INTRODUCTION

The Metals Extraction Industry has seen many changes in operating practises and
technology in the latter part of the 20th century. These changes have been vitally necessary
in many parts of the world to maintain economically viable operations as grades have fallen
and metals were required to be extracted from ores derived from more complex geological
deposits.

Solvent Extraction,( SX ),processes have been used on a commercial scale for the recovery
of uranium and copper since the 1960's. These processes are now well established and
generally considered as the low cost production routes by which all other metallurgical
options are judged. Specific metals separation circuits using SX processing technology
have also been developed for the recovery of nickel, cobalt, zinc, palladium, molybdenum,
germanium and gallium and for the removal of arsenic from copper tankhouse electrolyte.
Only copper and uranium processing by SX has, thus far, resulted in large scale commercial
application, although the recovery of nickel and cobalt from latterite deposits will
increasingly rely on the SX route as new processes begin to come on stream.

For the copper industry the introduction of the solvent extraction process is arguably the
most important change in technology that has been introduced for the recovery of high
quality copper from both primary and secondary copper sources.

The information presented here is designed to introduce those unfamiliar with solvent
extraction technology to the basic concepts involved and to provide specific information on
how to test aqueous solutions and design circuits for the recovery of metals by application
of SX technology. It also provides information on how SX reagents are formulated and
selected for particular duties as well as providing extensive information on the complete
concept of hydrometallurgy as applied in particular to copper recovery.

The key components of a hydrometallurgical process are:

• LEACHING

This process is designed to take the desired metal efficiently into aqueous solution.

• SOLVENT EXTRACTION

To separate the desired component from the other components of the leach solution and
provide a concentrated, purified solution of the desired metal in a form which is suitable
for the final metal recovery step.
 • METAL RECOVERY

Processes used in hydrometallurgy differ according to the chemistry of the metal in

question and the form in which that metal is required by the user. Copper, for instance,
is recovered as 99.9+% pure metal at the cathode of an electrowinning cell. Uranium is
recovered as 'yellow cake' (approximately 80% U308) by precipitation and calcining of
ammonium uranyl sulphate.

Clearly, the key enabling step in the overall recovery process is the solvent extraction step
and the key component is the solvent extraction reagent. Reagents which meet the highly
specific demands of selective metal extraction are highly desirable as they make the
subsequent recovery of the desired metal much less complicated and eliminate expensive
processing steps during the metal recovery process.

Avecia's Metal Extraction Products Business, MEP has been a pathfinder in this technology
since the early 1970's and is one of the leading supplier of copper solvent extraction
reagents in the world today with sales to plants in all major copper - producing countries.

1. The Chemistry of the Solvent Extraction Process

The solvent extraction process, as applied to metals extraction, can be defined as:

"The selective transfer and concentration of metal ions from an impure aqueous phase via
an organic phase to a second pure aqueous phase from which the desired metal can be
recovered in a usable form."

In the recovery of copper from sulphuric acid leach solutions, for instance, divalent copper
ions are selectively captured at the interface of the organic and aqueous phases by a
specially designed organic molecule to form a copper/organic complex. This complex is
insoluble in the leach solution but soluble in organic solvents. If the organic compound,
also known as a ligand, has been diluted with, for instance, a hydrometallurgical grade of
"kerosene" prior to contact with the leach solution then the copper complex will transfer
into the bulk organic phase. If, in addition, the organic and aqueous are totally immiscible
and the ligand is designed to form an organic complex only with the species to be extracted
then we have established the basis of an effective metals separation process.
 The Solvent Extraction Process

1. Copper-bearing ore is sprayed with dilute sulphuric

acid. The acid percolates through, dissolving the
copper while on its way to step 2.
2. The copper-bearing liquor is collected and stored here
prior to feeding to step 3.
3. The extraction mixer-settler equipment, where the
copper bearing liquor is contacted with the
appropriate Avecia extraction reagent to form an
organic soluble complex. The copper-loaded organic
solution is then advanced to step 4.
4. The stripping mixer-settler equipment, where the
copper-loaded organic solution is contacted with acidic electrolyte, arising from the tankhouse.
This allows re-extraction of the copper by sulphuric acid to form a concentrated, purified
electrolyte solution. This solution is then passed on to step 5.
5. The electrowinning tankhouse, where 99.99% pure copper is deposited from the electrolyte at the
cathode.

The acid generated is returned in copper-depleted electrolyte to step 4 to strip more copper from the
circulating loaded organic solution. The organic reagent is regenerated during the stripping process (step 4)
and is returned to the extraction section (step 3) to extract more copper.

Following successful extraction, a final processing step is required to recover the desired
metal in a usable form. In the copper industry this is achieved rather elegantly by
interfacing the SX operation with an electrowinning process. Purified copper metal is
recovered at the cathode of a series of EW cells from an electrolyte solution arising from
the second stage of the SX process. This process is known as stripping and is carried out
using "spent" or "lean" electrolyte which has been partially depleted of copper in the EW
cells.

The Solvent Extraction process can therefore be represented by the following chemical
equations:
Clearly, the extraction reaction will be favored by conditions of low acidity (higher pH) and
stripping will proceed under conditions of high acidity.

The pH-dependent nature of this equilibrium reaction is extremely important in the

extraction and recovery of copper from sulphuric acid-based solutions by the LEACH-SX-
EW process and a thorough understanding of its implications is essential to allow organic
ligand molecules to be designed in an optimized way for the SX step of this process.

The dependence of ligand performance on pH can be conveniently represented graphically

by plotting pH on the horizontal axis against % extraction on the vertical axis. Curves for
hydroxy oxime ligands typically used in the extraction of copper from acid solutions are
shown here in Fig 1. .

Fig 2. , shows how the extraction performance of different classes of oxime reagents
varies with pH. The first products developed for the extraction of copper by SX were
ketoximes which, as is seen, have limitations with regard to their ability to extract copper
from solutions of high acidity (low pH) or solutions containing a high concentration of
copper (remember acid is produced during the copper extraction reaction and determines
the position of the equilibrium in equation (I) above).

The alternative to the ketoxime is the aldoxime, a ligand type having higher strength and
superior kinetic performance to the ketoxime but which, relatively speaking, forms copper
complexes that are difficult to strip with "spent" electrolyte compositions typically
available from an EW tankhouse operation although they can be stripped with higher
concentrations of acid. For that reason aldoximes are rarely used alone and are "modified"
by blending them with a carefully selected group of organic compounds developed by
Avecia. These are known as equilibrium or "strip" modifiers; their function will be
discussed in detail later.

The Information and recommendations in this publication are to the best of our knowledge, Information
and belief accurate at the date of publication. Nothing herein is to be construed as a warranty, express or
otherwise. In all cases, it is the responsibility of users to determine the applicability of such Information or
the suitability of any product for their own particular purpose.

Figure 1:
 Figure 2:

2. Aldoximes and Ketoximes (Hydroxy-Oximes)

Among the hydroxy-oximes, aldoximes, as a class, have performance advantages in the
copper extraction process over ketoximes particularly in their ability to:

1. Treat effectively a wider range of feed solution compositions in regard to

both copper and acid concentration.
2. Extract copper rapidly across the solution interface and maintain this
excellent kinetic performance even under low temperature conditions.
3. Reject ferric iron during the extraction process.

In all other respects except one, aldoxime-based extractant systems can match or improve
on the performance of products containing ketoximes. Because of their intrinsic high
"strength" aldoximes are more difficult to strip than ketoximes although the difference
tends to be reduced at acid concentrations above 170 g/l. The discovery by our research
chemists of a range of commercially available organic chemical compounds which can
modify the stripping performance of the aldoxime ligand, Acorga P50, was a key
breakthrough in the development of extractants.

The study of how these equilibrium modifier compositions affect the performance of
copper extractants under the many and varied conditions of operation existing in the world
of operating copper SX plants has been the focus of the Avecia Metal Extraction Products
team for more than 25 years. This experience is available to users in the industry as part of
Avecia's comprehensive service package wherever in the world they are located.

3. Chelating Extractants
These are compounds that complex with a metal ion to form an organic soluble chelate. The
terminology for this class of extractant is derived from the Greek word for claw and
accurately describes the reaction between a bidentate (or multidentate) ligand and a metal
to form a closed ring of atoms, of which the metal forms a part. It is well known that the
ability of a ligand to form such closed rings adds considerably to the stability of a metal
complex (the Chelate Effect).

The chemical reaction involved in the chelation step for o-hydroxy-oximes is exchange of a
proton (H+) from the ligand with the metal ion in solution, and coordination of the nitrogen
atom of the oxime functional group to give a chelate ring. A repeat of the process to give a
second coordinated ligand gives an electronically neutral, extractable metal species.

Before a candidate ligand can be considered for selection as a practical metal extractant it
must meet several important chemical criteria.

I. The reactive grouping on the ligand must have an available proton to allow the
exchange reaction to take place. The "strength" of the ligand is determined by the
ease with which this proton is released and is a particularly important feature of
ligand design.
II. The chelation process with hydroxy-oximes is an interfacial process so that the
stereo-chemistry of the ligand must allow the metal ions to approach the
organic/aqueous interface without undue hindrance otherwise very slow and
incomplete extraction will take place. As the number of organic molecules involved
in producing the complex must equal the valency of the metal to be extracted (to
achieve electronic neutrality) adverse steric influences are more likely to be brought
to bear as the valency of the metal increases. Thus mono- and divalent metals or
metalloids form chelation compounds with hydroxy-oximes relatively easily while
trivalent species or those with even higher valency form chelates with greater
difficulty.
III. Selectivity of an extractant for a particular metal over others may be achieved by a
combination of factors.

4. Equilibrium Modifiers for Aldoxime Ligands

Metallurgical Aspects
Equilibrium modifiers were originally developed to allow aldoximes to achieve the
stripping performance of the weaker ketoximes ligands while retaining the superior
strength, kinetics and selectivity of aldoximes. They affect the degree of completeness of
the stripping reaction by a mechanism which involves a hydrogen bonding reaction
between the o-hydroxy group on the oxime molecule and key groups in the modifier
molecule itself.

The common factor in all organic species which have been identified as modifiers is that
the modifier molecule has a satirically accessible oxygen or nitrogen atom in its structure
with "lone pairs" of electrons available to partake in the hydrogen bonding process. Thus
phenols, alcohols, esters, ketones, aldehydes, ethers organic acids, amines, amides and even
other hydroxy-oximes all qualify to a greater or lesser degree as equilibrium modifiers. It is
also important that candidate organic modifiers are screened for their solubility
characteristics. To be acceptable they must have very low aqueous solubility thus avoiding
differential losses in the aqueous streams of the operating SX circuit. This requirement
imposes fairly severe restrictions on the selection of suitable modifiers if the conditions
also imposed that the modifier should be commercially available at an acceptable cost.

In addition, it has emerged from our studies (Table 2) that modifiers differ in the degree to
which they affect the stripping process and do not all have the same ability in this regard.

Table 2 "Strength" of Modifier by Chemical Type

Modifier Type Example Effect

Alkyl Phenols Nonyl Phenol Weak
Dodecyl Phenol Weak
Ketoximes Lix 84 Weak
Esters TXIB Moderate
Alcohols Tridecanol Strong
Iso-octadecyl Moderate

The relatively weak modifying effect of nonyl phenol means that it has to be blended with
the aldoximes in relatively large proportions to increase stripping efficiency to acceptable
limits. Its effect on the extraction performance of the ligand is, however, modest.
Tridecanol, on the other hand, only requires to be added to the aldoxime in relatively small
quantities to achieve a marked change in stripping performance. However, it has a more
pronounced effect on the extraction performance of the reagent system.

Esters, on the other hand, are moderate in their influence on stripping performance scarcely
at all until very high concentration has been reached .

Thus, other things being equal, they remain the modifier of choice when formulating
blended aldoxime products for metallurgical performance.
In addition to the thermodynamic advantages of ester modifiers it also became clear during
our modifier research program that other properties were influenced by the chemistry of the
modifier and that modifiers had a far wider influence on the behavior of the extractant
system than previously recognized. For instance, it soon became apparent that the Cu/Fe
selectivity of ester and tridecanol-modified products was significantly superior to that of
aldoximes blended with more widely used modifiers such as nonyl phenol and substantially
greater than that obtained with ketoxime-modified compositions .

It is generally recognized that those aspects of aldoxime chemistry which allow improved
strength, selectivity and kinetics over ketoximes also adversely influence their rate of
hydrolytic degradation by concentrated sulphuric acid. This is not a serious disadvantage in
the operating SX process as the ligand is in contact with concentrated acid only during the 2
minutes it is mixing with the "spent" electrolyte in the strip mixer i.e. for about 10% of the
time it spends in the SX circuit. Clearly, though if matters could be improved without
adversely influencing other performance properties this would be an acceptable outcome.
This has proved to be possible as it unexpectedly emerged from our modifier work that the
chemical make-up of the modifier molecule had a significant influence on the rate of
hydrolytic degradation. Thus nonyl phenol, actually accelerated the rate of degradation
while an ester modifier selected by Avecia actually reduced the hydrolysis rate as described
in US patent 4,978,788.
 Hydrolytic stability of hydroxy-oxime formulations stirred

continuously with strip acid at 30 deg C.

Commercial Formulation Modifier Rate of Loss (% day) Half Life (Years)

Acorga M5640 Ester 0.016 10.99
LIX 622 Tridecanol 0.057 3.59
LIX 984 Ketoxime 0.073 2.60

5. Hard - Soft Donor Atom Preferences

Changes in the normal order of complex stability can be brought about by recognition of
different metals preferences for certain donor ligands according to the classical Lewis acid-
base, hard-soft donor atom (HSAB) rules. Copper (II) forms strong complexes with "hard"
donor atoms such as oxygen and nitrogen, whereas some metals form stronger complexes
with "soft" donors atoms such as sulphur.

All these factors are relevant in giving exceptional strength to the P50 oxime - copper
complex and high selectivity over other metals.
It is important that an effective extractant composition is robust enough to remain stable
and active under typical operating conditions. In the case of hydroxy-oxime extractants the
most important factors which can affect reagent degradation to species which will not act as
extractants are:

(a) the concentration of acid in the electrolyte used for stripping copper from the metal
complex.

(b)the temperature of the operating circuit.

(c) the presence of contaminant metals such as manganese or other oxidizing species such
as nitrate or chloride ion which are potentially able to create aggressive oxidizing
conditions under which severe degradation of the organic ligand, and/or SX diluents, to
species which often have emulsifying properties can take place. As such species will
prevent effective separation of the organic and aqueous phases following the contacting
process it is essential that steps are taken to avoid the presence of such contaminants.

The boundaries of the acid concentration problem are determined by the corrosion rate of
the lead anodes used in the EW tankhouse and the acid, strength required to achieve
effective stripping of the metal from the ligand complex. Experience to date in the copper
industry has shown that an acid concentration of 165-180 g/l sulphuric acid is required to
achieve a suitable compromise between corrosion rate and stripping efficiency. At this level
of acid concentration degradation of aldoximes by hydrolysis to the corresponding
aldehyde is modest.

The effect of increased temperature is to accelerate the rate at which hydrolytic degradation
occurs. Solution temperatures in excess of 50oC are not recommended.

I. Early tests on aldoximes showed that the composition of the organic diluent
played an important part in optimizing the performance of the extraction
system. Kinetic performance tended to be optimized in the presence of
aliphatic diluents such as isoparaffins, while solubility of both the extractant
and its metal complex was optimized in the presence of aromatic solvents
such as the tri-alkyl benzenes. Modern diluent compositions used with
hydroxy-oximes in the copper industry for solvent extraction processes
therefore contain both aliphatic and aromatic components to achieve an
acceptable compromise.
II. Although the ligand needs to have a certain degree of surface activity to
allow it to orientate itself correctly at the organic/aqueous interface it is
important in a two-phase operating system that the degree of surface activity
of the whole system remains at a low level otherwise clean phase separation
, which is vitally important following the contacting stage of the industrial
SX process, will become excessively slow and require the construction of
uneconomically large settler units. Testing SX reagents and diluents for their
effect on phase separation is therefore a highly important part of the quality
control system operated by manufacturers of reagents and diluents.
 III. In ligand design it is also critical that the extractant composition developed
be compatible with the system in which it is expected to operate. Thus it
must be robust enough to interface not only with the aqueous solution which
it is required to treat but also with the process of metal recovery. This
requirement places further limitations on the structure of the ligand.

From the above comments it is clear that organic ligands suitable for use in SX processes
require to satisfy a large number of performance criteria simultaneously. The structure of
the ligand molecule, therefore, has to be highly specific. Also the candidate ligand has to be
synthesized in a cost/effective manner and the development of a robust, inexpensive and
environmentally suitable manufacturing route is one of the greatest challenges facing
today's process chemist. Thus it can be seen that the skills necessary to become an effective
supplier of SX reagents are complex and varied and research requires to be funded at a high
level if progress is expected to continue. Avecia Metal Extraction Products Business has an
expertise that is second to none in reagent development.

6. The Irving-Williams Series

The order of stability of complexes of the divalent metals of the first transition row
generally follow the well known Irving-Williams Series, which is Mn<Fe<Co,Ni
<<Cu>Zn. Thus, among these metals, copper would be expected to form the stronger
complexes.

7. Steric Preferences
The preference for a particular steric arrangement of ligands round a metal ion, e.g. planar,
tetrahedral or octahedral, and the ability of a ligand to satisfy this steric preference can have
a marked effect on complex stability. Divalent copper has a preference for forming square
planar complexes with chelating ligands and this configuration is readily satisfied by many
sterically unhindered o-hydroxyaryl oximes such as 2-hydroxy-5-nonyl benzaldoxime
(Acorga P50). Considerable additional stability is conferred on the complex by hydrogen
bonding interactions which give a pseudo macrocycic structure composed of two five-
member, and two six-member rings.
 Hydrogen bonded square planar structure of the copper complex of P50 oxime.

8. Phase Separation
It is also important in an increasing number of operating SX plants to be able to maximize
production by increasing the flow rate of the aqueous stream feeding the extraction stages.
The limiting factor in doing this is almost invariably the rate of separation of the phases
after mixing. Blends of aldoxime and carefully selected modifiers have been shown to
allow very fast phase separation rates. Copper operations using Acorga M range products
have achieved increases in feed flow rates of up to 20% using Avecia's advice on reagent
composition. It must be stressed, however, that for best effect careful formulation of the
extractant is required as too rapid phase separation can increase O in A losses by
entrainment due to a phenomenon known as "secondary haze" in which very fine particles
of organic can remain suspended in the aqueous phase if phase separation is too rapid.
These very fine particles have great difficulty in coalescing.

There are also strong indications that the presence of a relatively deep dispersion band in
the settler can act as a "filter," assist coalescence and reduce O in A entrainment levels.

9. Physical Transfer of Contaminants

After the first extraction stage in an SX plant the organic phase in the counter-current
process is fully loaded and, following separation from the aqueous phase passes to the
"stripping" section of the plant. Industrial phase separation processes are constrained by the
time made available for separation and are never totally complete. Thus the advancing
organic phase normally contains low concentrations (ppm) of the aqueous feed entrained in
it. The degree to which this becomes a problem will be determined by factors such as feed
composition and SX circuit equipment design.

In the former case, contaminating species such as chloride ion are becoming more common,
particularly in Chile where SX/EW cathode now has to be produced regularly from the
chloride-containing copper-bearing ore atacamite. The resultant chloride ion in the leach
solution can potentially be entrained via the organic into the EW tankhouse electrolyte and
will cause major corrosion problems if stainless steel permanent cathodes are used in the
electrodeposition process. It is thus vitally important that aqueous entrainment from such
feeds is kept to an absolute minimum.

Earlier SX plant designs often located the organic surge tank between the extraction and
strip sides of the circuit. This was useful in that the tank acted as a barrier to the
entrainment of impure leach solution being carried over into the electrolyte. In modern SX
plants it is now more usual for the surge tank to be located between the final stage of
stripping and the extraction circuit. By designing the surge tank with a format and feed
system which produce flow down the tank length and by careful location of de-entrainment
baffles, aqueous entrainment can be reduced to levels which allow a normal electrolyte
bleed system to satisfactorily control the build-up of contaminants such as chloride ion.

Again it has been discovered during our modifier evaluation program that the chemistry of
the modifier can influence the degree to which undesirable Organic in Aqueous (O in A)
entrainment occurs. Acorga products are therefore formulated with modifier compositions
which can help minimize this.

10. Control of Solids

Unless special precautions can be taken to eliminate solids entering the SX plant via the
leach liquor feed these will invariably create problems which must be managed. Objective
testwork and operating experience by Avecia personnel has determined the following facts
(reported at the AIME meeting in Denver, CO, 1991):

1. "Crud" cannot be "generated" or "created" by modifiers or by any other

means although this may appear to have happened if test conditions were
selected which resulted in inefficient packing of the crud layer at the
interface. Certainly conditions can exist under which solids introduced into
an SX circuit can be made to appear quite voluminous. However, careful
selection of operating conditions, particularly phase continuity, will ensure
that crud is well packed at the interface. Avecia's field specialists can
provide specific advice in this area.
2. If the ingress of solids cannot be prevented, crud is most easily controlled in
operating plants by regularly removing it from the oil/water interface as part
 of a planned operational maintenance program. Failure to implement such a
program can result in higher-than-necessary organic losses.
3. Removal of "crud" will be made easier and organic losses reduced if the crud
is packed at the interface, particularly if it can be moved into the lower
aqueous region of the dispersion band. Packing in this way will generally be
encouraged if the organic phase is chosen to be the continuous phase in the
contracting stage under consideration.

Silicaceous Feeds

SX feed solutions containing silica are notoriously difficult to deal with due to the many
different physical forms which silica can adopt in acid "solution." The use of nonyl phenol
as all or part of the modifier in extractant compositions for feeds containing silica is
recommended. See "Aspects of Crud Formation in Solvent Extraction Plants" by Dalton,
Maes and Severs presented at the Annual Meeting of the Arizona Conference of the AIME,
Tucson, December 1983.

An interesting method for pretreating feeds containing colloidal silica was developed at the
Olympic Dam copper/uranium SX operation in South Australia. This involved a two stage
flocculation process in which a primary flocc was produced using a long chain water-
soluble polymer. This was in turn further treated with a conventional flocculant to produce
a secondary flocc which was settled and removed through a standard clarifier. This process
has been used successfully for many years. Further information can be obtained from your
local Avecia representative.

11. Physical Effects

Organic Losses
In an operating SX plant losses of circuit organic arise from several sources. One of the
major sources of such losses is by entrainment of the organic phase in the aqueous streams
exiting the circuit and from the enriched electrolyte stream feeding to the EW tankhouse.
The former are normally considered to be more important than the latter as:

1. the flow rates involved are much larger;

2. organic recovery systems for the latter tend to be more efficient.

A laboratory study of factors controlling organic, in aqueous entrainment of this type, has
shown that the molecular geometry of the modifier can play a major part in containing
organic losses generated in this way. This information, used to formulate the most recent
additions to the Acorga M range of copper extractants, is the basis of Avecia patent US
4,978,788.
 12. The Industrial Leach-SX Process

The industrial scale solvent extraction process is a counter-current multi-stage contacting

operation which consists of an extraction and a stripping section. If required, scrubbing or
washing stages can be incorporated into the circuit to remove unwanted impurities
entrained into the organic phase from the feed solution. Feed solutions to SX circuits
typically arise from leaching processes and the product from the strip stage generally
consists of a purified, concentrated solution of the desired metal ion species in a form from
which the metal can be recovered. Copper and zinc, for instance, can be recovered as
cathode from a suitable electrolyte solution while the former can also be isolated in the
form of solid hydrated copper sulphate by means of an evaporative crystallization process.
Minas de Almagrera in Spain operate this latter type of process using Acorga M5640 as
extractant.

A typical LEACH-SX-EW circuit for copper consists of three closed loops as shown in the
schematic diagram below.

The raffinate from the SX plant (containing the acid generated during the extraction
reaction) is returned to the dump or heap to leach out more copper thus closing the
LEACHING loop. Sulphuric acid used up during the previous leach cycle is added back
into the raffinate during this process.
In the SX loop the organic extractant solution is contacted with the feed solution and the
loaded organic stripped with spent electrolyte to regenerate the active extractant in the
stripping process. This loop is closed when the regenerated extractant is returned to the
extraction circuit to recover further copper from the leach solution.

The EW loop is closed when the spent or lean electrolyte from the tankhouse is returned
with the additional acid generated during contact with the extractant as an advanced or rich
electrolyte. Some acid make-up is required to replace handling losses in the tankhouse and
to counter balance acid lost through the electrolyte bleed which is used to control minor
impurities.

a) Leaching

In the recovery process for copper by LEACH-SX-EW copper-bearing materials, typically

in the form of low-grade ore or tailings are contacted by 15-20 g/l sulphuric acid. The
contacting process used will depend on the source of the copper to be recovered. For low-
grade ores percolation of the acid through heaps or dumps is standard procedure in most
parts of the world followed by collection of the "pregnant leach solution" (PLS) in shallow
ponds sited for convenient transfer of the PLS to the solvent extraction circuit. In the US a
number of dump leach operations have used "acid curing" stages ahead of the standard
percolation process to assist the leaching process for many years. For tailings and copper
matte products, agitated tank leaching is the preferred contacting process. Acorga products
are used in conjunction with such processes in Zambia (Tailings Leaching by ZCCM), in
Australia (oxidative leaching of a ground copper matte by Pasminco at their Port Pirie lead
smelter).

b) solvent extraction

Industry almost universally uses mixer-settler equipment in the SX contacting process.

Static mixers, centrifugal separation systems and even electrostatic separation methods
have all been tried over the years but the majority of SX plants operating in the 90's consist
of simple mixer boxes, sometimes arranged in series, discharging the organic/aqueous
dispersion into a shallow settler typically 1 meter deep. The moving dispersion is allowed
to separate by gravity as it passes down the length of the settler. Final phase separation is
affected by a simple weir system with the organic phase flowing over the upper weir and
into a collection launder and the aqueous phase passing under the upper weir, over a lower
weir and into a similar launder as illustrated below.
Earlier SX plants were designed with up to four extraction and three stripping stages as at
the Bagdad Copper operation in Arizona. However, the introduction of the stronger Acorga
aldoxime-based extractants in the late 1970's ensured that, in future, plants would comprise
of less stages. In contrast to ketoxime reagents, such as those developed under the LIX
trademark by General Mills Chemicals Inc. in the United States (now Dusseldorf based,
Henkel Corporation), the aldoximes have steeply rising and sharply bowed extraction
distribution isotherms thus allowing very low raffinate and high percentage recoveries to be
achieved with fewer extraction stages. For copper-bearing leach solutions typical of
dump/heap leach operations only one or two extraction stages are now necessary for
efficient extraction and a single stripping stage is all that is required in most circumstances.
The fast kinetic properties of aldoxime-based reagent systems means that mixer residence
times have been reduced from 3-4 minutes to 2-3 minutes and mixer boxes are now
consequently smaller and less expensive. Settler sizing has been similarly down-sized as
phase separation times have been reduced and specific flow values increased from 1.0 - 1.5
US gallons/ft2/min (2.5 - 3.6 M3/M2/hr) to 1.8 - 2.5 US gallons/ft2/min (4.4 - 6.1
M3/M2/hr). Design of mixer boxes, impellers and dispersion distribution systems vary in
detail from plant to plant depending on the specific requirements of the operation but the
above features are common to all plants.

A photograph of a typical copper SX plant is shown below:

The improved new reagents have also made various alternative SX circuit configurations
such as cross flow circuits more attractive. The most common use of this concept is in the
parallel/series circuit. In this design of plant a 2 + 1 configuration is typically augmented by
construction of an additional extract settler and the PLS flow increased and dividend into
two. One stream typically feeds a single extraction stage and produces a raffinate for return
to leach while a parallel stream feeds the original two-stage extractor train and generates a
separate raffinate. Meanwhile, the organic phase advances through each of the extraction
stages in series and the loaded organic passes to a conventional stripping section.

Clearly the amount of copper recovered in the single extraction stage will be lower than
that from the parallel stage and the overall recovery reduced from the high levels obtained
on the original 2 + 1 plant. However, this shortfall can be compensated for simply by
increasing the reagent concentration. The overall effect, however, is a substantial increase
in copper production as the PLS flow is now doubled. This type of plant modification is
clearly of most interest where additional flow is readily available and makes more efficient
use of scarce capital resources than constructing an additional 2 + 1 facility.

c) electrowinning

The technology used in the recovery of copper at the cathode of an EW cell from solutions
purified by SX processing has been established for many years and while conceptually
simple modern operators now use fairly sophisticated methods to ensure a smooth running
operation and produce a high volume of good quality cathode which can be sold at
premium prices in the market.

Electrowinning is carried out by passing a rectified current through a copper-bearing

electrolyte from the anode to the cathode of an EW cell. During this process copper is
deposited at the cathode over a period of several days after which time the cathodes are
"pulled" and the copper sheet stripped, washed and stacked ready for shipment. Modern
EW tankhouses typically use lead-based alloys as the anode of the electrolytic cell and
stainless steel as the cathode. Use of the latter allows the concept of "TOTAL
PRODUCTION STRIPPING" to be implemented. This is both cost effective in terms of
reduced manpower requirements and allows closer spacing of the electrodes.

Cell construction is often carried out in concrete with PVC liners. However, the
introduction of "POLYMER CONCRETE" has allowed one-piece construction without the
potential for leakage. Modern EW plants tend to be constructed in this way.