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