ZENECA - CHINA - SYMPOSIUM

Leach, SX-EW Production of Copper - A Global View.

by G W Seward, Technical Manager, Zeneca Specialties, Metals Extraction Products

Introduction

The copper bearing mineralogical veins of principle importance to companies wishing to produce
copper by leaching, SX-EW run from the far Northern Western reaches of Canada, through the
‘copper belt’ states of Western USA and Northern Mexico and through Peru and Chile in South
America. Small prospects exist in other countries of the Americas - Cuba. Argentina, Brazil Panama. In
addition SX-EW is important in treating copper deposits in Australia as well parts of Central Africa.
The leaching methods being used to produce feed for SX-EW are also discussed.

Historical

It is often quoted that the first production of copper metal as a result of leaching ore occurred in the
18th Century at the Rinto Tinto mine in Huelva, Southern Spain. The metal being precipitated from
solution by iron. This may be true in terms of what we know in the West but I suspect that you can
probably tell of earlier examples of the cementation process in China.

As far as the use of selective organic extraction reagents being used to purify and concentrate leach
solutions in order to make possible the commercial production of pure copper metal from the
electrowinning process, it was almost certainly the pioneering operations of the Bluebird Mine and
Bagdad Mines in Arizona, USA in the late 1960’s that represented the beginning of the SX-EW
technology as we know it today.

The first commercial plant started operation at the Rancher’s Bagdad mine in 1968 with a production
capacity of 6,000 t p.a. In 1973, the first large plant was brought into operation in Zambia to produce
100,000 t p.a. and by 1980 new plants were on stream in the USA, Mexico and Chile to produce a
total production capacity of approximately 180,000 t p.a. Today, in 1997, there is a total world
production capacity of copper by SX-EW of 1.4 million t p.a., and by 1998, the thirtieth anniversary of
the technology there will be a production capacity of approximately 1.65 million t p.a. or about 20% of
the total world production of copper metal.

This growth in production will almost certainly begin to slow by the end of this century because there
has been a rush to exploit the large, primarily oxidic, high grade deposits in the last decade and almost
certainly new projects will in future be developed that are hydrometallurically treating sulfidic ores, in
regionally more diverse areas of the world.
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Background to Growth and Development

The commercial interest in SX-EW of copper began in the North America and was initially the result of
leaching studies of low grade oxidic minerals that were not available for upgrade and concentration by
flotation techniques. Their loss to waste dumps represented poor management of natural resources and
importantly a loss of potential revenue that the mining companies in the USA could not afford because
of their high labour costs and overall low mineralogical grades, relative to other copper producing
countries. With copper being an internationally traded commodity the concept of producing the metal at
the lowest possible cost was important otherwise the copper industry in the US would be at a significant
disadvantage relative to other nations.

Early plants therefore developed the technology based on dump leaching of ‘‘run of mine’’ low grade
oxide ores and flotation tailings. The consequence of this was that the concentration of copper in the
leach solutions was always relatively low (about 1.2 - 2.0 gpl Cu2+ and at a pH of approximately 2.0).
The low concentrations meant that the solvent extraction reagent did not need to load very high
concentrations of copper and the low acidity of the solutions meant that high recoveries could be easily
achieved. The plants at Ranchers Bluebird (which shutdown in 1980) and at Cyprus Bagdad were
typical of these types of plant and demonstrated very effectively the commercial potential of this
technology.

Leach testwork progressed and techniques were soon developed to allow both oxides and sulphide
mineral to be leached. In some cases agitation leaching was introduced both of ground oxidic tailings
material and sulphide flotation concentrates after roasting.

The large plant installed in Zambia was an example of the former as was the leach plant installed by the
Anamax company near Tucson in Arizona in the early 70’s (TwinButtes).

Others, particularly in Chile and Peru, were looking at the treatment of both lower grade solutions from
mine waters and higher grade solutions from vat and heap leaching techniques.

The El Teniente mine in Chile with a long history of ownership by an American copper producer,
Kennecott, began to look at SX-EW as a means of obtaining value from its mine water run off problems
and at the same time to control the environmental concerns that such mine waters were causing. Clearly
this was a very cheap source of copper but the plant suffered from a wide variation in aqueous flowrates
with considerable seasonal fluctuation. This has always caused El Teniente problems but the plant
continues to operate at low production rates. The current owners of El Teniente are the Chilean State
Copper Company, CODELCO, and the experience gained was very valuable when they expanded the
technique at their Chuquicamata mine in Northern Chile a few years later.

Other plants in North America have considered the treatment of mine waters as a reason for introducing
SX-EW. Included in this category of plant is the Gibraltar mine which operates in the very cold climatic
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conditions of British Columbia, Canada. Gibraltar mine began operation in 1986 treating low grade
solutions from dump leaching of ROM waste material but also introduced as a means of controlling mine
water environmental impact. This plant continues to operate successfully.

The treatment of solutions from VAT leaching and heap leaching of high grade ores lead directly to the
development of ACORGA P-5100. This was a new type of solvent extraction reagent particularly
suitable for treating leach solutions containing higher concentrations of copper and was first introduced
commercially at the Inspiration Consolidated Copper plant and the Kennecott Ray mine plant’s in
Arizona in 1979 and 1980 respectively.

High grade copper sulphate solutions, often with high concentrations of iron sulphates present required
strong extractants to allow high copper loadings on the reagents, good recovery and good selectivity
against iron. ACORGA P-5100 was the best reagent to achieve this for a number of years but in recent
years has been replaced with new ACORGA reagents such as M 5640 and PT 5050 both of which
have better selectivity and recovery characteristics. These new class of modified aldoxime extractants
have greatly contributed to the growth trend in SX-EW technology.

Leaching Development

VAT leaching used in combination with cementation or direct electrowinning of the copper was one of
the earliest techniques practised to recover copper from oxidic ores in both the USA and Chile.
Inspiration Consolidated Copper, located in Arizona and currently named Cyprus Miami by its current
owners, built a VAT leach plant in 1926 following on from one built at Chuquicamata in 1915. These
plants where large installations producing high copper recoveries which, by having two or more stages
of leaching, where able to build up high concentrations of copper suitable for direct electrowinning. A
number of disadvantages where evident from this technology including the inability to produce high
grade copper cathode due to impurities in solution and the low current efficiencies due to high levels of
iron in the electrolyte. The equipment costs where also high.

Overwhelmingly now, heap leaching has become the accepted technology of choice for most
operations around the world and particularly for new Leach-SX-EW operations installed in recent
years in the USA, Chile and Australia.

Two options exist when developing a heap leaching operation:

(1) Heaps built on PERMANENT pads or

(2) Heaps built on REUSABLE pads

Permanent pad heap leaching was the predominant technology in both North and South America until
the recent construction of large new L-SX-EW operations at El Abra (1996) and Radomiro Tomic
(1997), both using reusable pads.
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The development of a permanent pad requires that either an impermeable clay substrate is present at the
site of the heap or a plastic lining is put in place before the heap is developed.
The heaps are then established as a single lift of up to 20 metres or can be made up of multiple lifts.
The benefit of this approach is that high recoveries can be achieved (60-90%) depending on the
mineralogy of the ore, the size profile of the ore and the height of the heap. In addition the percolation
rate of acid addition can be adjusted to assist recovery or ‘‘curing’’ of the ore can be used in order to
improve the leach kinetics. Strong acid is first used to wet the ore, then larger volumes of more dilute
acid is percolated through the dumps. This strategy is a technique developed by Cyprus Miami about 15
years ago to maximise the leaching characteristics of their mine to a leach operation which today
produces about 60,000 tonne of copper per annum by the technology. This is particularly important
when the ore body contains a large proportion of chalcocite or other only partially acid soluble copper
minerals.

In addition the ability to add lifts to already leached deposits further assists in improving the overall
recovery of the ore body. Permanent pad technology is the choice of the Quebrada Blanca operation in
northern Chile. At this operation, located at an altitude of 4400 m above sea level, bacterial leaching of
a sulfide deposit is successfully accomplished by agglomeration of ore in a rotating drum prior to
distribution in 6 m lifts to the permanent heap. The leach area under irrigation is currently some 1.6
million m2 and 80% recovery is achieved in 300 days assisted by the use of air being blown into the
heap via 6 cm pipes. A drip irrigation system is used at a rate of 0.1 litres/min/m2. The top of the heap
is compacted between lifts and the air lines installed.

The mineralogy is principally chalcocite (1.3% grade) and produces a feed solution to SX containing
approximately 3.5 gpl Copper and 2.5 gpl iron.

Similar technology is used in Australia at the Girilambone mine, owned by Straits Resources. Again the
mineralogy is mainly chalcocite and leaching is promoted by the presence of bacteria and forced
aeration of the heaps to achieve better than 80% recovery in 300 days. Aglomeration and a radial
stacker is used to prepare the 6 m high heaps.

The growth in the technology of permanent pad leaching, particularly in Chile where compared to the
US ore grades are high, has lead to some very large operations being established in short periods of
time. The concentrations of copper in solution are relatively high and pH is very variable. Solvent
extraction reagents such as the Acorga M-5640 are therefore needed to ensure that production at
these mines is maximised. This has proved to be the experience at the Manto Verde operation, owned
by Empresa Minera de Mantos Blancos SA, will began operations in November 1995. The leach
solution arises from heap leaching of primarily oxidic mineralisation, such as Brocantite,
CuSO 4.3Cu(OH) 2 . Agglomeration leaching is be used with the agglomerated ore conveyed to the
permanent heaps by means of conveyers. The grade of the ore is such that copper concentrations of 5
gpl at a pH of between 1.8-2.0 are expected as feed to the SX plant and in this case 18% M5640 will
be used to treat this solution in a plant consisting of 2 stages of Extraction, 1 wash stage, 2 stages of
Stripping. High recoveries are achieved and importantly good selectivity against the high level of iron in
solution is demonstrated.
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The wash stage is incorporated in this plant to prevent chloride transfer to the tankhouse. In most places
in Chile there is an abundance of chloride mineralisation that either ends up being leached ( such as
Atacamite, CuCl2.3Cu(OH) 2 ) or that arises with the wash water.

Some locations favour the Reusable pad concept of heap leaching. This technique was pioneered at
the Societe Minera de Pudahuel (SMP ) mine, Lo Aguirre. In the late 70’s they developed a technology
that they called ‘‘thin layer leaching’’ which involved crushing, followed by ‘ ‘wetting’’ of the ore in a
rotating drum, followed by removal with front- end- loaders to pre-prepared leach pads. The finally
crushed ore was agglomerated in the drum and then irrigated, to provide an SX feed solution, on the
pads. In a manner analogous to Vat leaching the ore had to be removed to a disposal area after leaching
was complete. The technique was considerably cheaper to install than a VAT system and proved very
effective at this operation, which although nearly depleted of leachable reserve is still producing about
10,000 tonne copper per annum.
Other small operations in Chile have seen the benefit of this technique when available space is at a
premium operations such as Minera Michilla’s Lince operation and Exxon’s, El Soldado mine., but the
new operations at El Abra (225,000 tpa copper from oxide ore) and Radomiro Tomic (150,000 tpa
copper) have taken it to the grand scale due mainly to the availability of reliable high capacity stacking
equipment such as produced by Rahco of Spokane, Washington, USA.
This equipment enables self propelled mobile stacking and reclaiming bridge conveyers to discharge
fresh ore at points along the stacking conveyer and has a bucket wheel excavator to reclaim spent ore
from the heap and feed it to the reclaim conveyer. The position of the bucket wheel reclaimer and
conveyer are aligned and controlled by satellite global positioning data.
The costs of this in operational terms is very low at about 1 to 12 cents per tonne of ore.

The chemistry of heap leaching determines the actual factors that are important in any particular leaching
situation. Performance predictions are generally made from column testing with test heaps constructed in
some cases. This is particularly the case in colder areas where the leach process already suffers the
natural disadvantage of low temperatures. Again the chemistry and indeed the biochemistry of the dump
is important in these circumstances where heat generated by the dissolution process or the
bacteriological process is very important in determining the eventual viability of an operation. The most
northerly and coldest locations in the Americas where dump leaching occurs successfully is the Gibraltar
mine in British Columbia, Canada. It is known that others are also considering leach operations in this
part of Canada where temperatures will be even colder and in these circumstances they have
considered it wise to invest in a test heap leach programme before making final investment decisions.

It is known that the solubility of the primary sulfides, such as chalcopyrite, is very low in sulphuric acid
unless assisted by the presence of ferric sulfate solution.

Indirectly the process mechanism can be shown to be significantly aided by the presence of ferric sulfate
which in turn is continuously regenerated in the heap by the presence of bacteria. Bacteria also play a
significant role in the oxidation of the sulfide minerals and in the oxidation of sulphur which is formed
during the leaching reaction as an intermediate product:
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CuFeS2 + 2Fe2 (SO 4 )3 = CuSO 4 + 5FeSO4 + 2S

5FeSO 4 + 1.25 O 2 + 2.5 H2SO 4 = 2.5 Fe2 (SO 4)3 + 2.5 H2 O
2S + 3O2 + 2H2 O = 2H2 SO 4

Directly the process can be represented as follows with the definite need for Oxygen to be part of the
leach reaction, hence the absolute need in heap or dump leaching for air to be allowed into the heart of
the dump.

Overall:

CuFeS2 + 4.25 O 2 + 0.5 H2SO 4 = CuSO 4 + 0.5 Fe 2 (SO 4 )3 + 0.5 H2O

The process of producing ferric sulfate during the leaching of chalcopyrite also leads to the potential for
the heap to be acid generating, particularly if pyrite mineralisation is also present. Although ferric
sulphate is consumed in the leaching process a proportion remains available for conversion to acid by
hydrolysis, viz:

Fe 2 (SO 4 )3 + 6H2O = 2Fe(OH) 3 + 3H2 SO4

Heap leach operations in which chalcopyrite and pyrite predominate can be difficult to control from an
acid generation point of view when linked to SX because, of course, acid is also returning with the
raffinate. In these circumstances care is taken when establishing the heaps to ensure that there are
enough acid consuming minerals available to keep the acid in balance. Apart from the oxides,
secondary sulfides such as chalcocite can very useful in this respect because of their overall consumption
of acid even though, as with chalcopyrite, their dissolution is greatly aided by the presence of ferric
sulfate and bacterial action, viz:

Overall:

Cu2S + 2.5 O2 + H2 SO 4 = 2 CuSO 4 + H2 O

In many cases however the acid is consumed by non-valuable minerals (gangue) or minerals that can
lead to percolation problems in the dumps or impurities in solution that can have an impact on the
performance of the solvent extraction and electrowinning.

In dump leaching operations in which chalcocite predominates, usually in the presence of pyrite, such as
at Giralambone or Quebrada Blanca the biggest challenge is to get an adequate conversion of ferrous
ion to ferric ion in order to allow the leach conversion of chalcocite to occur by the two step reaction
mechanism described as follows:
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step 1 Cu2S + 2Fe3+ = CuS + Cu2+ + 2Fe2+

step 2 CuS + 2Fe3+ = S + Cu2+ + 2Fe2+

As described this can occur by forcing air into the dumps and bacterial action. An alternative to this is to
use an autoclave to to reoxidise ferrous to ferric using pressurised oxygen although it is known to be
difficult to fully oxidise all the ferrous in this way and the ferric level at the end of the leaching process is
at a minimum which generally results in the very slow leaching of covellite ( CuS) in step 2. In order to
overcome this at the Gunpowder operation in Queensland, Australia a low temperature autoclave leach
will be used on ore. Raffinate from SX contains ferric ion and this is repulped with fresh ore to produce
a partly leached, highly reduced autoclave feed. This allo ws for ‘’in situ’’ regeneration of ferric to drive
the leaching process to near completion. The conditions will be mild at less than 100 oC and relatively
low pressure and a post autoclave leach reaction will allow the ferric reaction with residual copper to
proceed. This process is currently being installed as part of a major expansion of the operation.

Pressure leaching of copper concentrates is currently undergoing a number of investigations and

developments, particularly in Canada. This will not be discussed in detail at this time but suitable
references are:

King, J A and Dreisinger, D B , ‘’Autoclaving of copper Concentrates’’,Proc. Copper ’95, Cobre95, (

1995), 511-534. Editors: Cooper, W C , Dreisinger,DB, Dutrizac, JE......Can. Inst. Min. Met.
Montreal, Canada.

Jones D L , ‘’CESL Copper Process’’, presented at the ALTA Copper Hydrometallurical Forum,
Brisbane, Australia, October, 1996.

Solvent Extraction Developments

Equipment changes for SX have been evolutionary rather than revolutionary. Early plants used a design
of mixer-settler in which the mixer was located at floor level whilst the settler was raised on stilts or
columns above ground level. This was believed to be the best way of ensuring that the settlers would
not have undetected leaks. It did however increase the capital cost of such plants and a change was
made in the late seventies to plants with settlers at floor level and mixers in trenches below ground level.

Broadly speaking the types of mixer settler in commercial use are categorised as being of conventional
design with the weirs being at the far end of a settler compartment and as a consequence the units are
alternatively arranged to reduce pipework, or they are the Krebs desig n in which the flow is carried to
the end of the settler by a launder and then is returned back towards the mixer in the settler
compartment. If this type of equipment is used then the mixers are all situated at the same end. A similar
concept is used by Bateman Engineering for plants they have built in Mexico and Zimbabwe.

Minera Rayrock brought on line a Krebs plant to treat their heap leach solutions during 1994.
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at their Ivan mine in central Chile. The plant is designed to treat two separate leach zones, one being
primarily oxide and the other being mainly sulfide mineralisation. The reason that the development is
made up of two separate leaching regions is to prevent the build up of chloride in the sulfide circuit,
present from leaching Atachamite in the oxide zone. If chloride was to be present in the sulfide circuit
then there is a danger that the bacterial activity in the heaps will be detrimentally effected and leaching
performance reduced. The plant is designed to produce 28,000 tonnes copper per annum.
Eventually when the sulphide leach is fully established the oxide reserve will be closed. The PLS from
the oxide circuit contains 7 gpl Copper, and as much as 25 gpl chloride. The PLS to the sulphide circuit
contains 5 gpl and much less chloride. The extraction stages from both sides of the plant feed to a
common wash stage and the to a single stage of strip. A feature of Krebs equipment is the higher
specific flowrates that are used compared to the conventional. In this case 9 m3 m2 Hr-1. was used
compared to a conventional specific flow rate of 5 m3 m2 Hr-1. The conical pump arrangement and the
top launder tend to make these higher throughputs possible. The compact nature of this plant meant that
the units could be fabricated off site ( in Canada ) and shipped to site for installation.

Another innovation being introduced is the use of VSF,Vertical Smooth Flow, mixers designed by
Outokumpu Oy in Finland. This innovation has been extensively piloted at Chuquicamata and is said to
significantly reduce the amount of entrainment in the raffinate stream, greatly reducing organic make up
losses. The actual performance of these mixers can know be judged on the large industrial scale
because they have been installed in the Zaldivar plant in Chile which came on stream during 1995. The
new Radomiro Tomic plant in Chile is also using the the Outokumpu VSF design of plant.

Originally all SX plants were fabricated in Stainless steel. In recent years there has been a shift to high
density polyethylene HDP, for lining settlers. Chuquicamata were the first to do this but now most plants
in South America use this material in the settlers. In north America stainless is still preferred.
Other innovations relate to techniques being introduced to expand capacity whilst minimising the capital
cost of the changes and methods introduced to allow the production of a better quality cathode product
produced at lower operating cost.

Expanding Capacity by use of Series-Parallel layout

One of the first companies to take advantage of this form of plant layout in order to expand production
at minimal cost was Phelps Dodge Corporation, at their Tyrone plant in Arizona.
This plant started production in 1984 with a production capacity of 39,000 tonnes copper. During 1988
Tyrone was able to produce 49,000 tonnes by expanding the existing plant through the addition of 2
new mixer settler units, 1 added to each stream of the existing plant.
The original plant treated 1820 m3hr-1 . of dump leach solution. By adding the extra mixer settler units to
each stream the throughput was increased to 3640 m3 Hr-1 The extra flowrates to the dumps reduced
the tenor of the copper in solution, but production was nevertheless increased an extra 26% at low
cost. Others have added the series-parallel option to expand production, such as Magma Copper at
their Miami division and Phelps Dodge at their Morenci division.

Improving Quality and Cost of Production.

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The principal means of addressing quality is to ensure that carry over of entrained aqueous and
entrained organic to the electrowinning tankhouse is minimised. Costs of production are also improved
as a result of recovering organic that would otherwise have been lost and improving current efficiency
through low levels of impurities in the electrolyte.
Most of the early SX EW plants installed a filter system in the electrolyte line to prevent carry over of
the entrained organic into the tankhouse. As all of the early plants electrowon copper on copper sheets
that were produced in the cells of the starter sheet section of the tankhouse, then there was a severe
danger of being unable to produce those starter sheets if the organic was allowed to enter the tankhouse
and coat the titanium or stainless steel cathodes. The most common device installed was a dual media
filter usually comprising of a course anthracite and garnet minerals. These units were generally effective
but required high levels of maintenance and where expensive to install. Magma Copper Company in
Arizona were innovative in introducing flotation columns in their operation to perform this duty at lower
capital and operational cost. since that date a number of operations have used flotation columns and a
number of companies offer these units for this duty, including Cominco Engineering in Canada. Some
operations prefer to further reduce the risk of entrained organic and other residues in solution by
backing up the column with a dual media filter.

The new plants owned by Manto Blancos in Chile fall into this category and will use Magma columns
and Disep dual media filters. In recent years a new design of Flotation cell has found favour with some
operations. It is the Australian device known as the Jameson Cell after the inventor. This unit is more
compact than the equivalent column and has higher throughput’s of solution. The largest version of this
unit is in operation at Phelps Dodge’s Morenci operation for electrolyte clean up and at their Tyrone
operation for organic recovery on their raffinate lines.

The other operation that has been improved in recent years is that of ‘‘crud or gunk’’ removal from
settlers and its subsequent treatment to recover organic which can be re-used in the plant. A number of
operations have been active in developing strategies to treat ‘‘crud’’. Chuquicamata in common with
most plants used a portable compressed air driven pump to suck crud from the settlers on a regular
basis. This material was the sent to a centrifuge for organic recovery and the solids for disposal. Again
maintenance of the centrifuge proved to be a problem and organic recovery was rarely more than 80%
so Chuquicamata began to study alternative means of treating crud and developed a technique in which
clean plant organic is added to an air agitated pachuca and the crud is then added to it , taking care to
maintain organic phase continuity throughout the agitation process. It was found that when the agitation
is stopped the separation of phases is clean and rapid with the solids forming a compact layer in the
aqueous phase and the organic trapped in the crud was released to the clean organic layer and could be
fed back into the circuit. The solids in the aqueous could be easily disposed of. This method has in fact
been patented by Codelco. Magma have gone on to further refine this technique and claim organic
recovery as high as 98%.

The recovery of organic from raffinate ponds has also been the subject of considerable improvement in
recent years with the organic being collected in floating booms and being skimmed from the surface of
the pond to a holding tank for subsequent treatment to restore the physical properties of the reagent
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before returning the organic to the plant. Usually this is done by the use of clay treatment. In the case of
Magma and soon to be introduced at Cyprus Miami operation is a system whereby the organic is
filtered through an acid activated montmorillonite clay before return to the SX circuit.
When following any of these strategies it is important that the organic is not added back into the circuit
until tests have shown that the quality of the product is such that it will not contaminate the existing
organic already in the circuit.

Conclusion

Leach SX EW has been a rapidly developing technology in recent years not only in the ‘Americas’ but
around the world. The ‘Americas’ have been able to demonstrate however that good technology can
always be helped by refinement of technique and large scale application of the technology. Policies in
South America in recent years have encouraged development of natural resources and investment has
been encouraged from internationally focused mining companies who have been able to bring their
techno/financial experience to bear on some very large projects.
In general this experience has been shared and now we find that many deposits around the world that
have previously not been regarded as suitable for economic exploitation are being re- considered and
this will hopefully lead to the valuable economic regeneration of other mineralogical areas.

November 1997.