is determined
by the extractant ratio V. The number of required
theoretical stages can be determined by con-
structing a series of steps.
Method 3. If the distribution ratio K is a
constant, further simplication is possible; in
analogy with the Colburn equation ( Absorp-
tion), the number of theoretical stages NTS can
be calculated:
NTS =
log 1(E1)
X
C; F
X
C; R
Y
C; S
X
C; R
_ _ _ _
logE1
where the extraction factor E is given by
E = Km_
s
=m_
F
The extraction factor thus is a quantitative
measure for the ratio of equilibrium capacity for
C between the countercurrent streams.
If NTS is known and the degree of depletion
X
C, R
/X
C, F
is desired, the following equation is
obtained:
X
C; R
X
C; F
=
(E1) 1
Y
C; S
X
C; F
_ _
E
(NTS1)
1
This equation can only be solved iteratively; a
graphical solution is shown in Figure 12.
Method 4. If none of the above-mentioned
conditions is satised, 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.
The specied compositions of the feed F
and solvent S streams are plotted on the phase
Figure 10. Construction of steps in the operating diagram to
obtain the number of theoretical stages (NTS)
Figure 11. Determination of the number of stages for a
variable distribution ratio and a high degree of depletion
equilibrium diagram for the ternary mixture
(Fig. 13). For material balance of the feed and
product streams, the column can be assumed to
be a black box with simple mixing behavior.
Mixing the product streams will lead to the same
overall mixture characterized by the point M as
mixing the feed F with the solvent stream S.
The composition M of the mixture thus lies on
the straight mixing line FS; the position of M on
the mixing line is determined by the ratio m_
S
:
m_
F
= MF : MS. The compositions of the raf-
nate R and extract E streams leaving the column
are obtained from the intercepts of the product
mixing line with the binodal curve. The rafnate
composition is determined by the desired mass
fraction of C in the rafnate (x
C, R
). The com-
position of the extract E is given by the point
at which the extended line RM intersects the
binodal curve. The ratio m_
R
: m_
E
is obtained by
applying the lever rule. The quantities and the
compositions of the incoming and outowing
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 rafnate stream R gives the composi- Figure 13. Pole point construction balance diagram
Figure 12. Dependence of the theoretical number of stages, the degree of depletion, and the yield on the extraction factor E
tion 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 composi-
tions 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 components in the pole point can be
> 1 or negative. If the material balance bound-
aries for the individual stages are taken as
shown in Figure 14, the above procedure gives
the stage extracts E
2
, E
3
, etc. from the mixture
of the imaginary stream P and the individual
stage rafnates in the proceeding stages R
1
, R
2
,
etc. The composition of the rafnates R
1
, R
2
,
etc. are linked to the corresponding extracts E
1
,
E
2
, etc. via the equilibrium condition, i.e., the
tie lines with the corresponding distribution
ratios.
2.5.2. Determining Equipment Behavior
Based on Drop-Population Balances
The population balance for the drop of diameter d
can be written as follows if, for the sake of
simplicity, mass transfer is neglected [8]:
The average number of drops with diameter d
at time t in a height element Dh at position h in the
column
= this number of drops at a time which is Dt
earlier
drops of diameter d sedimented into Dh in Dt
drops with d leaving Dh in Dt by sedimentation
drops with d that were formed by coalescence
of smaller drops in Dt and Dh
drops with d that disappeared in Dt and Dh due
to coalescence with other drops
drops with d that were formed by splitting of
larger drops in Dt and Dh
drops with d that disappeared in Dt and Dh due
to splitting into smaller drops.
Each of these expressions can be described by
appropriate model equations, also including
mass transfer. The coupled equations can then
be solved either directly [91] or by using sto-
chastic methods. Today the stochastic method
represented by the ReDrop model of HENSCHKE
[90] is able to take more independent drop vari-
ables into account, i.e., drop diameter, drop
concentration, and lifetime of the drop. The
last-named must be considered when accurate
description of mass transfer is desired. Based on
the drop-population balances the transient be-
havior of the extraction equipment is described,
and it is even possible to determine the limits of
operability of the extraction column, i.e. ood-
ing. Thus, no separate ooding-point correlations
are necessary when solving drop-population
balances.
The principal procedure of the ReDrop ap-
proach is sketched in Figure 15. Since a variety of
Figure 14. Pole point construction operating diagram
equations are combined for this complete de-
scription of extraction-column behavior, the
reader is referred to the original work of
HENSCHKE [90] for details. The basic idea behind
ReDrop is to follow the individual behavior of a
certain number of individual drops (Representa-
tive Drops). The trajectories of these drops are
calculated on the basis of their sedimentation
velocities. On their way through the column,
mass transfer with the continuous phase takes
place, andcoalescence andsplittingare accounted
for by appropriate probabilities in comparison
with random numbers. It turns out that roughly
1000 drops per meter of column height are suf-
cient for very stable simulations, a number which
can easily be handled by any PC. In Figure 15 the
time loop and drop loop of ReDrop are shown.
The individual effects acting on the drops are
accounted for in the drop loop with the corre-
sponding models, where an advantage of ReDrop
is that this canbe formulated ina modular fashion.
The parameters of the models are determined in
appropriate standardized laboratory-scale mea-
suring cells. In contrast to the other design meth-
ods, applying drop-population balances no longer
distinguishes betweenthe thermodynamic andthe
uid-dynamic design of a column. Both aspects
are accounted for simultaneously.
This method has been developed for a variety
of types of extraction columns to an extent where
it is possible to obtain the parameters of the
models characterizing the single-drop behavior
from simple experiments in standardized labora-
tory cells and then to join these models together
with the population balances. Thus, the behavior
of pilot-scale extraction columns can be pre-
dicted on basis of the behavior of single drops
with a set of appropriate model equations. It has
been shown that this method is able to correctly
predict extraction-column behavior with differ-
ent internals for clean standard test systems as
well as for technical systems [90, 92, 93]. The
major advantage of this method is that only a
rather small amount of substance is required for
performing the laboratory-cell experiments,
these experiments take roughly two weeks, and
the prediction of various column types can be
based on the same set of experimental results.
Thus, this method is more reliable and faster
than the other design methods that generally
require experiments in appropriate extraction
columns with a diameter between 32 and 150
mm as a basis for determining HTU, HDU, or
HETS.
An example of a laboratory-scale measuring
cell is shown in Figure 16 [9496]. The continu-
ous phase, which here is chosen to be the heavy
phase, is pumped through the cell from top to
bottom. A single drop of exactly known volume
is then generated with a nozzle connected to a
computer-driven syringe. The drop detaches
Figure 16. Laboratory-scale measuring cell for determining
mass transfer of single drops
Figure 15. Schematic representation of the ReDrop algo-
rithm [90]
from the nozzle and rises until it reaches a stable
position in the conical part of the cell. There it can
be kept levitated for an arbitrary time. After a
preselected contact time the countercurrent ow
of continuous phase is stopped, and the drop rises
further until it reaches the collection funnel, from
which it is removed again with a computer-
driven syringe. Measuring the composition of
the dispersed phase after drop withdrawal gives
information on mass-transfer rate as function of
drop diameter and contact time, which can then
be correlated with appropriate models that are
then are used in solving the drop-population
balances. In the measuring cell, internals can be
incorporated to determine their inuence on mass
transfer [92, 97]. An interesting result is that
mass-transfer rate is apparently not inuenced
by the packing. The effect of the packing is rather
the reduction of sedimentation velocity, which in
turn increases residence time. This of course has
an effect on the mass transfer observed within a
given height of equipment.
2.5.3. Evaluation of Stage-Number
Calculation for Process Design
In order to determine suitable operating condi-
tions and the dimensions of the equipment used
for extraction, the results of several stage-num-
ber calculations must be plotted in a diagram
showing the relationship between the solvent
circulation, the number of stages, and the residual
content of solute in the rafnate. Such a diagram
is shown in Figure 17 for mixture II (see also
Fig. 6). It represents the extraction of a 10 %
solution of caprolactamin trichloroethylene with
water as the extraction solvent. The favorable
operating region is usually located in the region,
which shows the most pronounced curvature.
Figure 17. Extraction of caprolactam from a 10 wt % solution in trichloroethylene with water as solvent
Other variables (e.g., the effect of temperature
and the residual loading of the solvent with
solute) may have to be taken into consideration.
3. Apparatus
3.1. Survey
Extraction apparatus can be classied into coun-
tercurrent columns, centrifugal extractors, and
mixer settlers. All industrial equipment designs
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 inuence the drop gener-
ation by energy input such as mixing or pulsing.
After the resulting droplets have been contacted
with the continuous phase long enough to allow
the extractable component(s) to migrate between
the phases, both liquids have to be separated
again. Densities will dene the ow directions
of the phases: The heavier liquid ows fromtop to
bottom, the lighter one from bottom to top. Ac-
cordingly, the uids have to be transported to the
apparatus and removed by pumps.
In the following chapter, a fewtypical designs
have been selected from the large number of
equipment designs actually used in industry. A
more detailed treatment can be found in litera-
ture, especially in [5] and [6]. A more recent
update on recommended choices for extractor
equipment together with cost estimations for
different extractor equipment is given in [8].
3.1.1. Columns without Energy Input
The simplest extractor is the spray column
(Fig. 18 A). The spraycolumnachieves onlyvery
small numbers of separation stages and is rarely
used nowadays. If the column of Figure 18A is
lled 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 continuous layer
oating on top of the continuous liquid.
The reverse procedure is possible as well, as
shown in Figure 18 B. Here, the distributor is
located at the top and the water interface, called
the principal interface, is controlled at the bottom
of the column by lling it mainly with the lighter
liquid. In this case, the heavier liquid is the
dispersed one, broken into droplets descending
in the lighter liquid. The principal interface can
be adjusted at any height (between top and
bottom) of the column as needed, thus the heavier
liquid being dispersed above and the lighter
liquid below the principal interface.
Countercurrent columns are equipped with
settling zones at the top and the bottom, with
coalescing aids provided if necessary. The liquids
should never be fed into the column in these
settling zones because this would cause hydrody-
namic instability of the column thus reducing the
operational performance. The dispersed liquid
often cannot be selected from theoretical consid-
Figure 18. 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)
erations, but only by aid of experiments using the
real material system.
Packed columns (structured and unstructured)
and sieve-plate columns have been adopted from
distillation technology ( Distillation, 1. Fun-
damentals). In packed columns drop formation
occurs on entry of the dispersed phase in the
packed bed (Fig. 18 B). The drops rise through
the packed bed without signicant further dis-
persion. Packed columns without energy input
generally show relatively low efciency [6,
Chap. 8].
In a sieve-plate column with downcomers, as
shown in Figure 18 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
ows throughthe downcomers fromstage tostage
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-ow
plates without downcomers [76].
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 without
energy input can reach efciencies 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
additional mechanical energy in form of super-
imposed agitation or pulsation, resulting in
higher turbulence near the drops and enlarged
mass-transfer area due to smaller drop sizes,
as well as leading to narrower drop-size distri-
bution that reduces axial dispersion of the
dispersed phase.
3.1.2. Pulsed Columns
The simplest design of pulsed column is the
pulsed sieve-plate column (Fig. 19 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 pulsation.
The downcomers used in the conventional sieve
plate column are thus superuous. The dispersed
phase does not coalesce above or belowthe plates
Figure 19. Pulsed and reciprocating-plate columns (Light phase dispersed) A) Pulsed sieve-plate column; B) Reciprocating-
plate column (Karr)
to give a continuous layer. The pulsation shock
ings the drops off the plate faster than would be
possible as a result of only the density difference.
This leads to a ne, uniform drop distribution
and hence enlarges the mass-transfer area.
Applications are limited by the physical proper-
ties of the substances concerned and high
throughputs. Systems which emulsify easily can-
not be processed in pulsed columns just as sticky
and greasy liquids. For very large throughputs
(column diameter > 0.6 m), the pulsed volume
and pulsing power become very high; however,
pulsing units for large column diameters have
been developed.
The separation effect of the column decreases
with increasing diameter, this has not yet been
fully investigated. The plate spacing is 50
100 mm. Larger plate spacings favor backmix-
ing and hence reduce the efciency of the col-
umn. Smaller plate spacings lead to a strong
decrease of the throughput. Sieve plates have
cylindrical holes and a triangular pitch. The
relationship between the fractional free area j,
the hole diameter d
i
and the pitch p is given by
j = pd
2
i
=
12 p
2
_
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 inter-
facial tensions. Free areas less than 20 %are used
for liquids with higher viscosities [77].
The plate material has a pronounced inuence
on drop formation and hence on the separation
efciency. The plate material and phase selection
must be matched in such a way that the 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 exactly face the ow di-
rection of the dispersed liquid 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 construction or by applying
edge-sealing elements made of materials which
are wetted by the continuous 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 to 15 mm (relative to
the column cross section). Pulsing amplitude is
dened as the distance between upper and lower
center of the pulsing motion in the active part of
the column. The dispersed phase has to be fed
into the column via a distributor. 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 distrib-
utor. The holes in the distributor should be very
sharp-edged to avoid very ne drops. Even in
packed columns, the separation effect can be
substantially improved by pulsing of the contin-
uous phase, at the expense of a reduced through-
put. The increased performance results from
greater shear forces causing a reduction in drop
size and an increase in interfacial area [6,
Chap. 8]. As in distillation columns, the phenom-
enon of maldistribution in randomly packed col-
umns 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 owrate of both phases
of approximately 100 m
3
m
2
h
1
compared to
30 m
3
m
2
h
1
for a randomly packed column.
Structured packings are particularly suitable for
low interfacial tension systems or for small den-
sity differences; separation efciency is nearly
independent of scale-up. Hydrodynamics and
mass-transfer performance are well investigated
[6, Chap. 8], [78].
Pulsing Units. The use of pulsed columns is
currently limited to small and medium through-
puts. The column diameter is limited by the
pulsing unit. For very large throughputs, the
pulsed volume becomes so large that the use of
a piston pump as the pulsing unit causes difcul-
ties. Consequently, pulsing units have been de-
veloped which operate without a piston pump.
The pulsator developed by MISEK (Fig. 20) is
based on a centrifugal pump. The pump (e) is
connected on both the suction side and the deliv-
ery 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
20 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. 20 B), the pump
delivers fromthe column via vessel (a) into drum
(b). The pump thus always delivers continuously
in one direction. Reversal of the direction of ow
in the pulse line is effected by the changeover
valve (c) in accordance with the pulse frequency.
A pulsator based on this principle has been
developed by Bronswerk/DSM (Fig. 20 C), and
is nowin operation for columns with a maximum
diameter of 2.7 m.
For large pulsed volumes, the hydraulic pul-
sator fromWepuko [79] is also suitable (Fig. 21).
It is anged directly to the lower bottom of the
column end and acts in the direction of the
column axis. The pulsing piston is connected via
a common piston rod to a working piston, the
hydraulic drive of the piston is a rapidly revers-
ible 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 development
of the reciprocating-plate column which can be
regarded as the converse of the pulsed sieve-plate
column. In the pulsed sieve-plate column, the
trays are xed and the entire liquid content of
the column is caused to vibrate; in the recipro-
cating-plate column, the plates are moved. In
both cases, the liquid undergoes an oscillating
motion relative to the plate.
In the Karr column (Fig. 19 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
eccenter.
Figure 20. Pulsator with rotating valve A) Principle
diagram of compression stroke; B) Principle diagram of
suction stroke; C) Technical design (Bronswerk) a) Suction
drum; b) Discharge drum; c) Rotating valve; d) Column;
e) Centrifugal pump
Figure 21. Hydraulic pulsator a) Pulsing piston; b) Working
piston; c) Rinsing; d) Hydraulic aggregate with radial piston
pump
The relatively large free area of reciprocating
plate columns allows much greater throughputs
than conventional pulsed columns. However,
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 [80].
Research on the established types of pulsed
columns has been very intensive since the 1970s.
3.1.3. Columns with Rotating Internals
Rotating Disk Contactor (RDC). In the
RDC (Fig. 22), stator rings are mounted at close
intervals. Disks are tted between the rings to a
rotating shaft. The rotating disks ing the drops
of the dispersed phase off centrifugally, onto the
stator rings where they are braked and deected.
The drop distribution is excellent and can reach
the emulsication limit as the rotational speed
increases.
The RDC has a relatively simple construction
with a large free cross-sectional area. It reaches
large throughputs, but it favors backmixing of
phases causing a decrease of efciency. A large
range of throughputs is possible without remark-
able decrease of efciency. 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 efciency decreases sharply with
increasing diameter. 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 prefer-
ably used to operate with large product ows
when the demands on separation performance are
only low as for instance in the oil industry or in
wastewater treatment [61].
As in pulsed columns, the wetting behavior
also inuences drop formation in the RDC, and
should therefore be taken into account when
selecting a material for the column internals.
K uhni Extractor. The Kuhni extractor
(Fig. 23 A) uses a turbine as the mixing element.
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. 23 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
Kuhni extractor (see Fig. 23 A).
For the Kuhni and RZE columns the choice of
rotor type can be regarded as being independent
of the choice of stator geometry in principle.
Graesser Contactor. The Graesser contac-
tor (Fig. 24) is another type of rotating equip-
ment. Here, not only the internals but also the
entire apparatus rotate. Internal half-tubes are
tted as scooping elements in a horizontal rotat-
ing cylinder. Due to the rotation, the half-tubes
transport part of the heavy phase into the overly-
ing light phase, and vice versa. To reduce back-
Figure 23. Columns with rotating internals A) Kuhni extrac-
tor; B) QVF RZE extractor
Figure 22. Rotating disk contactor (RDC)
mixing, the extractor length is divided into
chambers by partition disks. Because of its low
dispersing effect, this equipment is particularly
suitable for systems which tend to emulsify.
The throughput is low compared with other
extractors.
3.1.4. Mixer Settlers
Mixer-settlers consist of single or several stages
in series (Fig. 25 A), each stage consisting of a
stirred vessel and a settling vessel (Fig. 25 B).
Various arrangements are possible such as cocur-
rent, countercurrent, or crosswise ow of phases.
The mixersettler is the only extractor that
reaches stage efciencies of nearly 100 % and is
almost insensitive for load uctuations.
This extractor has the advantage that back-
mixing can be completely precluded due to the
complete phase separation in each stage. As a
result, there are no transfer problems in scale-up.
The favorable efciency is almost completely
retained 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
mixersettlers in industrial processes for many
decades. Unfortunately the operating volume of a
mixersettler, and hence the residence time, is
rather high. Thus, application of mixersettlers is
limited if reactions can occur in one of the phases.
However, early mixersettler equipment 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 interface level
control. The horizontal arrangement resulted in
a large area requirement.
In an effort to overcome these disadvantages
of the mixersettler batteries without giving up
any of their advantages, a number of different
designs were developed. Mixersettlers are
Figure 24. Graesser contactor
Figure 25. Principle of a mixer settler A) Flow Sheet; B) Arrangement
used in two different areas. Industrial-scale
equipment is used to obtain extremely high
throughputs when a small number of stages is
needed, e.g., in the extraction of metal salts.
Laboratory-scale devices are employed in
process development 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 aqueous
solutions. The basic design is a box-type mixer
settler according to Denver (Fig. 26). The mix-
ing and separating zones are combined in a single
unit and are separated by an overowweir for the
light phase and an underow 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 dis-
perses and conveys the liquid phases. These
functions may conict with one another. The
rate of rotation necessary to overcome the con-
veying height may be too high when unstable
systems must be dispersed, causing problems in
phase separation, e.g., a high degree of entrain-
ment. Mixing pumps with low shearing forces,
and thus a low mixing intensity, have been
developed to avoid these difculties. Examples
are the Pumpmix impeller used with the Davy
McKee mixer settler (Fig. 27 A) and the IMI
turbine pump-mix unit (Fig. 27 B).
A further development of the Davy McKee
mixer settler has been described [62]. Each
stage consists solely of a vessel in which mixing
Figure 26. Box-type mixer settler (Denver) A) Side view;
B) Ground plain
Figure 27. 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
and separation occur. The product inlet and the
agitator are located in the middle and create a
dispersion zone. The light phase separates out at
the top and the heavy phase at the bottom.
In the Lurgi tower extractor, the battery of
adjacent settlers is replaced by a space-saving
tower design in which the settlers are arranged on
top of each other. External centrifugal pumps are
used for mixing (Fig. 27 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 mixersettlers 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 laboratory mixer
settlers are shown in Figure 28.
3.1.5. Centrifugal Extractors
Centrifugal extractors are used when the density
difference between the two phases is insufcient
to produce a countercurrent under gravity. The
best known of these devices is the Podbielniak
centrifugal extractor (Fig. 29 A), in which cy-
lindrical perforated sheets are concentrically ar-
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 interface must
be located near the shaft. Thus, the Podbielniak
centrifugal extractor can be viewed as a sieve-
tray column coiled around a rotating shaft. De-
pending on the system the number of stages
which can be combined in one unit is limited to
3 to 4 theoretical stages.
The Robatel centrifugal extractor is based on
a totally different principle and allows greater
numbers of stages (Fig. 29 B). Disks serving as
the mixing element are centered on a vertical
stator. 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 re-
view on operation 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 they
have advantages which no column can provide.
Phase separation is possible even in systems
Figure 28. Laboratory mixersettlers A) Normag mixersettler; B) Schott/QVF mixersettler
having a density difference as low as 15 kg/m
3
.
Systems with large differences in viscosity can
be processed, since the high shear forces assist
intensive mixing.
As a result of its compact design, the centrif-
ugal extractor is a space-saving apparatus with
an extremely small operating volume and a
short residence time. These advantages can be
desirable if expensive solvents or substances of
limited 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 uid-dynamic
fundamentals is given elsewhere ( Fluid
Mechanics).
3.2.1. Problems and Process Strategy
In Section 2.5, it was shown how the number of
theoretical stages and the ow diagram of the
unit operation extraction are calculated on
the basis of equilibria. The selection and design
of apparatus until now based on uid dynamics
and are not carried out until the thermodynamic
design is completed. At present, model experi-
ments on pilot-plant scale are still necessary for
the design of extraction apparatus. For this
reason, knowledge of the operating character-
istics of the various types of apparatus is of
great interest so that the number of experiments
can be substantially reduced, and preselection
and preliminary sizing can be carried out at a
relatively early stage of process development.
In future the approach based on drop-popula-
tion balances and laboratory-scale experiments
will be further developed and increasingly
relied on. In drop-population balances uid-
dynamic and thermodynamic considerations
are accounted for simultaneously. In this sec-
tion the more conventional approach is
presented.
The uid-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
Figure 29. Centrifugal extractors A) Podbielniak extractor;
B) Robatel four-stage countercurrent extractor
the operating conditions affect (1) the loading
limit and hence the column diameter and (2) the
separation efciency and thus the column height.
Measures for increasing the loading limit have an
adverse effect on the separation efciency, and
vice versa.
The sizing of the column diameter depends on
the ooding point, i.e., the maximum loading
limit at which a column can be operated. On
ooding, accumulation of the dispersed phase
occurs at individual points within the column and
blocks countercurrent ow. Consequently, the
light phase appears in the discharge of the heavy
phase, and vice versa. This phenomenon is
detectable by holdup measurements. On ood-
ing, the holdup increases continuously and
indicates an unstable operating state.
The ooding limit depends on the drop size.
Small drops rise less rapidly than large drops and
therefore cause a greater holdup. The more ener-
gy is supplied to the system either by pulsing or
by rotating internals the smaller are the drops,
so that the ooding limit decreases.
Internals also effect dispersing. The smaller
their open area, the more the ooding limit
decreases.
The sizing of the column height is deter-
mined 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 coefcient, the mass-transfer
area and the concentration difference between
the two phases. A great progress in scientic
research has been achieved as regards measure-
ment and calculation of the quantities of
inuence on mass transfer (see for instance
[6, 6468, 70, 8184, 87, 90, 92, 96, 97]). But
in practice, the various inuences on mass
transfer in an extraction column are best sum-
marized in the expression height equivalent
of a theoretical stage (HETS), as a measure
for the separation efciency of the column, as
mentioned in Section 2.5.
Measurements in pilot-plant columns will be
used below to demonstrate the way in which
various parameters affect the loading limit and
separation efciency. The test systems recom-
mended by the European Federation of Chemical
Engineering (EFCE) are used for this demonstra-
tion [63].
3.2.2. Operating Characteristics of Pulsed
Columns and Columns with Rotating
Internals
Loading Limit. Figure 30 shows the load-
ing limit v
C
v
D
as a function of the pulsing
frequency for plates of small free area j for the
toluene water system, i.e., for high interfacial
tension. v
c
and v
d
are the volume ows of con-
tinuous (c) and dispersed (d) phase related to the
total cross-sectional area of the column, the so-
called supercial velocities. This ooding-point
curve starts at the origin of the coordinates; in
other words, without pulsing, no signicant
throughput is possible. With increasing pulsing,
the throughput also rises up to a maximum. This
part of the curve is calledthe lower ooding limit;
here, pulsing has mainly a transport function.
With increasing frequency, however, the dispers-
ing function predominates, the drops become
smaller and the loading limit falls. The interest-
ing region in practice is that in which dispersing
predominates.
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 j = 0.6, a
modest throughput is possible even without
pulsing.
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 [72].
Figure 30. Loading limit as a function of the pulsing fre-
quency at different free area for toluene water [69]
a = 6 mm; v
d
/v
c
= 1 ~ j = 0.60; d = 6.5 mm & j
= 0.40; d = 4.0 mm *j = 0.23; d = 2.5 mm
Of all the physical properties, the interfacial
tension has the greatest effect on the uid dy-
namics of an extraction column. Figure 31
shows a comparison of three test systems with
different interfacial tensions. As can be seen, the
throughput optimum is shifted to higher pulsing
frequencies with increased surface tension, i.e.,
high surface 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 32 shows the
effect of the parameter v
d
/v
c
[71]. As the phase
ratio increases, the throughput decreases.
Afurther parameter affecting the loading limit
and separation efciency is the direction of the
mass transfer. Curve b in Figure 33 A shows the
ooding point curve of the pure two-component
mixture toluene water, where no mass transfer
takes place [73]. Curve a for mass transfer from
the dispersed organic phase to the continuous
aqueous phase lies substantially higher by com-
parison. 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 dispersed phase), the
drop size is reduced by the component being
transferred, leading to a lowering of the ooding
point [72, 74]. The effect of the direction of mass
transfer on the drop size also causes differences
Figure 33. Inuence of mass transfer on loading limit and
separation efciency for the toluene acetone water sys-
tem (j = 0.60)
~Mass transfer fromthe disperse to the continuous phase; &
System without mass transfer; * Mass transfer from the
continuous to the disperse phase
Figure 32. Relative loading of a pulsed sieve plate column as
a function of ow ratio [71]
*Toluene water; &MIBK water; ~Butyl acetate
water; 3 n-Butanol water
Figure 31. Loading limit as a functionof pulsation frequency
at different interfacial tension [69]: j = 0.23; v
d
/v
c
= 1
a) Butanol water: s = 1.8 mN/m; b) Butyl acetate wa-
ter: s = 13.5 mN/m; c) Toluene water: s = 36.1 mN/m
in the separation efciency. In the case of mass
transfer from the continuous phase to the dis-
persed phase (into the drop), smaller HETS
values result, i.e., better separation efciency is
obtained (Fig. 33 B).
PILHOFER [75] 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 Efciency. However to obtain a
high separation efciency a large mass-transfer
area, i.e., the greatest possible holdup of
dispersed phase, is required. The holdup rises
with decreasing drop size. Any input of energy
has the purpose of producing the optimal drop
dispersion. The interrelation of separation ef-
ciency and pulsation can be demonstrated by
measurements on the toluene water acetone
system, which has a high interfacial tension [60].
Figure 34 shows the measured height of a theo-
retical 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
efciency. The curves show an important inu-
ence of the plate geometry: with increasing free
area, the separation efciency decreases sharply.
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 signicant loss in separation
efciency.
A comparison of these two systems clearly
shows the pronounced inuence of the interfacial
tension on separation efciency. This uid-
dynamic aspect should also be taken into account
when selecting solvents for extraction processes.
Hitherto, this selection has been made almost
exclusively under thermodynamic criteria.
The relationship between plate geometry,
interfacial tension, and separation efciency, 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
tension, 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 classied into three catego-
ries. The rst category consists of empirical
correlations which are based on physical and
geometrical data, and energy input. The second
category is based on uid-dynamic models and
presupposes knowledge of the drop size. Both
method classes are applicable only to two-com-
ponent systems and thus neglect the effect of
mass transfer, as shown in Figure 33. The effects
of wetting and of drop coalescence are likewise
disregarded. Moreover, the empirical correla-
tions in particular are frequently restricted to
certain geometries and cannot be extrapolated
to other designs; they can therefore only be used
to obtain an approximate estimate. For nal
equipment sizing based on these two approaches,
an experimental determination of the loading
limit in the particular type of equipment with
the original process streams is absolutely neces-
sary. The third method for calculation of the
ooding limit is based on drop-population bal-
ances as described in Section 2.5.2. This is shown
in Figure 35, where the general loading diagram
Figure 34. Separation efciency measured as a function of
interfacial tension [60] a) c) Toluene water acetone; d)
Butanol water succinic acid
j = 0.60; *j = 0.40; !j = 0.23
has been calculated with ReDrop without further
assumptions.
In the following the classical ooding-limit
correlations are presented.
Packed Column. Unpulsed packed col-
umns have essentially no industrial signicance
any longer. A review on empirical equations to
calculate holdup, drop size, ooding, mass trans-
fer, and axial dispersion 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 as-
sumed to cause the load limits to fall by 20
30 % as compared with the unpulsed column.
Still, no equations for calculation are known.
Sieve-Plate Column. The conventional
sieve-plate column has been investigated by
PILHOFER [85] for toluene water systems.
HIRSCHMANN [98] expanded the investigations
of PILHOFER to liquid systems with lower surface
tensions and density differences than toluene
water and to dual ow plates. For calculation,
see [98].
Sieve-Plate and Rotating Columns.
Special empirical equations are given in the liter-
ature for each type of extraction columns in order
to calculate the ooding condition, so, e.g., for
sieve-plate columns in [85] and [86], for pulsed
sieve-plate columns in various chapters of [6],
and for rotating columns in [6] and [5]. How-
ever, since important effects are disregarded as
mentioned before, here it will be sufcient to
introduce a rough method based on a uid
dynamic model [85]. The model, originally
developed for unpulsed sieve-tray columns,
proved to be applicable to all types of columns.
It is assumed that the liquids occupy a share of
the cross-section according to their holdup e and
ow toward each other as layers of segregated
phases. If their supercial velocity v, i.e. their
volumetric ow rate V related to the complete
column cross section S, is
v
c
=
V
c
S
; v
d
=
V
d
S
(1)
they have an effective velocity v
c
/(1 e
d
) or v
d
/
e
d
. That yields the relative velocity v
r
, also
called slip velocity, between the two liquids
v
r
=
v
d
e
d
v
c
1e
d
(2)
Either v
r
or e
d
can be calculated from Equa-
tion (2) if one or more relationships between the
two terms are known. In [64] a simple empirical
equation is given to calculate v
r
v
r
v
p
= (1e
d
)
k
(3a)
k = 4:60:13 ln Ar (3b)
when 1 < Ar < 10
7
and 2.5 < k < 4.6
v
P
is the individual drop velocity given by [85]
for circulating drops
Re
p
= K
0:15
L
(Ar
0:523
K
0:1435
L
0:75) (4a)
if
1:83 K
0:275
L
< Ar < 3:94 K
0:275
L
for oscillating drops
Re
p
= K
0:15
L
(4:18 Ar
0:218
K
0:00773
L
0:75) (4b)
Figure 35. General loading diagramfor water butyl acetate
acetone in a pulsed sieve-tray column of 3 m height,
pulsation af = 11.7 mm/s, 4 mm hole diameter, 39 % open
area, 0.1 m plate distance
if
Ar > 372:9 K
0:275
L
(4c)
The dimensionless numbers are dened as
follows:
particle Reynolds number
Re
p
=
v
p
d
p
n
d
(5)
Archimedes number
Ar =
d
3
p
g r
c
Dr
h
2
c
(6)
characteristic number of liquid
K
L
=
r
2
c
s
3
D r gh
4
c
(7)
density difference
D r = [r
c
r
d
[ (8)
Mathematical formulation implies the fact
that an increase of the owrate at ooding cannot
increase the drop holdup:
dv
d
de
d
= 0 (9a)
when v
c
= constant,
dv
c
de
d
= 0 (9b)
when v
d
= constant.
With Equation (2) for the slip velocity v
r
the
equations for calculating the supercial veloci-
ties v
c
, v
d
at the ooding point are obtained in a
dimensionless form:
v
c
r
c
D rv
c
g
_ _
1=3
= Ar
1=3
(1e
d
)
2
Re
r
e
d
dRe
r
de
d
_ _
(10a)
v
d
r
c
Drv
c
g
_ _
1=3
= Ar
1=3
e
2
d
Re
r
(1e
d
)
dRe
r
de
d
_ _
(10b)
Equations (10a) and (10b) together with Equa-
tion (3) for v
r
and Equation (4) are the basis for
ooding point diagrams according to Figure 36.
Ordinate and abscissa contain the supercial
velocities v
d
and v
c
, i.e., the phase ow rates,
modied by physical data groups to a dimension-
less form. The diagram shows the calculated
ooding curves of circulating drops as solid lines
with the parameter Ar. Dashed lines of constant
phase ratio v
d
/v
c
and the total throughput as the
sum of v
d
and v
c
are also shown.
It can be seen from Equation (4b) that Re
P
is
approximately proportional to Ar
0.3
and therefore
tod
P
. That means that the dropvelocityv
P
is nearly
independent of drop diameter d
P
in the region of
oscillatingdrops. Therefore Figure 36canbeused
also for oscillating drops if Ar is replaced by K
L
using Equation (4c). Otherwise the diagram is
valid for a certain K
L
value in the region of
circulatingdrops, incaseof Figure 36, K
L
= 10
11
.
The dependence of drop diameter d
P
upon
parameters of inuence must be known in order
to use Figure 36 and to calculate ooding curves.
Many scientic investigations on drop disinte-
gration in various extractors are found in the
literature, but often without considering the in-
uence of mass transfer and the interaction of
dispersing and coalescence. Furthermore, partic-
ularly for higher interfacial tension systems a
considerable height of column is required to
reach a steady-state drop size, and this height
varies with liquid system and inlet arrangement
for the dispersed phase. Nowthe concept of mean
drop sizes is applied normally reported as the
Sauter mean or surface percentage mean drop
size dened by
d
32
=
i
n
pi
d
3
pi
i
n
pi
d
2
pi
(11)
where n
pi
represent the numbers of drops of the
class i of diameter d
pi
.
Finally, discussion will be restricted to empi-
rical equations by KUMAR and HARTLAND
Figure 36. General loading diagram [71, 75]
[Chap. 17] which give the best t to experimental
data and have the broadest range of validity:
Pulsed sieve tray and reciprocating extractor
d
32
s
D
_
r
g
=C
1
e
0:74
h
0:05 m
_ _
0:10
exp 3:00
a f Dr
1=4
gs
1=4
1=4
_ _
exp 28:65
a f Dr
1=4
gs
1=4
1=4
_ _ _ _
(12)
The best values of the parameter C
1
are 1.51,
1.36, and 2.01 for no mass transfer, c d, and
d c direction of transfer, respectively. The
product a f is considered as the agitation vari-
able in the equation, since the t could not be
improved if a and f were treated separately. The
average absolute value of the relative deviation in
the predicted values of d
32
fromthe experimental
points is 16.3 %.
Rotating disk extractors
d
32
D
R
=
C
1
0:07

Fr
R
_
_ _
h
c
s
_
r
c
D
R
_ _
0:12
r
d
r
c
_ _
0:16
D
2
R
r
c
g
s
_ _
0:59
h
D
C
_ _
0:25
D
D
R
_ _
0:46
(13)
The optimized values of C
1
are 0.63, 0.53, and
0.74 for no mass transfer, c d and d c
directions of transfer, respectively. The effect of
holdup is ignored due to lack of data. Equa-
tion (13) predicts the drop size with an average
absolute value of the relative deviation of 23 %.
K uhni columns
d
32
D
R
= C
1
e
0:37
n
0:11
S
[0:14exp (18:73Fr
R
)[
h
c
s
_
r
c
D
R
_ _
0:20
D
2
R
r
c
g
s
_ _
0:24
(14)
The values of the constant C
1
are 9.81 10
-2
for no mass transfer and c d transfer and 0.31
for d c transfer. The stage number n
S
, which
varies from2to17inthe present set of data, shows
a rather weak effect on drop size. Equation (14)
predicts the drop diameter with an average
absolute value and relative deviation of 17.6 %.
3.3. Apparatus Design
Extraction apparatus can be approximately
designed purely by calculation using uid-
dynamic models [68, 99]. For reliable design,
however, pilot-scale tests are indispensable.
Based on modeling with drop-population bal-
ances, it has been shown that laboratory-scale
experiments may be fully capable of replacing
these pilot-plant scale experiments in the near
future. Even for technical systems good agree-
ment between ReDrop prediction and pilot-scale
experiment has been achieved [92].
If pilot-plant experiments are to be performed,
they should be carried out with the original
operating mixture in the type of apparatus which
is also envisaged for the large-scale unit.
Desirably, the geometry of the internals should
be the same in the pilot-scale and industrial
apparatus. However, this condition cannot
always be satised. Generally, a column diame-
ter of at least 50 80 mmis necessary for design
tests. Tests in smaller columns generally cannot
be used as the basis for equipment sizing (for
criteria on equipment selection, see Section 3.4).
Only for Kuhni columns has it been shown that
scaleup is possible on the basis of experiments
with a column diameter as small as 32 mm. The
number of tests can, however, be substantially
reduced if knowledge of the operating character-
istics is utilized.
The physical data and the phase ratio are
determined by the process used. The following
parameters are available for optimization: puls-
ing or rotation, geometry of the internals, mate-
rial of the internals, and phase selection, i.e., the
direction of mass transfer. Energy input and the
geometry of the internals are selected on the basis
of the physical data.
Here the advantage of using drop-population
balances for equipment design must be pointed
out again. While in the conventional method
pilot-plant scale experiments are required to be
performed for the column internals identical to
those in the technical process, the parameters of
the drop models used in the population balances
are determined for the original mixture but es-
sentially independent of the choice of column
internals. The different column types can then be
simulated on the basis of available models taking
into account the uid dynamics of various col-
umn types. These simulations can then be used to
optimize the column performance for a selection
of different column internals and operating con-
ditions. The choice of column internals can -
nally be based on these optimized column simu-
lations, while in the conventional approach this
choice must be based on experience very early on
in the course of process design.
3.3.1. Internals and Operating Conditions
The following guidelines apply for the selection
of the free area in pulsed columns. An increase in
the free area is recommended in systems with a
low interfacial tension where it leads to a great
reduction in the column volume. At moderate
interfacial tension, the column diameter can be
reduced by a greater free area, but at the expense
of the column height. In the case of extremely
high interfacial tension, there is no point in
increasing the free area.
The material of the internals should be select-
ed so that the continuous phase, but not the
dispersed phase, wets the plates. As a rule of
thumb, metal plates can be used when the organic
phase is dispersed; if the aqueous phase is dis-
persed, the internals should be of plastic, both in
pulsed columns and in rotary-agitated columns.
In deciding which phase should be dispersed,
the direction of mass transfer must be taken into
account. In accordance with Figure 33, mass
transfer should be from the continuous phase to
the dispersed phase, if possible. In the nal phase
selection, however, uid-dynamic considera-
tions frequently conict with operating and safe-
ty requirements. The position of the interface in
the column determines the phase which is dis-
persed. Figure 37 summarizes the possible
combinations.
The separation efciency determines the col-
umn height and the load limit determines the
column diameter. For optimization, the two
parameters are related by the ratio q =
HETS/(v
c
v
d
) which can be used to optimize
the column internals and energy input. A mini-
mum value of this expression is equivalent to a
minimum column volume. Figure 38 shows that
optimum pulsing is obtained between the maxi-
mum of the ooding point curve and the mini-
mum of the HETS curve. In this gure the drop
diameter, which is the key parameter in HETS
and maximum load, decreases from left to right.
An analogous procedure is used for rotary agi-
tated columns. The design point for industrial-
scale columns is chosen to be 75 80 % of the
load limit. The operating point with respect to
Figure 37. Selection of phases and plate materials
load and pulsing (rotation) is xed by this
procedure.
3.3.2. Column Diameter
Assuming the same column geometry, the spe-
cic throughput of the test column is adopted for
the large-scale column:
(v
c
v
d
)
2
= (v
c
v
d
)
1
with
(v
c
v
d
)
1
= 0:75(v
c
v
d
)
1 max
Index 1 = pilot scale
Index 2 = large scale
Here it has been assumed that the optimal opera-
tion conditions occur at 75 % of ooding load,
which is a good choice in many cases. This gives
the column diameter:
D
2
=
4
m_
F
r
F
m_
S
r
S
_ _
2
p(v
c
v
d
)
2
_
3.3.3. Column Height
The separation efciency 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, scientic investiga-
tions of this problem are rather poor and mainly
empirical knowledge of industrial engineers
exists. The different chapters of [5] list formulae
from experience with countercurrent extractors
as described here, including
Pulsed sieve tray columns [100]
HETS
2
HETS
1
= exp [1:64 (D
2
D
1
)[ (15)
(in Equation (15) the factor 1.64, given
by THORNTON, is only valid for small columns.
Figure 39 shows an empirical dependence of the
Thornton factor from the column diameter pub-
lished by REISSINGER [68])
Reciprocating columns [101]
HETS
2
HETS
1
=
D
2
D
1
_ _
0:38
(16)
Figure 38. Optimization of pulsation
Figure 39. Dependence of Thornton factor on column
diameter
When the plate geometry and amplitude of the
vibration are left unchanged in the large-scale
column, the frequency should be reduced, ac-
cording to:
f
2
f
1
=
D
1
D
2
_ _
0:14
The following applies to stirred columns
[102]:
HETS
2
HETS
1
=
D
2
D
1
_ _
0:33
A more detailed description of column and
rotator design for stirred extractors is given in [8].
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,
exibility 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
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 difcult;
systems with such physical properties require a
higher dissipation of energy than in the converse
case. Phase separation is favored by a high
density difference and interfacial tension, where-
as a high viscosity makes phase separation more
difcult.
The lower limit for the density difference can
be taken to be 50 kg/m
3
. 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 sepa-
ration problems. In industrial units, approximate-
ly s = 1 2 mN/m can be taken as the lower
limit. Therefore, mixer settlers can certainly
not be used for mixtures of relatively low inter-
facial tension; because of the shear eld gener-
ated, centrifugal extractors also have a dispersing
effect which should not be underestimated. In
such cases, the energy input must be very care-
fully controlled. Rotary-agitated columns and
pulsed columns can be used, in which the energy
input 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 efciency. 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 continuous shaft. In
centrifugal extractors, the Robatel design pro-
vides 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.
Generally, extraction columns have diameters
not signicantly above 3 m, while mixersettlers
have been built with huge dimensions.
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
efciency at large diameters is no longer
satisfactory.
The literature contains some publications
which recommend criteria for the selection of
the best apparatus. However, most of these re-
commendations 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 uid-dynamic studies to
be carried out under comparable conditions [63].
The following 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, inves-
tigations by different authors are not always
mutually comparable with respect to the absolute
HETS values. Evidently, the column length and
the phase ratio have an unexpectedly large effect.
Also certain electrolyte effects which depend on
the quality of the water used may play an impor-
tant role [57].
For the toluene system, PILHOFER compared
the different operating characteristics of various
groups of equipment. Analogous studies on the
liquid system butyl acetate water acetone
were carried out by GOLDMANN [83]. Figure 40
shows a diagram of GOLDMANN with the number
of theoretical stages NTS per meter of column
height, as a function of the load. The gure
contains data for QVF and Kuhni columns the
latter with ve different free areas of the perfo-
rated partition disks and for pulsed sieve plate
extractors (PSE) with ve different free areas j
and one reciprocating column (Karr). The rotary
agitated columns of QVC and Kuhni with the
smallest free areas j clearly achieve the highest
NTS values, but allow only low loads. Also, the
other Kuhni columns show higher NTS values
than the pulsed columns but smaller ranges of
load. Generally speaking, all measures which
improve the separation efciency reduce the load
capacity.
A comparison between pulsed sieve trays
and structured packings with the test system
toluene water acetone was published
[103]. Figure 41 shows the diagram with the
extractor efciency in dependence on the load.
It is obvious that structured packings have the
broadest range of load capacity and reach the
same or higher efciencies as pulsed sieve trays.
From the results for two structured packings
without pulsation the positive inuence of puls-
ing can clearly be seen: The pulsed unstructured
packing, Pall rings 15 15 mm, has a clearly
smaller load range.
In Figure 42, the range of loads is compared
for sieve trays and structured packings with
pulsation [104]. According to that, packed
columns have signicant advantages. As shown
in [104] and updated in [8], the investment costs
of pulsed structured packed columns are 30 %
lower than the ones of pulsed sieve tray columns
and 20 % lower than pulsed unstructured packed
columns.
In [105] a systematic study on extractor se-
lection is given. Ascheme for systematic column
selection is presented in Figure 43 [8].
Adaptation of the Column Geometry to the
Separation Problem. In the early days of ex-
traction, various types of apparatus were restrict-
ed to clearly dened geometries and were thus
sharply distinguished from one another. Recent
apparatus developments allow adaptation 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 uid-dynamic description of related
types of apparatus is feasible. The optimization
Figure 40. Comparison of the number of theoretical stages NTS in dependence of total load for Kuhni, QVF, Karr and pulsed
sieve plate extractors (PSE) [83] (system butyl acetate water acetone, phase ratio v
d
/v
c
~ 1.12, measurements of various
authors cited in [83])
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 nal selection of equipment is
often based on product-specic 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 volume
ow 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 oper-
ating conditions are given below.
RAUSCHER [81] 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 conrmed the experience that
the separation efciency declines for phase ratios
unequal 1 and found the following causes: By
dispersion of the smaller volume ow (phase
ratio 1), stronger backmixing of droplets by
the continuous phase will occur, leading to a
broader drop-size distribution. By dispersion of
Figure 42. Range of load of pulsed structured packed col-
umns in comparison to pulsed sieve tray columns in depen-
dence of the mass density difference for aqueous systems and
systems similar to water
Figure 41. Comparison of efciency versus load of packed columns with and without pulsing and pulsed sieve tray extractors
a f = pulsation intensity, B
f
= ooding load, j = relative free area
Figure 43. Systematic selection of extraction equipment [8]
the larger volume ow (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 [77] investigated the uid dynam-
ics of pulsed sieve tray and Kuhni rotating
extractors using liquid systems with viscosities
up to 50 mPa s, mixed from parafn oil and
n-hexane as organic phase and of glycerol
and water as aqueous phase. I. WAGNER [106]
continued the work with mass-transfer investiga-
tions using the system tridecanol as drop phase
(h = 42 mPa s), water, and propanol. The ex-
periments showed that the mean Sauter drop
diameter increases with increasing drop viscosi-
ty; holdup is decreased, while the ooding curve
is shifted to higher throughputs. In case the
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 inuenced in a broader range
than in pulsed columns; yet, more energy will
be required for a certain drop dispersion. Inten-
sive stirrers as in Kuhni 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 inuenced by the
rotating or pulsating internals. Here, lower inten-
sity 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 Internals
In gravity settlers each extraction stage consists
of two steps: (1) dispersing and (2) phase sepa-
ration by coalescence of drops, thus generating a
homogeneous layer of drop phase. Figure 44 A
shows a vertical settler at the top of a column for
the case that the drop phase has a lower density
than the continuous phase. The drops rise against
the sinking continuous liquid and are blocked
by the upper level of the continuous phase, which
is the principal interface. There, coalescence of
the dispersed phase will occur both between
adjacent drops and at the principal interface. The
coalesced drop phase leaves the extractor at the
top of the column.
In a horizontal settler, as shown in Figure
44 B, both phases ow in the same direction.
Drops of lighter dispersed phase rise to the
interface where they coalesce to form a homoge-
neous layer. In the lower part of the settler a layer
of the continuous phase remains, growing in ow
direction due to decreasing drop numbers. The
wedge-shaped zone of dispersion should end
before the placement of phase outlets. Typical
ow rates for all types of horizontal settlers are
around 12 cm/s.
As impurities and especially small amounts of
ionic species present in technical liquid systems
change the interfacial properties relevant for
Figure 44. Vertical (A) and horizontal (B) gravity settlers for drop separation from a continuous liquid
coalescence [5355], an exclusively theoretical
modeling, as developed by many authors (see for
instance [109]), is insufcient. However, the
length of a horizontal settler can be estimated
by a combined procedure of calculations and
simple and cheap batch settling experiments
[108]. The calculation is based on a model of
the physical processes in a settler, while experi-
ments supply one empirical parameter to include
surface phenomena that could not be modeled so
far (see Figs. 45 and 46).
A glass cylinder as shown in Figure 45 A,
lled with about 1 L of the original liquid
liquid 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 45 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 sufcient repro-
ducibility of measurements it should be made
sure that the glass ask is washed with deionized
water, that the distribution of drop sizes is narrow
and the temperatures of the liquid liquid sys-
tem in the glass cylinder and the continuous
settler are equal [107]. The reproducibility can
be improved if the system is not shaken by hand
but rather a specic small apparatus, designed by
HENSCHKE, is used [108]. The special features of
this thermostatted equipment are stirrers
mounted on two counter-rotating shafts that
avoidintroduction of an overall circulation inside
the ask and a special top which avoids air being
sucked in from the surface.
The concept of settler dimensioning is shown
in Figure 46. All equations mentioned in the
following are given in [108]. Settler dimension-
ing starts with evaluation of settling experiments
according to Figure 46 A. The linear curve of
sedimentation supplies the velocity of sedimen-
tation; a model of drop swarm sedimentation
supplies the diameter of the starting drop swarm
[85]. The thickness of the dense layer of drops
follows from a balance of sedimenting and coa-
lescing drops in time steps. The next stage is
calculation of drop deformation in vertical steps
[109]. 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 homo-
phase formed by coalescence [109]. The coales-
cence model contains a tting parameter F
p
to t
the calculated and measured coalescence curve
in Figure 46 B. This parameter is the link be-
tween the settling experiment and the settler
dimensioning; F
p
can be used for the settler
calculation, given in Figure 46 B.
The settler needs an inlet length L
in
which can
be calculated by a model equation in dependence
on settler diameter, operation parameters, and the
mean drop size at the settler inlet, coming from
the extractor outlet. For calculation of coales-
cence in the dense drop layer the same equations
that were modeled for the settling experiment can
be applied using the tting parameter F
p
derived
from these experiments. The result is the geom-
etry 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
equation system needs computer aided solving.
A computer program is offered by [110]. A
simplied method is given in [108].
4.2. Settlers with Coalescing Aids
Gravity settlers are often equipped with coa-
lescing aids to t a settler to special conditions
of the liquid system or of the operational behav-
ior. The internals allow the required settler
length to be reduced by a factor of 25 in many
cases. Since settler volume is one of the major
Figure 45. Experiments on batch settling
problems of mixersettler units, this reduction is
very signicant for economic performance. In-
dustrially proven coalescing aids are inclined or
corrugated plates, xed beds of small packings,
ber beds, porous sintered materials, and mem-
branes. In some cases, when the drop sizes to be
settled are smaller than 1 mm or if surfactants
render the settling more difcult, centrifuges [6,
Chap. 8] or electrical elds must be applied
[111]. The most important coalescing aids are
inclined packages of plain or corrugated plates
and ber bed lters.
Inclined Plates. Figure 47 shows one pos-
sible arrangement of inclined plates in a horizon-
tal settler. Other plate congurations 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, lled with inclined plates. Several
major effects can then be observed which lead to
a reduction of required settler length. The plates
shorten the sedimentation distance of drops and
provide a larger interfacial area for the coales-
cence. Since in many cases the viscosity of the
dispersion is higher than that of the clear phases,
the internals induce a larger ow resistance to
the dispersion, which leads to an increased
retention of the dispersion as compared to the
clear phases. Also, due to the large diameter of
technical settlers, rather small ow rates may
already lead to Reynolds numbers in the turbu-
lent regime. In this case internals reduce the
characteristic dimension of the settler and en-
sure laminar ow.
Figure 46. Dimensioning a continuous settler [108] A) Evaluation of settling experiments; B) Fitting of measured and
calculated curve
The drops coalescing at the plates form trick-
ling lms which ow off to the horizontal, prin-
cipal interface due to a hydrostatic pressure
difference. A plate material wettable by the drop
phase is preferred but not necessary. Several
scientic investigations and experiments with
liquid systems of a wide range of properties were
made [112119]. The main results are:
1. Thin laminar lms should ow on the plates,
because the coalescence of drops is promoted
by the shear stress of lm ow near the plate;
the larger the volume ow of cocurrent con-
tinuous phase, the smaller the lm thickness
and the better the coalescence.
2. The plate should preferably be wettable by the
drop phase (advancing contact angle < 70
,
receding contact angle > 15
).
3. The drop swarm has to be distributed equally
over the width of plates.
4. Constructions that can thin the trickling lm
increase the settler performance.
5. Short lengths of plates of about 400 mm are
sufcient for coalescence of drops riding on
the lm.
6. The width b
p
of a plate can be calculated by
the empirical equation of the Reynolds num-
ber of trickling lm
Re
f
_ 80 K
0:19
L;d
b
p
= 0:03
V
d
(Re
f
k v
d
)
3=2
D r g sin a
h
d
_ _
with the liquid number of trickling lm
K
L;d
=
s
3
r
d
g h
4
d
r
d
D r
where a is the plate inclination, V
d,1
= V
d
/n
the volume owof dispersed phase on a plate,
and n the number of plates.
7. The optimumof plate inclination is within the
range 10
< a < 15
.
8. The trickling lm continuously carries sur-
factants to the outow of a plate and thus
prevents their accumulation. Therefore sur-
factants hardly inuence coalescence and set-
tling performance up to medium ow rates of
drop phase.
9. Under certain conditions, the drop coales-
cence leaves very small droplets, so-called
secondary drops, due to partial coalescence,
which generate a droplet entrainment at the
settler exit. Its occurrence is primarily a ques-
tion of liquids involved, i.e., their viscosity
ratio [115].
The coalescence time of secondary drops is
signicantly higher than that of primary drops,
due to their small sedimentation velocity. Set-
tling of secondary drops requires other coales-
cers, for instance ber-bed or membrane coales-
cers or centrifuges.
HuLSWITT [119] has shown that the design of
horizontal settlers with internals can be de-
signed based on an experiment similar to that
of HENSCHKE [108] where the internals are in-
cluded in the settling ask (see also [90, 119]).
The reduction in settling time due to the inter-
nals as compared to the empty ask roughly
corresponds to the reduction in required settler
length. If internals tend to hinder the direct ow
of the dispersion like random packings the
required settler length appears to be further
reduced.
Figure 47. 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
Fiber bed lters are built from short bers
stuffed to rectangular mats or to disks of 15 to
25 mm thickness, held in a suitable support, or
from ber eeces as shown in Figure 48. These
ber eeces can also be tightly wrapped around a
permeable support tube which is sealed at one
end. These tubes are then mounted on a plate with
their open end. With this construction the ow
rate through the ber bed can be reduced while
retaining a high overall ow rate through the
settler vessel.
The ber beds have a denite, large voidage of
about 95 %; nevertheless they are sensitive to
solid dirt particles in the liquid. The droplets
couple to the bers while owing through the
ber bed, succeeding drops coalesce with them
and enlarge the size of adhering drops until the
liquid ow pulls them out of the bed due to
increasing ow resistance. A ber bed is able to
enlarge the sizes of incoming drops at least by
one order of magnitude so that they can coalesce
in a subsequent gravity settler with their homo-
phase. Fiber bed lters are restricted to drop
concentrations < 10 vol % to avoid redis-
persion.
REBELEIN [120, 121] and MAGIERA [122, 123]
dened heuristic rules for the design of ber beds
on the basis of careful experiments with a broad
variation of parameters of inuence, which have
been supported to a large extent by SPETH [124,
125]:
1. Fiber materials as glass or stainless steel with
high energetic surfaces provide different in-
teraction sites (e.g., hydrogen bonds and ion
dipole interaction) for the liquid and improve
the ber bed performance compared to mate-
rials with low energetic surfaces as for in-
stance Teon. High energetic surfaces im-
prove the wetting properties of the bers.
2. The drop enlargement in a ber bed decreases
with increasing owrate, i.e., with supercial
velocities > 1 cm/s.
3. Small ber diameters of about 15 mm are
favorable.
4. The bed depth required for coalescence in-
creases with the ber diameter.
5. The concentration of droplets in the incom-
ing liquid hardly inuences the bed perfor-
mance.
6. The larger the surface tension of the liquid
system, the better the separation perfor-
mance.
7. 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 inuence within 50 and
5000 mPa s.
All attempts to calculate the bed performance
in advance via lter coefcients were fruitless
[120123]. MAGIERA developed a mathematical
model of physical mechanisms inside a ber bed
and was able to simulate the bed behavior and
drop enlargement by introduction of two experi-
mental tting parameters. Later, SPETH continued
his work and showed quantitative agreement
with experiment [124, 125]. Therefore, a reliable
Figure 48. Combined ber bed coalescer and gravity settler
dimensioning of ber beds needs experiments
with the liquid dispersion which is to be
separated.
Membrane Coalescence. This method to
separate ne droplets down to 1 mm from emul-
sions, stabilized by surfactants, was discovered
and investigated by HOFFMANN [126] (Fig. 49).
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 polytetrauoroethylene
(PTFE), held in place by a support, is permeated
by two-phase ow of emulsion. The emulsion
leaves the membrane as a liquid foamwith large
oil domains which will immediately coalesce at
the principal interface in a succeeding settler. A
supercial velocity through the membrane is
possible within the range of 0.1 to 19 cm/s, the
pressure drop is comparable with that in ber
beds. The main advantages are huge separation
performances of about 98 %, in combination
with a large range in throughput; the ability to
separate droplets one order of magnitude smal-
ler than in ber beds; and the insensitivity
against hydrophobic surfactants. Hydrophilic
surfactants are without inuence, too, if their
amount is clearly lower than the critical micelle
concentration.
Selection of Appropriate Settler. Most
important and the rst step in selection of a settler
is a careful analysis of separation problems [107,
127]. The ow 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 systemand settling experiments in a
glass cylinder show, if and why a phase separa-
tion can be problematic. Drop sizes smaller than
100 mm 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
partial coalescence, resulting in very ne drops,
so that a ber bed or a membrane coalescer will
be necessary.
The presence of solid particles or mud require
lters before the settler. The wetting behavior of
coalescing aids can signicantly change the op-
eration of the process. This should be accounted
for in the process. The phase ratio 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.
A major parameter which has long been over-
looked is the electrostatic behavior of the inter-
face which is, e.g., strongly inuenced by elec-
trolytes present in the system [5355] leading to
changes in settling times by several orders of
magnitude. The electrolytes determine the elec-
trostatic potential difference between the
phases, which in turn affects the approach of
two interfaces, i.e., coalescence. The concen-
trations at which the electrolytes have an inu-
ence on the coalescence behavior may be as low
as some few mmol/kg, which means that all
other properties of the system like density,
viscosity, and interfacial tension are not affect-
ed. When designing a settler this has to be taken
into account appropriately. It has been shown
that adding, e.g., 50 mmol/kg of a well-chosen
salt to the system can stabilize coalescence
behavior [57]. The added salt must have a higher
concentration than any other ionic species pres-
ent in the system by a signicant factor, which
means that this addition is of technical relevance
only if the concentration of all other ionic
species is relatively low.
Figure 49. Membrane coalescer [126]
5. Liquid Liquid Extraction
Processes
5.1. General
The quality of the rafnate in liquid liquid
extraction can be controlled easily by changing
the ratio of solvent to feed and the extraction
temperature. The quality of the extract is gov-
erned 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 mini-
mize solvent requirements. In such a system, a
maximum extract purity is obtainable and some
components that should end up in the rafnate
leave with the extract.
Additional steps are, therefore, required to
enhance extract purity and thus rafnate yield.
If the extract is the product desired, improving
extract purity is the most important in fact, the
only objective. Different solutions to this prob-
lem 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. 50 A). In the triangular diagram, this means
that the binodal curve is changed from a to b
(Fig. 50 B).
Because the composition of the rst extract is
now inside binodal curve b, it separates in a
settler b in a purer nal extract phase and a small
amount of intermediate rafnate phase. The latter
is returned to the main extraction system.
The selectivity of separation in the additional
stage is not very high because the loading of the
rst extract phase is rather high and separation
takes place near the plait point. This system can
be used when the main systemis operated at high
temperature for other reasons or when an in-
crease in extract purity and the resultant increase
in rafnate 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 Section
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 nal extract phase. In
this way, no unwanted inuence is exerted on the
main extraction system.
However, because water must be separated
from the solvent by distillation before its reintro-
duction 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
Figure 51, a second solvent can be fed into one
end of the extraction system, on the opposite side
Figure 50. Use of cooling stage A) Process ow scheme: a) Extractor; b) Settler B) Triangular diagram: a) Binodal curve at
higher temperature; b) Binodal curve at lower temperature
of the solvent entry point. The feed in this case is
introduced somewhere in the middle of the
system.
The countersolvent should be only slightly
soluble in the solvent and, therefore is generally
similar in chemical structure to the key compo-
nent of the rafnate 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 rafnate and the extract
(i.e., either a much lower or a much higher
boiling point). Because the countersolvent does
not contain any rafnate components when it
enters, it can wash out the rafnate components
in the solvent at the feed point.
Additionally, some extract components are
washed back by the countersolvent, thus
increasing the load in the top section. In this way,
a very pure nal extract can be produced, depend-
ing on the ratio of countersolvent to feed used.
A disadvantage of this system is that the
countersolvent enters the top section. Conse-
quently, the phase ratio of B-rich to A-rich phase
is reduced, resulting in a less pure rafnate (this
also means a lower yield of extract). To restore
rafnate purity, more B-rich phase must be ap-
plied. Such a systemis thus costly and sensitive to
changes in feed composition, solvent-to-feed
ratio, and ratio of countersolvent to feed.
Some improvement can be obtained by carry-
ing out the extraction in two parts (Fig. 52).
In the rst extractor (a), the feed is extracted
with the primary solvent. The intermediate
extract phase is fed to a second extractor (c) and
brought in contact with the countersolvent. The
mixture of countersolvent and intermediate
rafnate is fed to a column (b) in which the
intermediate rafnate and the countersolvent
are separated by distillation. The pure interme-
diate rafnate is then fed to the rst extractor,
while the countersolvent is charged to the second
extractor. In this way, some of the disadvantages
can be overcome.
5.2. Combined Processes of Extraction
and Distillation
Azeotropic Distillation. Usually it is nec-
essary to combine extraction and distillation
processes for recovering the solvent from the
Figure 51. Extractor for separation using a countersolvent
(a) Extractor
Figure 52. Use of countersolvent with intermediate recovery
a) First extractor; b) Distillation column; c) Second extractor
extract phase and also fromthe rafnate phase, if
the solvent is soluble in the rafnate.
Figure 53 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 advanta-
geous because of the very high energy demand of
a water-rich feed distillation. The triangular dia-
gramof Figure 53 shows that the binary systemof
solvent MTBE and water has a heterogeneous
azeotrope. As a consequence, extraction has to be
combined with azeotropic distillation as shown in
the owsheet of Figure 53 B. Byextractioninthe
extractor E extraction feed F is changed to raf-
nate 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 extract 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 triangle diagram. The acetic
acid-free rafnate 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 puried 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 reux 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. Mixed integer nonlinear
programming (MINLP) has been successfully
introduced in optimization of such processes
[128, 129]. MINLP can be used as a process
synthesis tool. It is necessary to generate a so-
called superstructure of the hybrid process
which contains a variety of alternative ow
sheets. Then MINLP is able to choose the best
solution for given parameters and also from
competitive unit operations like extractive dis-
tillation, processes with more than one solvent
or processes with reextraction for solvent
recovery.
Extractive Distillation. Another possibility
to separate azeotropic mixtures is extractive
distillation. Asolvent with a much higher boiling
point than the feed is fed at the top of a distillation
column to entrain one component of the distilla-
tion feed that enters the column at the bottom
( Distillation 1. Fundamentals). The combined
system of liquid liquid extraction and extrac-
tive distillation is applied in nearly all processes
used to manufacture very pure light aromatics. N-
Formylmorpholine is a suitable solvent to sepa-
rate the light aromatics benzene and toluene used
as feedstock for the petrochemical industry
[130135]. Due to the selectivity of N-formyl-
Figure 53. Triangular diagram (A) and ow sheet (B) of a
hybrid extraction distillation process for separation of wa-
ter and acetic acid with MTBE as solvent [128]
E = extraction; C-1, C-2 = distillation; S = settling;
H = condenser
morpholine (NFM), extremely high yields of
very pure products are obtained.
A simplied process ow scheme for N-for-
mylmorpholine extraction is given in Figure 54.
Feed enters the extractor at an appropriate point
in the bottom half of the column. The exact
location depends on the composition of the feed
and can be optimized for each feedstock. Solvent
enters at the top of the extractor at the selected
temperature. Because NFM has a high solvent
power, this must often be reduced by addition of
water. In general, 4 10 % water is sufcient to
ensure a lowsolubility of saturated hydrocarbons
while still maintaining a high solubility of aro-
matics. The rafnate 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 dissolved solvent. The wa-
ter solvent mixture from this washing opera-
tion is charged to the bottomof the main extractor
to increase the water content of the solvent phase
as discussed above.
The solvent aromatics mixture from the
bottom of the extractor still contains some
alkanes. This stream is routed to an extractive
distillation column. In the lower part of this
column, saturated hydrocarbons are stripped off,
which results in high-purity aromatics at the
bottom. Because 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 evap-
orated at the feed point. The resulting top prod-
uct, therefore, has a very low aromatic content
and is very effective as a reux in the bottompart
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
available as product or can be routed to a distil-
lation train to separate the individual compounds.
Some of the aromatics are returned to the top of
the distillation column as reux. 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 rafnate washing. Some-
times, part of the water is used as reux instead of
extract. In this combination, ultimate use is made
of the solvent characteristics in both the extrac-
tion 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
Figure 54. Morpholine solvent process a) Extractor; b) Washing; c) Extractive distillation column; d) Distillation column;
e) Settler
used to alter the properties of inorganic cations
that are to be extracted from an aqueous solution
to make them soluble in the nonpolar organic
solvent. The reaction mechanism can best be
compared with a cation exchange process. The
solvent acts like a liquid ion exchanging the ion to
be extracted for protons.
The use of this process for extraction of anions
is far less known but is of the same importance.
The mechanism of this type of reaction proceeds
most of the time through ion pair formation and
can best be compared with an anion exchange
process.
A third possible mechanism is the solvating
and/or chelating reaction. In a reaction of this
type, one or more molecules of water in the
hydrate layer of the ions are replaced by the
active solvent. The new complex will be insolu-
ble in water but soluble in the solvent.
Generally, the formation of a complex is a
slow reaction. Therefore, in many cases, it is not
possible to use columns for this type of extrac-
tion. In many applications mixer settler are
used to make the extraction possible.
A reactive extraction will need a re-extrac-
tion to isolate the extracted substance from the
solvent. The active solvents used in reactive
extractions are water insoluble compounds.
They are used undiluted or in solution in an
inert solvent.
For reactive extraction an EFCE standard test
system has been selected, and data and models
describing equilibrium and reaction kinetics
have been published [136, 137]. The extraction
of zinc from aqueous solution with di-2-ethyl-
hexylphosphoric acid (D2EHPA) dissolved in
isododecane was chosen. Thus, if principal in-
vestigations on reactive extraction are per-
formed, it is recommended that this system is
used for reference to allow comparison of, e.g.,
extractor performance.
5.3.2. Extraction Mechanism of Different
Types of Solvent
Classical Complexing and/or Chelating
Agents. The active solvents are usually large,
polyfunctional molecules. Most of them are de-
signed to extract specic cations. Dioximes,
hydroxyoximes, quinolines, b-diketones, etc.,
are rather expensive but widely used solvents to
extract metal ions such as copper and nickel from
the aqueous phase.
Metal complexes are formed in the water
phase in a substance-specic 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,
nontoxic, 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.
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 coefcients on pH is shown in
Figure 55.
The different curves give the variation of the
distribution coefcient D in dependence of pH
for different cations. These solvents are not
specic for certain cations, but are very suitable
to concentrate and recuperate trace elements
from efuent streams [146, 147].
Ethers and Thioethers. Reactive extraction
with ethers and thioethers can be described by:
R
2
OHXR
2
OH
R
2
SHXR
2
SH
where HX stands for a strong acid, e.g., H

2
SO
4
or HCl, and Xis the anionic rest of the acid. Most
metal ions that are capable of forming anionic
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-ex-
tracted from the organic phase with water. Most
of these anionic complexes form strong acids
which protonate with the ether group to form
oxonium(thionium) salts. These salts, however,
are soluble in ether or thioether. It is also
possible to extract Cl
from water with (R

2
O)
2
H
2
SO
4
, the sulfate ion being replaced by the
chloride. This type of solvent is normally used in
undiluted form [143].
Ketones extract the same anionic com-
plexes as ethers, but in most cases at lower acid
concentration. Complexes with weaker acids can
also be extracted. Methyl isobutyl ketone and
cyclohexanone are industrially used in the sepa-
ration of Nb Ta as F
complexes [149] (
Niobium and Niobium Compounds, Section
4.3.1.) and in the separation of Zr Hf as CNS
complexes ( Zirconium and Zirconium Com-

pounds, Section 1.4.2.) [153]. The solvents are
used in undiluted form. A great disadvantage of
this and of the former type of solvents is that they
are not completely insoluble in water. A distilla-
tion is needed to remove the dissolved solvent
from the water phase.
Trialkylphosphine Oxides; Trialkyl Phos-
phinates, Phosphonates, and Phosphates.
These extractants function according to:
R
3
POHXR
3
POH
ROR
2
POHXROR
2
POH
(RO)
2
RPOHX(RO)
2
RPOH
(RO)
3
POHX(RO)
3
POH
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 TiOSO
4
[151]
from a sulfuric acid solution with dibutyl butyl-
phosphonate (DBBP) as the solvated complex
2 DBBP TiOSO
4
H
2
SO
4
5 H
2
O. These
organophosphorus solvents are, due to their out-
standing chemical stability and good physical
properties, most widely used in reactive extrac-
tion [144, 145].
Free acids can also be extracted, the basicity
of the solvents decreases from phosphine oxide
to trialkylphosphate. The distribution coef-
cients are rather small so that large volumes of
solvent are needed in an extraction process [141,
142, 148]. These extractants are used as such or
diluted in an inert solvent (petroleum fraction)
with or without modier. The distribution coef-
cients in metal extraction are usually very high
and depend on the acid concentration. The
products are rather expensive.
Figure 55. Plots of log D vs. pH for extraction of metals
Trialkylsulfonium (Selenium, Tellurium),
Tetraalkylammonium, and Tetraalkylpho-
sphonium (Arsonium, Stibonium) Salts.
These reagents extract according to
[R
4
N
[
Solvent
[B
[
Raffinate
[R
4
N
[
Solvent
[A
[
Raffinate
These onium compounds form ions both in
acidic and basic medium. The mechanism of
extraction is practically always anion exchange
[143]. The onium compounds are regenerated in
the same way as anion exchanger resins by re-
extraction with a base. These solvents are used in
the production of Cr, V, Re, Tc, Mo, and W as a
solution in a petroleum fraction.
Amine and Phosphine Salts. These re-
agents extract according to:
R
3
NHXR
3
NH
R
3
PHXR
3
PH
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
HVO
3
, chromium as H
2
Cr
2
O
7
, and manganese
as HMnO
4
. Most used are the tertiary amines
because 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 coefcient at different
temperatures. At low temperature (20

C), the
distribution coefcient solvent/rafnate is > 10.
At high temperature (130

C), the coefcient 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 coefcients for
different anions.
[R
3
NH
[
Solvent
[B
[
Raffinate
[R
3
NH
[
Solvent
[A
[
Raffinate
For trioctylamine in an aromatic solvent the
order of extractability is
I
Br
> NO
3
> Cl
> S
2
O
2
3
> PO
3
4
> SO
2
4
This series is dependent on the type of amine,
the diluent, and the temperature and must be
determined for any given system [5]. This series
can be enlarged for organic compounds, capable
of forming ion pairs with the amine. Phenols
and substituted phenols can be extracted with
better distribution coefcients than chlorides.
In this series thiophenols and some mercaptans
are situated between bromide and nitrate and
all sulfonic acids are better extracted than
phosphate. This makes the sulfate salts of amines
a very good choice for new extraction systems.
(R
3
N)
2
H
2
SO
4
(R = octyl) is capable of ex-
tracting Cl
and/or NO
3
[150] from a mixture of
both anions with SO
2
4
. The value of the distribu-
tion coefcient of the anions is surprisingly high.
D
Cl
=D
SO
4
~ 100
D
NO
3
=D
SO
4
~ 400
A disadvantage of these solvents is the fact
that per mole amine one mole of salt is formed
after regeneration. However, most of the time,
the anions to be removed are present in the
solution only as trace impurities, so that this
drawback is not signicant. Another disadvan-
tage of amines is the poor solubility of ammoni-
umsalts in aliphatic hydrocarbons. To avoid third
phase formation, the use of aromatic solvents
(smell) or aliphatics with modiers is necessary.
Amines can also act as solvating agents in an acid
medium. Iron, zinc, and uranium salts can be
extracted in this way [143].
5.3.3. Uses
1. Ableed froma (NH
4
)
2
SO
4
crystallization unit
in a caprolactam plant contains 40 %
(NH
4
)
2
SO
4
, 10 % NO
3
, 50 ppm Cl
and
3 4 % organic sulfonic acids. The solution
is extracted by trioctylammonium sulfate, 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 Shell-
sol AB (aromatic hydrocarbon). The rafnate
is returned to the crystallization plant for
(NH
4
)
2
SO
4
recovery.
The re-extract contains 35 % of nitrate,
0.016 % of chloride, the sulfonic acids, and
only 0.1 % of sulfate and is treated sepa-
rately.
Compared with a conventional stripping,
the use of chemicals in this systemis strongly
reduced. 80 % less NaOH is consumed be-
cause the base is only used to liberate the
amine and not to neutralize the NH
3
from
(NH
4
)
2
SO
4
[150].
2. Traces of phenol (20 200 ppm) and bisphe-
nol (20 100 ppm) can be extracted fromthe
wastewater of a polycarbonate plant to values
< 1 ppm. The re-extract containing sodium
phenolate and bisphenolate (300 500 times
more concentrated) can be returned to the
polycarbonate plant. The solvent used is
5 % trioctylamine in Shellsol AB [154].
3. From a plant for the production of vulcaniza-
tion 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 Shellsol
AB [150].
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
carried out with various types of amines as
HCl or H
2
SO
4
salt [143].
5. Mg
2
can be removed from a saturated solu-
tion of (NH
4
)
2
SO
4
by extraction with the
ammonium salt of diethylhexyl phosphoric
acid (DEHPA) at pH > 5. It can be recovered
by lowering the pH to < 3 [152].
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, Section 5.8.). With an
aqueous feed of 200 3000 m
3
/h a whole
new technology had to be developed. Copper
can be extracted after acid or ammoniacal
leaching. The aqueous stripping phase is used
directly 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, 139, 148].
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 solution by
precipitation or extraction. From a medium
concentrated aqueous chloride solution
(100 200 g/L), Co can be extracted by
amines together with only traces of Ni. After
scrubbing with 4 5 MHCl, 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 acidication of the aque-
ous solution). Some Ni is co-extracted and is
removed by scrubbing with a Co solution thus
replacing any extracted Ni by Co. Co is nally
stripped by HCl, H
2
SO
4
, or HNO
3
depending
on the use.
The use of monooctyl octylphosphonic
acid (MOOP) to replace D2EHPA [138] per-
mits 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 oxi-
dized to the Co
3
state. Nickel is stripped rst
with dilute acid, Co remaining in the solvent.
Cobalt is then reduced to the Co
2
state and
stripped with diluted acid [5, 139, 141, 142].
All these examples are used in industry or in
pilot plants. Elaborate process and ow control
are essential to use this technology in a economi-
cal and meaningful way.
5.3.4. Setting up an Extraction System
A solution R contains three components: acid,
metal Aand 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 newextraction
system with these data is typical for any reactive
extraction system [151, 155].
The distribution coefcients 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 56.
The diagram shows a poor, practically con-
stant distribution coefcient Dfor the acid and an
increasing one for both metals A and B at in-
creasing 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 togeth-
er. The extraction coefcients E are related in the
same way as are the distribution coefcients,
E DS=R:
To extract metal A completely and in a rea-
sonable number of steps extraction has to be
carried out in zone 4 of Figure 56, the extraction
zone. At the same time, metal B and the acid are
only partially extracted into the solvent. The
number of steps can be calculated with the
Kremser formula. The Kremser formula calcu-
lates the efciency Z in the extraction
Z E
n1
E=E
n1
1
over n stages. For this equation the number of
stages can easily be calculated
n log f1=1Z11=E1=Eg=log E
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 56, the scrubbing zone. The amount of
water to be used is given again by the distribu-
tion coefcients 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 concentration of the dilute
acid should be such that the acid solution can only
take up the amount of acid to be removed fromthe
solvent. By scrubbing with pure water only a
limited amount of scrubbing uid can be used
because of the low distribution coefcient of the
acid. By adding a calculated amount of acid the
amount of scrubbing uid can be increased and
more component B can be removed without
removing component A. The rafnate, leaving
the scrubbing zone contains 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 56, the stripping zone,
metal Ais 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 coefcient, 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 56, the washing zone, the
acid and the rest of metal Aare washed out of the
solvent. After this step, the solvent is completely
regenerated and can be reused.
General Flow Sheet. Figure 57 shows a
general ow sheet of a reactive extraction
system.
Solvent Make-Up. Due to the poor distri-
bution coefcient of the acid several extraction
steps are needed to load the solvent with suf-
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 rst steps of
the solvent make-up any metal A present in the
solvent will be re-extracted in the rafnate.
Figure 56. Distribution coefcient in dependence on acid
concentration
Reactive Extraction. If sufcient 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 concentrationis 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
component, with a lower distribution coefcient,
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
solvent contains only metal A and acid. Using
water or a dilute acid solution, the puried metal
A can now be re-extracted into a water phase.
Solvent Washing. The solvent must be
completely regenerated before it can be recycled
to the solvent make-up. This is done by adding
some supplementary washing steps to the system.
The amount of water is chosen according to the
requirements in the scrubber and the number of
steps is calculated as a function of that amount.
5.3.5. Diluents and Modiers
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 solubility
to 175 mg/L. The choice of diluent is very
important. Higher amines are completely soluble
in aliphatic diluents. Their salts, however, are
only slightly soluble in the same solvents. There-
fore it is essential to test the solutions in all steps
of the process. If third-phase formation occurs in
one of the steps, the diluent must be changed or a
modier is to be added. These modiers are
normally long chain alcohols, monoesters of
polyhydric alcohols, or phosphate esters. These
modiers may considerably inuence the kinet-
ics of the extraction. Especially in the extraction
of copper the choice of modier is very impor-
tant. The different types of solvent are sold mixed
with a suitable modier which greatly enhances
the extraction performance of the solvent.
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S. M. Khopkar: Solvent Extraction Separation of Elements
with Liquid Ion Exchangers, New Age Science 2009.

Liquid-Liquid Extraction: Ckart Ller Osemarie Erger Ckhart Lass Omien Luyts Ndreas Fennig

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2012 Wiley-VCH Verlag GmbH & Co.

where HX stands for a strong acid, e.g., H

from water with (R

complexes ( Zirconium and Zirconium Com-

With this type of extractants most metals from

Primary, secondary, and tertiary amines must

] [sulfonic acid]. In three stages

, Ind. Eng. Chem.

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