d.

Solvent Extraction
Solvent extraction is a common form of chemical extraction using organic solvent as the
extractant. It is commonly used in combination with other technologies, such as
solidification/stabilization, precipitation and electrowinning.
Solvent extraction is a selective separation procedure for isolating and concentrating a
valuables metals from an aqueous solutions with the aid of an organic solution. In the
procedure the aqueous solution containing the metal of interest, often at a low
concentration and together with other dissolved substances, is mixed (extraction) with
an organic solvent containing a reagent. The metal of interest reacts with the reagent to
form a chemical compound, which is more soluble in the organic than in the aqueous
solution. As a consequence, the substance of interest is transferred to the organic
solution
Subsequently, in order to recover the extracted substance, the organic solution is mixed
(stripping) with an aqueous solution whose composition is such that the chemical
compound between the metal and the reagent is split and, thus, the metal is recovered in
the "new" aqueous solution, in a pure form. The concentration of the metal in the "new"
aqueous solution may be increased, often to 10-100 times that of the original aqueous
solution, through adjustment of the liquid flow rates. The organic solution is returned
for further extraction, either directly or after a fraction of it has been cleansed of
impurities.
McCabe Thiele Diagrams
In general terms the use of McCabe Thiele Diagrams enables the metallurgist or
engineer to calculate the number of stages required, or alternatively, to predict the
performance of a given set of conditions. Phase separation times are critical as they
have a direct bearing on the size of the settler required and on the overall process
efficiency.
Metal loading refers to the solvent phase and is a function of the solution properties,
namely pH. Competing ions will also have an effect on the metal loading. The
significance of the determination of loading is in the definition of optimum plant
operating conditions in terms of inventory of organic, O/A ratio and recirculation rates.
The rate of which the metal is transferred from one phase to another (kinetics) can be a
significant factor in the design and operation of the plant, whether in extraction or in
stripping.
Continuous Counter Current test
The basic equipment to perform a continuous mixing and coalescence process on a
technical scale is called a mixer-settler. It is often used in laboratories as an ideal tool
for basic system design of continuous solvent extraction processes because it offers
reproducable phase flow and contact times.
The device comprises a continuously fed and stirred mixing compartment (see sketch
below) and a gravity settler compartment where the liquids are allowed to separate. At
the end of the settler two individual weirs care for good separation of the liquid bulk

phases. The flow capacity of a mixer-settler is reached when the emulsion phase
dispersion band overflows the light phase weir or underflows the heavy phase weir.
In technical mixer-settler devices the volume of the settler compartment is often 10-fold
the size of the mixer compartment to provide sufficient settling time even for systems
with low coalescence rates (in case of high viscosity and/or low density and/or low
interfacial tension).

Solvent extraction theory and applications

INTRODUCTION
In chemistry, liquid-liquid extraction, or more briefly, SOLVENT EXTRACTION, is an
useful method to separate a substance selectively from a mixture, or to remove
unwanted impurities from a solution.
Solvent extraction (SX) is based on the transfer of a solute from one liquid phase into
another liquid phase. The success of this method depends upon the difference in
solubility of a compound in various solvents and becomes a very useful tool if you
choose a suitable extraction solvent.
In the practical use, usually one phase is a water or water-based (aqueous) solution and
the other an organic solvent which is immiscible with water.
Solvent extraction is used in nuclear reprocessing, ore processing, the production of fine
organic compounds, the processing of perfumes and other industries.

GENERAL CONCEPTS
Solvent extraction (SX) is the traditional term of liquid-liquid distribution that involves
the distribution of a solute between two immiscible liquid phases in contact with each
other. The principle is illustrated in Figure 2.1.
The vessel (a separatory funnel) contains two layers of liquids, that one is usually water
(Saq) while the other, an organic solvent (Sorg).
The organic phase often settles as the upper layer when it has a lower density than
water, but the opposite situation also occurs. A solute A, which initially is dissolved in
one of the two liquids, eventually distributes between the two phases. When this
distribution reaches equilibrium, the solute has one concentration [A]aq in the aqueous
phase and another concentration [A]org in the organic phase.

Figure 2.1. A schematic representation of solvent extraction (liquid-liquid distribution).

A solute A is distributed between the upper layer, an organic phase (Sorg), and the lower
layer, an aqueous phase (Saq).

Distribution ratio
In solvent extraction, a DISTRIBUTION RATIO (D) is often quoted as a measure of
how well-extracted a species is. The distribution ratio of the solute A is expressed as:
D = [A]org/[A]aq
where D is defined as "the total analytical concentration of the substance in the organic
phase to its total analytical concentration in the aqueous phase, usually measured at
equilibrium", irrespective of whether the organic phase is the lighter or heavier one.
If a second solute, B, is present, the distribution ratios for the various solutes are
indicated by DA , DB , and so on. If DB is different from DA , A and B can be separated
from each other by (single or multistage) solvent extraction. D is also called the
distribution coefficient or the extraction coefficient.
Depending on the system, the distribution ratio can be a function of temperature, the
concentration of chemical species in the system, and a large number of other
parameters.

Separation factors

The SEPARATION FACTOR(SF) is one distribution ratio divided by another, it is a

measure of the ability of the system to separate two solutes.
For instance if the distribution ratio for nickel (DNi) is 10 and the distribution ratio for
silver (DAg) is 200, then the silver/nickel separation factor (SFAg/Ni) is equal to DAg/DNi =
SFAg/Ni = 20.

DESCRIPTION OF THE SOLVENT EXTRACTION PROCESS

Solvent extraction is applicable in any instance where it is desirable to selectively,
remove or extract a species from one solution into another.
In metal recovery operations, the valuable component is normally a metal ion or a metal
ion complex contained in an aqueous solution. This aqueous solution is mixed intimately
with an immiscible organic phase containing the active extractant at which time the
active extractant transfers the desired metal from the aqueous phase into the organic
phase.
The "loaded organic" phase, now containing the desired metal, is then transferred to the
stripping section. Here the "loaded organic" phase is mixed intimately with an aqueous
stripping solution containing a chemical that provides the driving force required to strip
the loaded metal from the organic phase into the aqueous stripping phase. The
"stripped organic" is recycled back to extraction while the aqueous phase, now
containing the desired metal, goes to final metal recovery.
Final metal recovery usually takes place from the aqueous solution. The recovery of
metal directly from the loaded organic phase is also possible but it is practiced
commercially in only special cases probably because of organic contamination of the
final product.

La extraccin por solvente es aplicable en cualquier caso

en que es conveniente selectivamente, remover o extraer una
especie de una solucin en otro.
En las operaciones de recuperacin de metales, el
componente de valor es normalmente un ion de metal o un
complejo de iones de metal contenido en una solucin
acuosa. Esta solucin acuosa se mezcla ntimamente con una
fase orgnica inmiscible con el extracto activo en ese
momento la transferencia de activos de extraccin del metal
deseado de la fase acuosa a la fase orgnica.
La "carga orgnica" fase, que ahora contiene el metal
deseado, luego se transfiere a la seccin de agotamiento.
Aqu, la "carga biolgica" fase se mezcla ntimamente con
una solucin de extraccin acuosa que contiene una
sustancia qumica que proporciona la energa necesaria para

quitar el metal cargados desde la fase orgnica en la fase

de extraccin acuosa. El "despojado orgnicos" se vuelva a
la extraccin, mientras que la fase acuosa, que ahora
contiene el metal deseado, va a la recuperacin del metal
final.
La recuperacin del metal final suele tener lugar de la
solucin acuosa. La recuperacin del metal directamente
desde la fase orgnica cargada tambin es posible pero se
practica comercialmente en casos especiales, probablemente
debido a la contaminacin orgnica del producto final.

Extractable Metal Species

If a metal is to be extracted from impurities or vice versa it is important to know the
various metal and other species present in solution. With respect to metals, the
extractable species can be divided into four categories:

Metal cations such as Cu2+, Ni2+, and Co2+

Complex metal anions.
Complex metal cations.
Neutral metal specials.

Reagent Requirements
It is obvious that if a metal species is to be transferred from an aqueous leach solution
into an organic solution, there must be some chemical interaction which causes this to
happen. The component in the organic phase, which chemically interacts with the metal,
is properly called the "extractant" but is also commonly called the "reagent".
At the present time, there are organic extractants known for virtually all metals in one
form or another. However, the requirements for a successful extractant in analytical
chemistry are much different than the requirements for a reagent to be successful in
large scale metal recovery operations, especially as they relate to process continuity
and economics.

For a solvent extraction reagent to perform satisfactorily in the recovery and purification
of metals present in aqueous leach solutions the reagent must meet a number of
criteria. The most important of these have been summarised as follows:
1. Extraction of the desired metal selectively from the aqueous solution containing
the dissolved metal. This solution is usually a specifically prepared leach
solution but can also be an acid mine drainage solution or a waste stream from
some metallurgical or industrial process.
2. Be able to be stripped to produce a solution from which the desired metal can be
recovered in an acceptable form. The metal may be recovered in a number of
forms including electrowon cathode, crystallised salts, or precipitated salts.
3. Be chemically and physically stable in the solvent extraction circuit so that it can
be recycled through extraction and strip many times without experiencing
undue physical loss or chemical breakdown.
4. The reagents must meet today's stringent environmental and work place
regulations (must be nonflammable, nontoxic, noncarcinogenic, etc).
5. The extraction and strip kinetics must be sufficiently fast to allow these
processes to take place in an industrially acceptable time frame.
6. The extractant must be soluble, both in the loaded and stripped form, in a
relatively inexpensive diluent which also meets the environmental and
workplace regulations. Alternatively the extractant may be capable of being
used at a volume concentration of 100%, in which case the reagent forms its
own diluent.
7. The made - up circuit organic must phase separate from the aqueous at a
reasonable rate and the separated phases must have acceptable levels of
entrainment.
8. The extractant must not transfer deleterious species back from the strip section
to extraction.
9. The extractant should be tolerant of crud and should not promote crud formation
or stable emulsions.
10. The extractant must have a reasonable cost, which will enable it to provide an
economically attractive recovery route for the metal being treated.

Meeting all or sufficient of these criteria to an acceptable level imposes great restrictions
on the number of chemicals which have found commercial use as extractants. While
there are many hundreds of reagents which have been developed and tested in the
laboratory only very few of these have found commercial acceptance.
Normally, reagent behavior with respect to the above list is not a black and white, pass
or fail situation. No one reagent is the best with respect to all of the properties in the
list; rather, successful reagents possess a good balance of all of the properties in the
list.
It should be realized that few if any reagents are selective for only one metal under all
conditions, but that many reagents are selective for only one metal under certain
conditions.

Solvent Extraction Isotherms

The most basic requirement for solvent extraction design is an understanding of
distribution coefficients and equilibrium isotherms. These data and curves are obtained
in the laboratory and to some extent by computer if enough basic data are in the
computer programme.
Distribution curves or EQUILIBRIUM ISOTHERMS merely illustrate the distribution of a
dissolved component, between two phases.
The laboratory procedure to make extractions isotherms is to place the solution to be
extracted in the separatory funnels (see figure 3.1).
As the organic solvent and water are not miscible with each other, you should be able to
see the two layers (organic and aqueous layers) clearly. You should also have two
beakers ready, one labelled "organic layer" and the other labelled "aqueous layer".

Figure 3.1. Laboratory equipment to obtain equilibrium isotherms.

To extract all inorganic substances from the aqueous layer, vigorous agitation will be
necessary to increase the contact between these substances and the organic layer.
It is imperative to vent the separatory funnels of any gas pressure. When the residence
time has finished, the layers allowed separating. At this point the two layers can be
separated into their respective beakers. Once the extraction process is completed,
drying agents can now be used and the product can be isolated from the organic
solvent.
After phase separation the aqueous phase is analysed with respect to an element and
the element content in the organic phase is calculated. The equilibrium isotherm for
extraction is obtained by plotting the concentration of the element in organic phase
against the concentration of the element in the aqueous phase in a diagram.

Distribution Curves
The objective of solvent extraction in the metallurgical industry is clearly to extract one
metal ion and to reject the others, either to recover the metal extracted or merely to
remove it as an impurity.
For example, the following reactions are valid for the extraction and stripping of Cu 2+ in
sulphate media:
EXTRACTION: 2RH(org) + Cu2+(aq) ( R2Cu(org) + 2H+(aq)
STRIPPING: R2Cu(org) + 2H+(aq) ( 2RH(org) + Cu2+(aq)
These reactions show that extraction is pH dependent. High pH favours extraction while
low pH favours stripping. LIX reagents are used industrially for copper extraction, due to
their ability to selectively extract Cu2+ from Fe3+, which is commonly encountered in
leaching solutions. For instance, the pH dependence for extraction and stripping is
greater for Fe3+ than for Cu2+, which also is evident from figure 3.2. By using a pH
between 1.5 and 2.0 Cu2+ can be extracted selectively.

Figure 3.2.- pH isotherms for one of the commercial LIX-reagents.

Also, figure 3.3 shows the distribution of several common metals between a sulphate
medium and di 2.EHPA as a function of equilibrium pH.

Figure 3.3.- pH isotherms for D2EHPA.

These isotherms, of the types shown in figures 3.2 and 3.3, form the basis of
preliminary design for any solvent extraction plant. It will not be possible for the
commercial plant to perform better than predicted by the isotherms (unless conditions
change, in which case a new isotherm is needed) and in all cases efficiency will dictate
that it performs somewhat worse.
First, the relevant extraction and strip isotherms are produced in the laboratory by the
method described earlier, using stripped organic at equilibrium with the spent
electrolyte.
The initial choice of organic phase is largely a matter of experience but at a loading
mentioned previously, i.e. about 0.5 gpl Cu per percent extractant in diluent, a
concentration of about 24% should be needed in theory: actually, since no system is
perfect or loads to 100 percent loading, in this case 30 percent is provisionally assumed.
It is also important at this early stage' to recognise that the organic phase is never
stripped down to zero copper content, in other words there is always a circulating load.
The copper content of stripped organic is a function of many parameters including those
in table 3.1:
Table 3.1.- PARAMETERS AFFECTING
COPPER CONTENT OF STRIPPED ORGANIC
1. The organic extractant chosen
2. The organic concentration
3. Acidity of strip liquor
4. Copper content of strip liquor
5. Number of strip stages
6. Temperature

The important value to consider is the transfer capacity of the system in gpl copper, i.e.
the difference in gpl copper between loaded and stripped organic per volume of reagent
used.

The McCabe-Thiele diagram

Properly generated extraction and stripping isotherms represent equilibrium conditions
and, as such, predict the best extraction and the best stripping which can be obtained.
These isotherms can be used to set the staging in a circuit.
The number of steps needed in a mixer-settler to reach desired separation, can be
determined by constructing a McCabe-Thiele diagram. The diagram is constructed by
determining the equilibrium isotherm for extraction or stripping via experiments.
The equilibrium isotherm obtained is specific for every particular system. Changes in
temperature, pH, and concentrations of extractant or metal will lead to another
equilibrium curve.
Consider, for example, the extraction isotherm in Figure 3.4 and suppose that the
stripped organic entering into the last extraction stage contains 1.80 g/l Cu and that the
advance flow rates of the leach solution and the organic phase are equal.

Figure 3.4.-Equilibrium extraction isotherm and McCabe-Thiele diagram for extraction of

Cu2+ with a LIX-reagent. (S.O. and L.O. stands for stripped- and loaded organic phase,
respectively).

After the equilibrium isotherm has been plotted into the diagram, an operating line
can be constructed by starting at the point where the copper content of stripped organic
(S.O.) intersects the equilibrium isotherm and drawing the line up and to the right with

a slope equal to the ratio of the aqueous / organic flow rates (one in this instance) until
the operating line intersects the vertical line representing the copper content of the
aqueous phase feed.
Next, a horizontal line to the isotherm curve and then a vertical line to the operating
line are drawn creating a step. This procedure is repeated until a satisfactory degree of
extraction from the aqueous phase has been obtained. Each horizontal line in the
McCabe-Thiele diagram corresponds to one step in the mixer-settler. A McCabe-Thiele
diagram for stripping is constructed in a similar way, see figure 3.5.

Figure 3.5.-Equilibrium strip Isotherm and one-stage McCabe-Thiele diagram with a LIXreagent. (S.E. and P.E. is the stripped- and pregnant electrolyte, respectively)

In figure 3.4, each triangle represents a single stage of extraction, in this case,
completing a two-stage McCabe-Thiele diagram. In this example, a raffinate of 0.22 g/l
Cu and a loaded organic of 4.30 g/l Cu are predicted in two stages of extraction. The
inverse of the slope of the operating line is the advance organic / aqueous flow rate.
Even though the McCabe-Thiele diagram shown in Figure 3.4 does not represent true
equilibrium, but only a first approximation, it is still quite useful. For example, if a third
stage of extraction were to be added to the McCabe-Thiele diagram in Figure 3.4, (note
the dotted line) a near perfect equilibrium McCabe-Thiele diagram would result. In
addition, a more accurate two-stage McCabe-Thiele extraction diagram can be drawn by
taking the two-stage McCabe-Thiele construction as shown in Figure 3.4 and choosing
as the point from which a new operating line is to be drawn a distance about 1/2 way
between the isotherm line and the raffinate line.
When this is done, and then a second two stage McCabe-Thiele diagram constructed as
described above, a raffinate of about 0.15 g/l Cu and a loaded organic of 4.17 g/l Cu are

predicted. The construction of a true equilibrium McCabe-Thiele diagram is an iterative

process.
With the example under discussion, the second step of iteration is all that is needed to
produce a near equilibrium McCabe- Thiele diagram. This will not always be the case.
The construction of an equilibrium McCabe-Thiele diagram depicting one stage of
stripping is very simple (Figure 3.5). A horizontal line is drawn from the loaded organic
line (3.90 g/l Cu) to the isotherm line at the value of the pregnant electrolyte (P.E.)
desired, 51 g/l Cu in this case. Then a vertical line is dropped from the point where the
P.E. line intersects the isotherm line to the horizontal axis. This gives the stripped
organic (S.O.) to be expected (1.77 g/l Cu). Next, the strip electrolyte (S.E.) line, 30.7
g/l Cu, is drawn horizontally from the vertical axis of the graph to the L.O. line. A line is
now drawn from the point of intersection of the S.O. and S.E. lines to the intersection of
the loaded organic and pregnant electrolyte lines. This is the operating line.
The slope of the operating line is equal to the ratio of the advance organic flow to the
advance aqueous flow needed across the strip stages to obtain the desired pregnant
strip solution. A two-stage McCabe-Thiele strip diagram, constructed as described above
for extraction, predicts a stripped organic of 1.12 g/l Cu when building a pregnant
electrolyte of 51 g/l Cu and operating at an O/A of 7.3/1.
One of the important decisions the designer or builder of an SX plant must make is to
decide on the staging requirements. The capital cost of a stage must be weighed against
the benefits the stage provides.

CLASSIFICATION OF THE MAIN TYPES OF EXTRACTANTS

There are five classes of metal extractants as characterized by structure, extraction
mechanism and the metal species extracted: chelation, ion pairing, neutral or solvating,
organic acids and ligand substitution. The five main classes of extractant compared are:

4.1.- CHELATING AGENTS

4.2.- ION PAIR EXTRACTANTS
4.3.- NEUTRAL OR SOLVATING EXTRACTANTS
4.4.- ORGANIC ACID EXTRACTANTS.
4.5.- LIGAND SUBSTITUTION EXTRACTANTS

Chelating agents
Chelating refers to "claw", which is a graphic description of the way in which the organic
extractant binds a metal ion. i.e., the extractant chemically bonds to the metal ion at

two sites in a manner similar to holding an object between the ends of the thumb and
the index finger.
In many cases, upon bonding with the metal ion, the extractant releases a hydrogen ion
into the aqueous solution from which the metal was extracted.
Table 4.1. summarise chelating agents properties.

Ion pair extractants

A second class of extractants is based on the principle of ion association whereby a

large, positively charged organic moiety causes the extraction of an anionic metal
complex into the organic phase, with concomitant expulsion of a common anion into the
aqueous phase.
Table 4.2. summarise chelating agents properties.

Neutral or solvating
extractants#Neutral_or_solvating_extractants
A third class of extractants are known as neutral or solvating type extractants.
Extractants of this class are basic in nature and will coordinate to certain neutral metal

complexes by replacing waters of hydration, thereby causing the resulting organo-metal

complex to become organic soluble and aqueous insoluble.
Solvating extractants have an atom capable of donating electron density to a metal in
the formation of an adduct and are classified according to that ability:
R3PO > (RO)3PO > R2CO > ROH > R2O
trialkylphosphine oxides > trialkylphosphates > ketones > alcohols > ethers
It takes little imagination to see that the above list is only a brief representation of the
organic compounds that could function as solvating extractants. In general, extractions
with solvating extractants are limited by:
1. the metal's ability to form neutral complexes with anions,
2. the co-extraction of acid at high acid concentrations, and
3. the solubility of the organometal complex in the organic carrier.
An important extractant of this type is tri-noctylphosphine oxide, (C8H17)3PO, called
TOPO. The extraction characteristics of TOPO with a wide variety of metals have been
investigated. One important commercial application of TOPO in solvent extraction is its
synergistic combination with di-2-ethylhexylphosphoric acid (DEHPA) for the extraction
of uranium from wet process phosphoric acid.
Other important extractants in this class are triutylphosphate (TBP), di-butyl
butylphosphonate (DBBP), 2,2'-dibutoxy diethyl ether (di-butyl carbitol) and methyl
isobutyl ketone (MIBK). Di-butyl carbitol and MIBK are used for the extraction of gold
from acid chloride solutions.
Table 4.3. summarise chelating agents properties.

Organic acid extractants.

A fourth class of extractant is the so-called acid extractants. The chemistry of this type
of extractant has some characteristics which resemble chelating extractants and some
which are similar to neutral or solvating extractants. Di-2-ethylhexyl phosphoric acid
(DEHPA), is representative of this class of extractant.
Table 4.4. summarise chelating agents properties.

Ligand substitution extractants

Ligand substitution extractants are similar to neutral or solvating extractants in that
they donate an electron pair to a metal ion, but they are different in that these
extractants form inner shell complexes with metals and, in doing so, will displace other
ligands.
Table 4.5. summarise chelating agents properties.

SOLVENT EXTRACTION SELECTIVITY

The selectivity of a solvent extraction circuit for a given metal is important because it
determines product purity, which is a key factor in determining the price, obtained for a
given metal product. In addition impurities can affect downstream processing, for
example in a typical electrowinning operation following solvent.
Although the thermodynamic selectivity of the extractant for one metal over other
competing metals is the single most important factor affecting the selectivity of a
solvent extraction circuit it is not the only factor. The factors that have an influence on
the selectivity of a solvent extraction circuit as opposed to the selectivity of an
extractant are listed below:

The structure of the extractant molecule and the chemistry involved in the
extraction process. This determines the thermodynamic selectivity.

The pH in extraction and stripping and the possibility of selective stripping

The influence of the diluent on selectivity
The aqueous chemistry of the PLS, in particular the relative concentrations of the
competing metals present, the speciation of the metal complexes and the
types of anion present.

Differences in the extraction kinetics of competing metals.

The use of scrubbing circuits for the loaded organic
The mechanical design of the equipment and the circuit layout employed.
Entrainment and crud effects
The strip chemistry, the possibility of selective stripping.
The control of one or more of these factors will in many cases allow solvent extraction
circuits using reagents having inherently low selectivity, such as ion pair extractants to
achieve high selectivity.

INFLUENCE OF THE SOLVENT EXTRACTION DILUENT

The diluent can influence the selectivity of a solvent extraction process through both
chemical and entrainment effects.
Diluents used in the solvent extraction of the major metals are usually either dearomatized hydrocarbons containing less than 0.5% aromatics or diluents containing
between 17 and 23% aromatic. Both types of diluent contain about 40% cyclo paraffins.
The selection of the diluent is usually made on the basis of flash point, viscosity and
environmental parameters. However the diluent can influence the selectivity of the
organic.
Aromatic components in the diluent can have three main effects on the chemistry of
solvent extraction.
1. To increase the solubility in the organic phase of the metal - extractant complex.
2. To act as an equilibrium modifier.
3. To influence the selectivity of the extractant.
Where a contaminant is being chemically extracted then the presence of aromatics in
the diluent may enhance the solubility of the metal - extractant complex in the organic
phase with a consequent decrease in selectivity.
The effects described above illustrate that while the choice of diluent can influence
selectivity the mechanism involved can vary with the system being used and
experimentation is usually required to predict the effect on selectivity of selecting a
particular diluent.

INDUSTRIAL PROCESS DESIGN

Typically an industrial process will use an extraction step in which solutes are
transferred from the aqueous phase to the organic phase, this is often followed by a
scrubbing stage in which unwanted solutes are removed from the organic phase, then a
stripping stage in which the wanted solutes are removed from the organic phase. The
organic phase may then be treated to make it ready for use again.
After use the organic phase may be subjected to a cleaning step to remove any
degradation products.

Solvent Extraction Process

Solvent extraction, as applied to Hydrometallurgy, is a unit operation for the

purification and concentration of a wide variety of metals. It consists of contacting an
organic phase containing an extractant, with an aqueous phase containing the metal of
interest. The extractant chemically reacts with the metal to form an organic-metal
complex that is soluble in the organic phase. Impurities normally do not react with the
extractant and remain in the aqueous phase. The organic phase, containing the organicmetal complex, is separated from the aqueous phase. The metal is recovered and
concentrated into another aqueous phase by reversing the chemical reaction.
Solvent extraction was first applied to higher value metals, but now due to availability of
new extractants with improved selectivity, faster kinetics and phase disengagement
times, and recent developments in efficient equipment with less area and reagent
inventory, the technology is now applicable to lower value metals.
Extraction: The operation of transferring the metal of interest from the aqueous phase
(SX Feed) to the organic phase. The extraction circuit produces a loaded organic
containing the metal value and an aqueous phase depleted of the metal known as
raffinate. The raffinate is sent for further treatment or effluent.
Scrubbing: The selective removal of impurity metals from the loaded organic phase by
treatment with either fresh scrub solution or a bleed of the strip liquor. The spent scrub
solution is normally combined with the SX Feed. The scrubbed organic containing the
metal of interest is advanced to stripping.
Stripping: The process of removing the metal of value from the scrubbed organic phase
by reversing the extraction chemical reaction. It is normally conducted under conditions
in order to produce a strip liquor containing a high concentration of the metal value. The
strip liquor is the product of the SX circuit.
Regeneration: The treatment of the stripped organic phase for removal of metals that
were not scrubbed or stripped, or for the removal of organic degradation products. The
operation produces a regenerated organic phase for recycle to the extraction operation
as organic feed. The spent regenerant is advanced for further processing or to effluent
treatment.

Figure 7.1. A schematic representation of hydrometallurgical solvent extraction process.

Equipment
While solvent extraction is often done on a small scale by synthetic lab chemists using a
separating funnel it is normally done on the industrial scale using machines which bring
the two liquid phases into contact with each other. Such machines include centrifugal
contactors, spray columns, pulsed columns and mixer-settlers.
Mixer Settlers
For the major metals recovered by solvent extraction the mixer-settler contactor design
predominates. However there is a range of mixer settler designs available and in recent
years there has been some attention refocused on the use of pulsed columns for plants
using the kinetically fast ion- exchange extractants.
Well established with literally hundreds of operating units.
Design parameters are well established and very large units treating over 1000 cubic
metres per hour of PLS can be designed from bench scale tests.
Excellent mixing characteristics with control of the optimum droplet size claimed to be
possible with modern turbine designs.
Prediction of capital and operating costs is accurate.
The phases are readily accessible for sampling and examination in situ.
Several design varieties are available
Column Contactors
Advantages claimed for the column contactor include:
Low area requirements
Multiple stages within one unit
Few moving parts
Low entrainment
Good vapour conservation
Column installations require piloting for each installation and the flooding conditions
for the column must be determined. The long residence times in a column compared to a
mixer settler can influence the selectivity of the extraction if contaminants have slow
extraction kinetics.

O/A Ratio
The O/A ratio of the phases in a mixer has a significant effect on entrainment as shown
in Figures 7.2 and 7.3. With organic continuous dispersions, aqueous entrainment in the
organic phase increases considerably at O/A ratios greater than 1.5:1. Organic
entrainment in the aqueous phase is very low for organic continuous dispersions and is
not dependent on the O/A ratio in the mixer.

For aqueous continuous dispersions, organic entrainment in the aqueous phase

increases sharply at O/A ratios of less than 1:1, and aqueous entrainment is lowest
between O/A ratios of 1:1 to 2:1. Therefore, the optimum O/A for both organic and
aqueous continuous dispersions is between 1:1 to 1.5:1.
The O/A ratio of the phases in a mixer can be maintained between 1:1 to 1.5:1 by
recycling either the organic or aqueous phase from the settler to its mixer. Another
important reason for maintaining the optimum O/A ratio is to improve the mass transfer
rate and stage efficiency.
At the optimum O/A ratio the rate of coalescence and redispersion of the dispersed
phase is enhanced.

Figure 7.2. Effect of O/A ratio on Aqueous entrainment.

Figure 7.3. Effect of O/A ratio on Organic entrainment.

Phase Continuity
A relationship exists between entrainment and phase continuity. Under organic
continuous dispersions, in which the aqueous phase is dispersed as droplets in the
organic phase, aqueous entrainment in the organic phase is common. Organic
continuous dispersions usually produce an aqueous phase low in organic entrainment.
Therefore, in order to produce a strip liquor and raffinate low in organic entrainment, it
is recommended to operate the first stage of stripping and the last stage of extraction
with organic continuous dispersions in the mixers.
Aqueous continuous dispersions, in which the organic phase is dispersed as droplets in
the aqueous phase, can produce an aqueous phase with organic entrainment and an
organic phase low in aqueous entrainment. Therefore, it is recommended to operate the
mixer in the last stage of stripping and the first stage of extraction under aqueous
continuous conditions in order to minimize aqueous entrainment in the organic phase.
This relationship between O/A ratio and phase continuity on entrainment can be used to
improve SX plant operation.

De-entrainment of Organic and Aqueous Flows

Entrainment of organic in aqueous and aqueous in organic can create significant
problems in both SX circuits and electrowinning. The main methods used for de
-entrainment of SX streams are Coalescers in the Extraction Circuit. These usually
employ some form of packed bed or porous media and may not work well when there is
significant crud present in the system. Examples of coalescers include:

PICKET FENCES IN THE SETTLER

Besides distributing a uniform flow in the

settler, these can bank up the emulsion
band on the upstream side and this band
acts as a coalescer.

PACKED BED COALESCERS IN THE

SETTLER

These can reduce entrainments but can also

blind and cause channel flow around the
edges of the packed bed or through nonblinded sections of the coalescer. For this
reason, provision must be made to
periodically remove the coalescers and to
clean them.

COALESCING MATERIAL IN THE

LOADED ORGANIC SURGE TANK

This can help reduce aqueous entrainment

to the tankhouse. Provision must be made
to remove and clean the coalescing
material. This can be easier to carry out
than cleaning of the coalescers from the
settler.

COALESCERS EMPLOYING MULTIMEDIA

Woven coalescers using an aqueous wetted

fibre (stainless steel) and an organic wetted
plastic fibre have given good results in pilot
plants but blockage by crud can be a
problem in larger installations.

PACKED BED RAFFINATE COALESCERS

FOR ORGANIC RECOVERY

A coarse packed bed of 1 - 2 cm sized coke

or silica particles is used in an upflow
mode. Provision is made to backwash with
air and water. The top of the coalescer has
a "thickener froth ring" type of launder and

coalesced organic remains inside this ring

and is removed from time to time.
ORGANIC RECOVERY FROM AN AFTER
SETTLER AHEAD OF THE RAFFINATE
POND OR FROM THE RAFFINATE POND
ITSELF

The after settler can be a purpose built unit

such as a multiplate coalescer or simply a
small raffinate pond. For small pond and for
raffinate pond recovery, floating booms are
used to "corral" the organic prior to
recovery from the top of the aqueous.

SOLVENT EXTRACTION OF METALS

The practice of hydrometallurgy contains examples of a great number of diverse solvent
extraction processes.
Besides the major metals there are or have been commercial solvent extraction
processes operated for the recovery of metals such as tungsten, rare earths, thorium
and vanadium.
Solvent extraction of metals such as copper, uranium, cobalt and nickel, besides being
of great economic significance has been the spur for the development of the engineering
aspects of solvent extraction.
Let us briefly examine the metals for which solvent extraction has succeeded and the
circumstances, which caused these metals to become candidates for recovery by solvent
extraction. They have some common features:
1. They are soluble in suitable lixiviants such as sulphuric acid, ammonia and
cyanide.
2. They are relatively valuable. Have a reasonable market price or have
environmental properties that financially support their recovery.
3. They can be recovered from the concentrated strip solution in a suitable
marketable or intermediate form by processes such as electrowinning or
precipitation.
4. Suitable solvent extraction chemistry has been developed for these metals.

Uranium
The first metal to be recovered in significant quantities using solvent extraction was
URANIUM.
Following the development of the nuclear industry during and immediately after World
War II, attention was focussed on developing technologies which could be used to
upgrade and purify uranium from low grade ores and in 1957 the first commercial
solvent extraction plant using amines was opened in the USA.

Today most of the world's uranium is recovered in hydrometallurgical circuits which

involve solvent extraction and a significant proportion of this uranium is produced in
circuits which use solvent extraction as the only recovery system.

Extraction and Stripping Chemistry

The vast majority of uranium is recovered from sulphuric acid leach solutions using C8C10 tertiary amines. When uranium is dissolved in sulphuric acid two anionic sulphate
complexes are formed:
UO22+ + 2SO42- ( UO2(SO4)22UO2(SO4)22- + SO42- ( UO2(SO4)34Uranium leaching normally involves an aggressive, oxidising agitation leach at elevated
temperatures of around 40 - 80C and such a leach is not selective for uranium. As a
result the SX feed will contain a number of anion species which can cause problems in
the solvent extraction of uranium.

Extractant and diluent Type

Tri-octyl and tri-decyl amines are used almost exclusively for uranium extraction
however trilaurylamines are used when molybdenum is present as the amine
molybdenate complex formed with the C8 and C10 amines may not be sufficiently
organic soluble.
In practice the theoretical maximum loading is not attained due to the presence of
competing anions in the leach liquor.
Ion exchange extractants are non-selective and, although the uranyl sulphate anion is
very strongly extracted by tertiary amines, other anions will also be extracted.
The uranium - amine complex formed from the C8-C10 tertiary amines has limited
organic solubility in the 1-20% aromatic diluents typically used and third phase
inhibitors are added to the circuit organic to improve this solubility.
Isodecanol at a concentration of about 50% of the amine concentration is the most
commonly used modifier although high aromatic diluents can also be used. The use of
isodecanol can increase phase separation times and increase crud formation. Isodecanol
is also a nutrient for bacteria and can lead to bacterial activity in the circuit. The
solubility of isodecanol in water is about 150-170 ppm compared to 5ppm for tertiary
amine and isodecanol losses to the raffinate will be similar to the amine losses.

Uranium Circuit Layout

The circuit configuration of any SX plant is dictated by the extraction and stripping
chemistry. A typical acid leach - SX uranium circuit is shown in Figure 8.1. Let us
consider some of the important features of this circuit.
. Clarification
Uranium circuits normally use an agitation leach. Clarification to remove suspended
solids may involve special equipment such as hopper clarifiers.
. Soluble silica removal.

The leach is sufficiently aggressive to leach significant quantities of silica and this can
cause crud formation and phase separation problems if allowed to go through to SX.
High molecular weight polyethylene oxides or similar chemicals with significant
hydrogen bonding capability are used, often in conjunction with floc bed clarifiers to
precipitate soluble silica.
. Extraction
Uranium circuits usually aim at recoveries in excess of 95% and four stages of
extraction is considered the minimum. The function of E4 may be more amine
protonation than uranium recovery. Competing anions may load in E3 and E4 but are
crowded off in E1.
. Scrubbing
Ion exchange is not a selective process and scrubbing to remove impurities such as
iron, silica, and zirconates is required.
. Stripping
Most circuits employ a deprotonation scrub using NH3 plus ADU precipitation spent
liquor as the strip aqueous. A carefully controlled pH profile is required in strip if ADU
precipitation is to be avoided. The pH decreases from about 5.0 in S4 to 3.0 in S1.
. ADU precipitation
Ammonia is used to precipitate ADU. The temperature must be maintained about 30oC
if the sulphate content and the particle size of the precipitate are to be optimum.

Copper
Today around 25% of the world's copper is recovered using solvent extraction and
solvent extraction is considered to be the lowest cost production route for the
production of quality cathode.
The scope of solvent extraction for copper is only limited by the availability of acid
leachable ore and it is not surprising that considerable attention is being directed
towards development of suitable leaching techniques for chalcopyrite, the most
ubiquitous of all copper minerals.
The use of solvent extraction for copper ores dates from the Ranchers Bluebird mine
which started operation in 1968. Acceptance of solvent extraction technology for copper
using Henkel's (previously General Mills Chemicals Inc) oxime based extractants took a
giant step forward in 1974 when ZCCM commissioned their 80,000 tonne per annum
SX-EW plant at Nchanga.

Extraction Chemistry
Copper extractants for acid leach solutions are exclusively oximes. For extraction from
ammoniacal solutions beta diketones may be used. The chemistry of oxime extraction of
copper is relatively simple:
2RH(org) + Cu2+ + SO42- ( R2Cu(org) + 2H+ + SO42There are other reactions which take place in copper extraction which can influence
extraction and stripping such as dissociation of H2SO4 or dimerisation of the oxime.

Extractant Types
Oxime based extractants for copper are largely based on salicyaldoximes which have
been modified with one of three modifier types. Examples of the three main extractant
types currently in use are:
1. A mixture of oxime and aldoxime in a high flash diluent. The acetophenone oxime
modifies the aldoxime and also performs as an extractant in its own right.An example of
this type of extractant is LIX(r) 984N
2. An aldoxime modified with an ester in a high flash diluent. An example is Acorga(r)
M5640.
3. An aldoxime modified with tridecyl alcohol in a high flash diluent. The LIX(r) 622N is
an example of this extractants.
Each of the extractants marketed by the major chemical suppliers has been designed for
a specific type of PLS with regard to pH and copper tenor. Used under the conditions for
which they were designed they all deliver very similar copper net transfer values.
The vol% concentration of the commercially available extractants is limited by organic
viscosity constraints to about 30-33% and this means that the maximum net transfer of
copper will be about 10g/l. For leach solutions containing significantly higher copper
tenors than this the throughput O/A ratio will have to be increased above 1.0.
Typical copper and acid concentrations for an SX plant treating a dump leach solution of
3.0g/l and pH1.8 are shown in the following figure:

Hoy en da alrededor del 25% de cobre del mundo se recupera

mediante extraccin por solvente y la extraccin por
solvente se considera la ruta ms bajos costos de
produccin para la produccin de ctodo de calidad.
El alcance de la extraccin por solvente de cobre slo est
limitada por la disponibilidad de mineral lixiviable cido
y no es de extraar que una considerable atencin est
dirigida hacia el desarrollo de adecuadas tcnicas de
lixiviacin de calcopirita, el ms numeroso de todos los
minerales de cobre.
El uso de la extraccin por solvente para las fechas de
minerales de cobre de la mina de Bluebird ganaderos que
comenz a funcionar en 1968. La aceptacin de la tecnologa
de extraccin por solvente de cobre utilizando (Henkel
previamente General Mills Chemicals Inc) extractantes
basados oxima dio un paso de gigante en 1974, cuando ZCCM
encargado sus 80.000 toneladas por ao la planta SX-EW en
Nchanga.
Extraccin de Qumica
Extractantes de cobre para las soluciones de lixiviacin
cida son exclusivamente oximas. Para la extraccin de las
soluciones amoniacal dicetonas beta puede ser utilizado. La
qumica de la extraccin de la oxima de cobre es
relativamente sencilla:
2RH (org) + Cu2 + + SO42-(R2Cu (org) + 2H + + SO42 Existen otras reacciones que tienen lugar en la extraccin

de cobre que pueden influir en la extraccin y agotamiento,

como la disociacin de H2SO4 o dimerizacin de la oxima.
Tipos de Separador
Oxima extractantes base de cobre se basan principalmente en
salicyaldoximes que han sido modificados con uno de los
tres tipos de modificadores. Ejemplos de los tres tipos
principales de extraccin que se utilizan actualmente son:
1. Una mezcla de oxima y aldoxime en un diluyente de flash
de alta. La oxima acetofenona modifica el aldoxime y
tambin acta como un agente de extraccin en su propio
right.An ejemplo de este tipo de extraccin que se LIX (r)
984N
2. Un aldoxime vez con un ster en un diluyente flash de
alta. Un ejemplo es Acorga (r) M5640.
3. Una aldoxime vez con el alcohol trideclico en un
diluyente de flash de alta. La LIX (r) 622N es un ejemplo
de este extractantes.
Cada uno de los extractantes comercializados por las
principales proveedores de productos qumicos ha sido
diseado para un tipo especfico de PLS con respecto al pH
y contenido de cobre. Utilizados en las condiciones para
las que fueron diseados todos ellos ofrecen una muy
similares los valores de transferencia neta de cobre.
La concentracin% en volumen de los extractantes
disponibles en el mercado es limitado por la viscosidad
orgnica a cerca de 30-33% y esto significa que la
transferencia neta mxima de cobre ser de unos 10g / l.
Para las soluciones de lixiviacin que contiene tenores de
cobre significativamente mayor que el rendimiento de este O
/ A razn tendr que aumentar por encima de 1,0.
De cobre tpica y concentraciones de cido para una planta
de SX el tratamiento de una solucin de lixiviacin de
volcado de 3.0g / l, y pH1.8 se muestran en la siguiente
figura:

Copper solvent extraction plant configurations

A variety of circuit configurations are used:

2E X 1S(The usual circuit for heap leach plants)

2E X 2S(Used where the copper tenor is above about 7-10 g/l or the PLS pH is
less than about 1.2. The decision to use a second strip stage is influenced by the
life of the project and the sensitivity of the circuit to the copper tenor of the
raffinate. Agitation leach plants for example are sensitive to the loss of copper in
a raffinate bleed or in the wash liquor used in the solid liquid separation stages.

3E X 2S(These can be justified when the PLS has a very high copper tenor, say
above 20-25g/l and a high 93% plus copper recovery is desired. It is possible to
use a 2EX2S circuit under these conditions but the throughput O/A ratios will be
high, in excess of 2.5:1 and the capital cost of the 2EX2S plant may be higher
than that of the 3EX2S plant. The 3EX2S plant will also be much more flexible in
operation).

2E X 1W X 1S(The wash stage is used to remove entrained impurities, usually

chloride, and entrained and chemically loaded iron).

2E X 1P X 1S(Series parallel circuits are used to treat high volumes of low tenor
leach solutions. The parallel stage is often retrofitted to maintain copper
production when the copper tenor of the PLS falls below project design and there
is also the possibility to increase the volume of the PLS flow. Extractant
concentrations are higher and copper recoveries are lower in series parallel
circuits than in series circuits).

Nickel
In comparison to copper and uranium the percentage of the world's nickel which is
recovered using SX is relatively small, however recent developments may well change
this situation.
Unlike uranium and copper extraction where one type of extractant and circuit
predominates there are a number of potential nickel extractants and circuit
configurations.
Sulphide nickel is usually treated using pyrometallurgical routes but in recent years
there has been intensive activity in the development of hydrometallurgical routes for
both sulphide concentrates and laterites. Nickel deposits can contain valuable quantities
of cobalt and copper and these must also be recovered by SX if they are present in
sufficient quantity.
1. The base metals (Ni, Cu, Co,Zn) may be precipitated as hydroxides from sulphate
leach solutions , redissolved in ammonia, the cobalt may be oxidised to Co(3) and the
copper and nickel co-extracted with ketoxime (LIX 84-I ). This is the process most
commonly used for treating Ni Laterite.

Figure 8.2. Nickel Laterite Treatment.

2. Direct solvent extraction of copper, cobalt and nickel from acid leach solutions using
oximes, phosphinic acids and versatic acids to extract copper, cobalt and nickel in
sequence. While this circuit may function on leach solutions derived from sulphide
concentrates, laterite leach solutions contain significant manganese and magnesium,
both of which are extracted by phosphinic acid extractants. In addition the aqueous
solubility of versatic acid at the pH used for extraction necessitates the inclusion of a
versatic acid recovery stage.

Figure 8.3. Nickel Recovery from Acid PLS.

3. Matte leach chloride solutions may be purified by iron extraction with TBP followed by
cobalt and copper co extraction as chloride complexes with tertiary amine. Nickel does
not form chloride complexes and remains in the raffinate. It may be recovered by
crystallization and hydrogen reduction.

Figure 8.4. Nickel-Cobalt Separation using Chloride Leach Solutions and tertiary Amine
Extractants

Precious Metals
Although the quantity of precious metals currently recovered using circuits that involve
solvent extraction is small the value of these metals is significant. A gold refining
process has been recently developed based on solvent extraction and there exists a
potential for gold recovery by solvent extraction. In the refining of platinum group
elements solvent extraction plays an important role.
A variety of solvent extraction processes are used in the refining of the platinum group
elements. Phosphinic acids have been used to remove cobalt from nickel in sulphate
leach solutions. The PGE's form a wide range of chloride complexes and this makes
possible the separation of these elements using ion-exchange extractants. The majority
of these separation systems are not widely discussed in the literature.
Gold as the aurocyanide complex can be extracted at pH values below 9.0 by tertiary
amines and over a wide pH band by quaternary amines. The relatively low pH required
for tertiary amine separation makes this an unattractive route for most circuits while the
quaternary amines can only be stripped in a two stage process using zinc tetracyanide
stripping followed by sulphuric acid regeneration of the organic and HCN recovery.

AUTHORS / CONTRIBUTORS
Maria Frades
Francisco Snchez

Hydrometallurgy & Electrochemistry

c/ Sierrra Nevada, 16 - P. Ind. San Fernando II
28830 San Fernando de Henares (Madrid)

ACKNOWLEDGEMENT
The authors gratefully acknowledge the EU commission for funding this
work within the Sixth Framework Programme.
Project: NMP2-CT-2005-500329
Acronym: BioMinE
Project Title: Biotechnology for Metal bearing materials in Europe
Instrument: Integrated Project
Thematic Priority: Priority 3 - NMP
Nanotechnologies and nanosciences, knowledge-based multifunctional
materials, and new production processes and devices