New Developments in Hydrometallurgical Treatment of

New Developments in Hydrometallurgical Treatment of

Copper Concentrates
David Dreisinger
University of British Columbia
Canada
[email protected]

Abstract
The treatment of copper concentrates by smelting converting and electrorefining has dominated the copper
industry since the 1800s. Research and development in searching for hydrometallurgical alternatives to
traditional pyrometallurgy processes has intensified in recent years. A whole range of chemical and biological
processes for copper recovery from concentrates have
emerged. These processes are all successful in (1)
dissolving copper from chalcopyrite concentrates, (2) purifying the leach solutions using modern separation
processes and (3) recovering a high value, high purity copper metal product.
The processes under development can be divided into predominantly sulphate and chloride processes. Within
the sulphate grouping, processes can be sub-grouped as either atmospheric or super-atmospheric in pressure
and chemical or biological in the leaching process. The chloride processes are less numerous but some
important advances in chemistry, equipment and process development have vaulted the chloride systems back
to competition with sulphate processes.
The recent developments in hydrometallurgical treatment of copper concentrates are surveyed in this paper.

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David Dreisinger

Introduction
The conventional treatment of copper concentrates involves smelting, converting and electrorefining to produce
a copper cathode product. Sulphur in the copper concentrates is oxidized to sulphur dioxide during smelting
and converting and is used to make by-product sulphuric acid. Iron in the copper concentrates reports to the
slag. Precious metals are recovered from the anode slimes produced by the electrorefining operation. The
conventional treatment of copper concentrates by this method works well.
There are however, a large number of reasons for pursuing alternatives to conventional processing.
1.

Capital Cost. The capital cost of smelter and refinery complexes is very high. The typical range of cost is
$3,000 - $5,000 (USD) investment per annual tonne of copper production (eg. $900 Million to $1.5 Billion
for 300,000 tpy Cu production). The unit cost will vary according to scale and location. The high capital
cost of smelters/refineries is partly offset by low operating costs. Nevertheless, a less capital intensive
copper production process would be advantageous.

2.

Impurity Tolerance. Smelters are limited in ability to treat concentrates that contain high levels of
deleterious impurities. Concentrates that contain high levels of impurities such as selenium, tellurium,
mercury, arsenic, antimony, bismuth, fluoride and chloride may incur large financial penalties under
currently prevailing smelter contract specifications. Alternately, at some impurity level, it may not be
possible at all for the smelter to treat the concentrate.

3.

Copper-Gold Concentrates. Gold is frequently associated with copper concentrates. In some cases, high
recovery of gold by flotation is accompanied by high levels of pyrite flotation resulting in a low grade
copper concentrate for treatment. Smelting of low grade concentrates incurs significant economic
penalties in shipping of concentrates to smelters, unit deductions in smelter contracts and treatment
and refining costs. These charges are justified in that the smelter must now treat large amounts of
barren pyrite to make slag and sulphur products. In this case, alternatives to smelter/refinery treatment
of concentrates may become attractive, especially where more dilute concentrate grades benefit
economics.

4.

Mine to Market Optimization. One of the trends in mining and mineral processing has been to optimize
the economics of the mining and milling operations in concert the so called mine to mill concept.
Increasingly, it makes sense to carry this global thinking right through to the copper production process
and the ultimate market. It may well make sense to the overall economics of a mining operation to
account for (1) production of a lower grade concentrate with higher overall recovery of copper from the
mine, (2) treatment of the lower grade copper concentrate at the Minesite to make copper metal and; (3)
use of by-product weak acid from the copper recovery process as a reagent to leach and recover copper
at the Minesite. The overall economics to be achieved using this approach may give an advantage to an
alternative to smelting.

5.

Recovery of Valuable By-Products. Copper concentrates may often contain significant levels of base and
precious metal by-products. Copper smelters are efficient at recovery of gold, silver and PGMs but often
pay poorly and with much delay for these elements. Base metals such as zinc, cobalt and nickel are
difficult to recover through a copper smelter process. In each of these cases, an alternative to smelting
may be attractive.

6.

Use of Existing Capital. In selected cases, copper heap leach- SX/EW process plants are running out of
ore feed. These plants have fully functional SX/EW plants available for further copper recovery as
electrowon cathode. In this case, it may make sense to adopt a copper concentrate hydrometallurgy
process as the front end of the process plant and further utilize existing capital.

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New Developments in Hydrometallurgical Treatment of

7.

Economics. Smelter economics are more scale sensitive than hydrometallurgical alternatives.
Hydrometallurgical plants are more suited to application of modular incremental project development if
required.

Copper hydrometallurgy has been extensively studied as an alternative route to chalcopyrite concentrate
treatment. Historically, a large number of hydrometallurgical treatment processes have been developed to treat
copper concentrates [1-12]. These processes have all failed to achieve sustained commercial production due to
one or more of the following list of shortcomings:
1.
2.
3.
4.
5.
6.
7.
8.
9.

Low copper recovery in the primary leach step.

Copper loss due to copper co-precipitation with iron hydrolysis products.
Difficult or incomplete precious metal recovery from leach residue.
Unconventional and difficult electrolysis step.
Difficult elemental sulphur recovery step from leach residue.
Excessive corrosion (especially chloride circuits).
Difficulty in fixing toxic by-products in a stable waste product.
Large energy requirements for mixing and oxygen dispersion.
Poor quality copper product that requires electrorefining.

It is beyond the scope of this paper to fully analyze all the reasons for failure of previous process developments in
copper hydrometallurgy. Beyond the technical factors involved, a number of additional factors are often
involved in preventing advancement of new technologies. These include:
1.

New technology risk. Many of the new processes have unique chemistry, processing conditions or
equipment. These processes have not had adequate commercial demonstration to mitigate risk.

2.

Cost of licensing. The potential cost of licensing new technology while also assuming the risk of being
first to commercially practice can mitigate against new technology selection. This is exacerbated by the
large costs of process development. Often millions or tens of millions of dollars are expended in process
development in the hopes of discovering and commercializing the ideal copper hydrometallurgy
process to replace copper smelting and refining. These sorts of costs are difficult to recover through
licensing. In addition, given the variable nature of copper concentrates, local economic and
environmental conditions and the variety of process options available, it is highly unlikely that a single
copper hydrometallurgy process will achieve global domination.

Against this backdrop, significant advances have been made over the last few years in advancing the use
of hydrometallurgy for copper ore and concentrate treatment. At the time of writing this paper at least 4
separate commercial plants have started or are under construction for copper recovery.
1.

Mt. Gordon Copper Process [13]. The Mt. Gordon Copper Process started in 1998 at the Mt. Gordon
Copper site in Queensland, Australia. This process recovers copper from chalcocite-pyrite ores or
concentrates by low temperature pressure leaching, copper SX-EW. The plant has operated at up to
50,000 tpa Cu production at a cash cost of as low as $0.31 USD per lb of copper from mining through to
metal production [14].

2.

Phelps Dodge Total Pressure Oxidation Plant [15]. The Phelps Dodge Total Pressure Oxidation Process
demonstration plant commenced in May 2003. The plant was designed to recover 16,000 tpa of Cu by
autoclave leaching at 220-230 C followed by CCD washing of the autoclave residue and copper SX-EW.
The key design feature of this plant is the use of the acid from the autoclave oxidation of concentrates
for acid makeup to an associated copper stockpile leach.

3.

Alliance Copper BIOCOP Process [16]. The Alliance Copper group is a joint venture between
BHPBilliton and Codelco to exploit the use of bioleaching for treatment of copper concentrates. The
BIOCOP process involves use of extreme thermophile bacteria for copper leaching. The process
involves a pre-treatment step and then two stages of bioleaching. The bioleach discharge solution is
recovered and sent to conventional SX-EW for copper recovery. Alliance have started a 20,000 tpa
copper production plant in Chile.

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David Dreisinger

4.

The Oxiana Sepon Copper Process [17]. Oxiana Resources are currently developing the Sepon Copper
project in Laos, South East Asia. The Sepon ore contains predominantly chalcocite with pyrite and
clayey gangue in the ore. The metallurgical flowsheet designed for the plant (and now under
construction) uses atmospheric leaching followed by SX EW recovery of copper. The barren washed
tails are floated to recover a pyrite elemental sulphur concentrate. The concentrate is oxidized at 225
C to produce a final solution containing acid and ferric sulphate. This autoclave solution is applied in the
atmospheric leach.

On the chloride side, Outokumpu have commissioned a 1 tpd Cu pilot plant for the Hydrocopper process.
The Hydrocopper [42] process produces chlorine, caustic and hydrogen using a conventional chloro-alkali cell.
These reagent products are applied to leach chalcopyrite (chlorine), raise the pH to precipitate cuprous oxide
(caustic) and reduce the cuprous oxide to metal (hydrogen). This process represents a significant innovation in
that electrochemistry is used in the manufacture of chemicals, not the winning of metals. This frees the
Hydrocopper process from difficulties associated with production of copper metal as dendrites. Experience at
the INTEC Copper Process pilot plant has shown that plating copper dendrites, stripping the dendrites from the
cathode and recovery of the dendrites from the cell is complicated.

Background
The Leaching Of Sulphide Minerals
The leaching of sulphide minerals can proceed by a variety of routes. These include oxidative, reductive and
non-oxidative chemistries. Reductive and non-oxidative chemistries, while interesting and potentially very
useful, are beyond the scope of this paper.
With oxidative leaching, sulphide minerals can be oxidized by various oxidants including for example, molecular
oxygen, ferric sulphate or ferric chloride, cupric chloride or chlorine. The sulphide mineral oxidation and the
reduction of the various oxidants is governed by the thermodynamics of the system. One way of picturing the
thermodynamics of a particular system is to draw a potential pH diagram. Figure 1 shows the potential pH
diagram for the Cu-Fe-S-H2O system at 25 C.
This figure shows that chalcopyrite is stable at reduced potential. Upon oxidation under acid conditions,
chalcopyrite will alter to bornite, chalcocite, covellite and finally to copper ion in solution. It should therefore be
possible to leach chalcopyrite under acid oxidizing conditions.

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New Developments in Hydrometallurgical Treatment of

Figure 1. The Eh pH diagram for the Cu-Fe-S-H2O system at 25 C; all solutes at 0.1 mol/L activity except Cu2+ = 0.01 mol/L
[18].

The Problem Of Chalcopyrite

Chalcopyrite is the one of the most difficult sulphide minerals to leach. Various reviews of chalcopyrite leach
chemistry have been conducted [19-30].
Chalcopyrite chemistry can be described in the chemistry of the individual elements of Cu, Fe and S. Copper is
typically leached in sulphate media to form copper sulphate in solution. Iron may be leached as either ferrous or
ferric sulphate and may subsequently hydrolyze as ferric hydroxide, goethite, jarosite or hematite. Sulphide
sulphur in chalcopyrite may oxidize to elemental sulphur or through to sulphate sulphur. The overall chemistry
of leaching can be dramatically impacted by the final state of the copper, iron and sulphur. Acid and oxidant
consumption can be affected. This is shown in the following series of chemistries.
Chalcopyrite leaching with ferrous sulphate and elemental sulphur reaction products

CuFeS 2 + O2 + 2 H 2 SO4 CuSO4 + FeSO4 + 2 S + 2 H 2O

Chalcopyrite leaching with ferric sulphate and elemental sulphur reaction products

CuFeS2 + 1.25O2 + 2.5 H 2 SO4 CuSO4 + 0.5Fe2 ( SO4 )3 + 2S + 2.5 H 2O

Chalcopyrite leaching with ferric hydroxide and elemental sulphur reaction products

CuFeS 2 + 1.25O2 + H 2 SO4 + 0.5 H 2O CuSO4 + Fe(OH )3 + 2 S

Chalcopyrite leaching with goethite and elemental sulphur reaction products

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David Dreisinger

CuFeS 2 + 1.25O2 + H 2 SO4 CuSO4 + FeO(OH ) + 2S + 0.5 H 2O

Chalcopyrite leaching with jarosite and elemental sulphur reaction products

CuFeS 2 + 1.25O2 + 1.67 H 2 SO4 CuSO4 + 0.333H 3OFe3 ( SO4 ) 2 (OH )6 + 2 S + 0.167 H 2O C
halcopyrite leaching with hematite and elemental sulphur reaction products

CuFeS2 + 1.25O2 + H 2 SO4 CuSO4 + 0.5Fe2O3 + 2S + H 2O

Chalcopyrite leaching with ferric sulphate and sulphate reaction products

CuFeS2 + 4.25O2 + 0.5 H 2 SO4 CuSO4 + 0.5 Fe2 ( SO4 )3 + 0.5H 2O

Chalcopyrite leaching with ferric hydroxide and sulphate reaction products

CuFeS 2 + 4.25O2 + 2.5 H 2O CuSO4 + Fe(OH )3 + H 2 SO4

Chalcopyrite leaching with goethite and sulphate reaction products

CuFeS 2 + 4.25O2 + 1.5 H 2O CuSO4 + FeO(OH ) + H 2 SO4

Chalcopyrite leaching with jarosite and sulphate reaction products

CuFeS 2 + 4.25O2 + 1.83H 2O CuSO4 + 0.333H 3OFe3 ( SO4 ) 2 (OH )6 + 0.333H 2 SO4
Chalcopyrite leaching with hematite and sulphate reaction products

CuFeS2 + 4.25O2 + H 2O CuSO4 + 0.5Fe2O3 + H 2 SO4

With elemental sulphur as a reaction product, the use of oxygen varies between 1 and 1.25 mole/mole Cu
(equivalent to 0.5 to 0.63 t O2/t Cu). With sulphate as a reaction product, oxygen consumption is 4.25 mol/mol Cu
(equivalent to 2.15 t O2/t Cu). The reagent consumption for the so-called total oxidation of chalcopyrite is
therefore large.
The sulphuric acid balance is interesting. According to the various chemistries shown, acid is consumed
when elemental sulphur and/or ferric sulphate are produced. Whenever sulphur is oxidized to sulphate and iron
is precipitated, acid is produced as a net reaction product of leaching. In the case of jarosite precipitation, the
production of acid is reduced due to the incorporation of sulphate in the jarosite iron precipitate structure.
The kinetics of chalcopyrite leaching are often slow in sulphate systems. At lower temperatures ( < 110
C), chalcopyrite leaches slowly and tends to accumulate elemental sulphur and iron precipitate product layers.
Diffusion through the product layers tends to slow leaching. It is also believed that a passive film forms on the
chalcopyrite surface that suppresses the rate of reaction. This passive film is believed to be a copper
polysulphide [26]. In this case the kinetics of copper leaching can be promoted by fine grinding or by addition of
small amounts of chloride. Silver catalyzed leaching has also been successful in breaking down the passive film
and promoting high extraction of copper.
At medium temperature (~150 C), chalcopyrite initial leaching kinetics are faster. However, liquid
elemental sulphur tends to block the chalcopyrite surface on partially leached particles and prevents full
extraction. This can be overcome with use of surfactants and a medium fine grind of the concentrate as will be
discussed later.
At higher temperature ( > 180 C), chalcopyrite leaches quickly and completely with high elemental
sulphur oxidation to sulphate. At 220 C, leach times of less than 1 hour are sufficient for copper extractions in
excess of 98% [27].
The challenge of process development for chalcopyrite leaching is to leach chalcopyrite quickly and
completely with high yield of elemental sulphur. To overcome the slow and incomplete leaching of chalcopyrite
at lower temperature, the two problems of (1) passive films on the chalcopyrite surface and (2) the potential
blocking and wetting of chalcopyrite by liquid elemental sulphur must be addressed.

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New Developments in Hydrometallurgical Treatment of

The Behaviour Of Elemental Sulphur

Elemental sulphur is a desirable reaction product for chalcopyrite leaching. Oxygen consumption is
minimized by formation of elemental sulphur. Elemental sulphur has a number of important chemistries.
1.

S8 ring structure. Sulphur forms 8 membered rings of sulphur. The rings are quite stable toward
oxidation at temperatures below about 155 C. Above 159 C, the rings start to open. At the points of
scission, the sulphur atoms are easily oxidized, leading to rapid oxidation of sulphur to sulphate at
elevated temperature.

2.

Melting point. Sulphur has two crystalline allotropes. Orthorhombic sulphur is stable to 95.5 C while
monoclinic sulphur is stable above this temperature. The solid-solid transformation between
orthorhombic and monoclinic sulphur can be slow. Accordingly, two melting points for sulphur have
been observed. Orthorhombic sulphur melts at 112.8 C while monoclinic sulphur melts at 119.3 C. To
avoid any possibility of molten sulphur formation in leaching, it is recommended to maintain
temperature below 110 C.

3.

Viscosity. The viscosity of liquid elemental sulphur decreases from the melting point through to about
159 C. Viscosity is about 8 poise at a minimum. Above 159 C, viscosity increases by at least 2 orders of
magnitude due to polymerization of sulphur after the opening up of the S8 ring structure. This is the
sticky black form of sulphur that is sometimes observed in chemical processing. Beyond about 190 C,
the viscosity of sulphur starts to decrease due to reduction of polymer chain length of the sulphur
polymers. The viscosity of sulphur with temperature is shown in Figure 2.

4.

Oxidation. Sulphur oxidation is thermodynamically favourable under mild oxidation conditions. The
wet oxidation of elemental sulphur to sulphuric acid proceeds by the following chemistry:

S + 1.5O2 + H 2O H 2 SO4
This reaction is slow under mild oxidation conditions. It has been found in practice that oxidation of
sulphur increases with higher oxidation condition. For example in a ferric sulphate/ferrous sulphate
solution (standard potential of 0.7 V vs. SHE), the oxidation of sulphur is slow. For this reason, a ferric
sulphate leach of chalcopyrite will have a high yield of elemental sulphur. For a nitric acid leaching
system (standard potential of 1.0 V vs. SHE), the oxidation of sulphur is rapid. The kinetic stability of
sulphur can therefore be portrayed using a modified potential - pH diagram for sulphur (Figure 3).

Hydro-Sulfides 2004

David Dreisinger

Figure 2. Viscosity Temperature Curve for Liquid Sulphur [33].

Surface Active Agents For Sulphur Dispersion

Sulphur dispersion using surface active agents is used in the zinc pressure leach process for the direct
leaching of zinc sulphide concentrates in spent electrolyte solutions. The two reagents that have found most use
for this purpose have been lignosulphonate and Quebracho. Owusu et al [35] have studied the dispersion of
sulphur in the zinc sulphide system and determined that (1) introduction of surfactants lowers the sulphur
aqueous solution interfacial tension (promotes dispersion of sulphur) and (2) surfactants adsorb on the zinc
sulphide surface and make the surface relatively less sulphophilic and more hydrophilic. The consequence is that
sulphur is easier to disperse from the mineral surface in the presence of a surfactant, allowing leaching to
proceed.
Hackl et al [36] have extended the study of surface active agents for sulphur dispersion to the chalcopyrite
system. A number of reagents were surveyed for sulphur dispersion behaviour. The most successful of these
were lignonsulphonate and ortho-phenylenediamine (OPD). Tables 1 and 2 show the change in interfacial
tension between sulphur/solution and contact angle between sulphur/solution/chalcopyrite due to the
introduction of surfactant.

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New Developments in Hydrometallurgical Treatment of

Figure 3. The Potential pH diagram for the S-H2O system, showing the region of sulphur stability and the
extended stability that is realized by a 300 kJ/mol barrier to the formation of sulphate [29].
Table 1. Effect of Surfactants on the Liquid Sulphur Aqueous Solution Interfacial Tension. Test conditions: 140 C and 0.69
MPa total pressure (nitrogen). The aqueous solution contained 30 g/L Cu, 10 g/L Fe3+ and 98 g/L H2SO4 [36].

Surfactant
None
Calcium lignosulphonate
Calcium lignosulphonate
Sodium lignosulphonate
Orthophenylenediamine
Orthophenylenediamine

Concentration
(g/L)
0
0.1
0.3
0.3
0.1
0.2

Interfacial Tension
(mN/m)
56
40
30
32
41
41

Table 2. Effect of Surfactants on the Liquid Sulphur Chalcopyrite Contact Angle. Test conditions as for Table 1 [36].

Surfactant

Concentration
Contact Angle
(g/L)
(mN/m)
None
0
69
Calcium lignosulphonate
0.1
146
Calcium lignosulphonate
0.3
148
Sodium lignosulphonate
0.3
157
Orthophenylenediamine
0.1
92
Orthophenylenediamine
0.2
133
The studies of Hackl et al [36] confirm that it should be possible to disperse liquid elemental sulphur from
unreacted chalcopyrite using surfactant addition. Unfortunately, the dispersal of sulphur is only one of the
problems of chalcopyrite leaching. The formation of a passive film (eg. CuS2) on the surface of the partially
leached chalcopyrite is also a problem that must be addressed. This passive film tends to form in sulphate
leaching systems but not in chloride.
The sulphate processes that have been commercialized or are under active development are listed in the
table below.

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David Dreisinger

Table 3. Sulphate Based Copper Hydrometallurgy Processes for Ore or Concentrate Treatment (Status: P = Pilot
Plant, D = Demo Plant, C = Commercial Facility)
Process

Statu
s

Temp.
(C)

Regrind
D80 (m)

Special Conditions

90-110

Pressur
e
(atm)
10-12

Activox Process

5-10

150

10-12

10-15

Fine grinding combined with high

oxygen overpressure overcomes
chalcopyrite passivation
Modest regrind combined with
surfactants
for
chalcopyrite
leaching

Anglo American
University
of
British Columbia
Process
Bioleach
Processes

P
and
C

35-75

5-10 (low
T)
37 (high
T)

CESL
Process

140-150

10-12

37

Dynatec Process

150

10-12

37

MIM
Process
Mt.
Process

Albion

85

5-10

Gordon

90

100

PLATSOL Process

220-230

30-40

15

Oxiana Sepon

P and
soon
C

80 Copper

Atm

100

30-40

50

200-230

30-40

37

Copper

Total
Pressure
Oxidation Process

220-230
Pyrite

Low T bioleach (35-50 C) requires

very fine grind to overcome
chalcopyrite passivation. High T
bioleach
(65-75
C)
uses
thermophilic bacteria
Chloride catalyzed leach of
chalcopyrite
producing
basic
copper sulphate precipitate in the
autoclave
Chalcopyrite is leached using low
grade coal as an additive
Atmospheric ferric leaching of very
finely ground concentrate
Pressure
oxidation
of
chalcocite/pyrite ore or bulk
concentrate in an iron sulphate
rich electrolyte
Total pressure oxidation in the
presence of 10-20 g/L NaCl.
Precious metals leached at the
same time as base metals
Atmospheric ferric leach for
copper from chalcocite. Pressure
oxidation of pyrite concentrate to
make acid and ferric sulphate for
copper leach
Extreme conditions of T and P
designed to rapidly destroy
chalcopyrite and other sulphides

The Activox Process, the CESL Process, the Dynatec Process and the MIM Albion Process have been known
for some time and are well represented in the literature. For the purpose of this study, the focus will be to review
a number of newer sulphate processes. These will include the Mt. Gordon Process for chalcocite/pyrite ore
treatment, the Phelps Dodge Total Pressure Oxidation Process for chalcopyrite treatment, the BIOCOP Process,
the Sepon Copper Process, the Anglo American Corporation/University of British Columbia process for
chalcopyrite concentrate leaching and the PLATSOL process for co-recovery of base and precious metals from
sulphide concentrates. On the chloride side, the INTEC copper process is well known and will not be discussed.
The Outokumpu Hydrocopper Process was developed more recently and will be reviewed here.

The Mount Gordon Copper procesS

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New Developments in Hydrometallurgical Treatment of

11

The Mt. Gordon Copper Process [13, 14] was developed to treat chalcocite ores from the historic
Gunpowder deposit in Northern Queensland, Australia. The process uses low temperature pressure oxidation to
directly leach copper from the ore followed by SX/EW of copper from the resulting leach solution. The plant
operation achieved an annualized copper production of 50,000 tonnes Cu as LME grade cathode in 2002.
Chalcocite is the dominant copper mineral in the Mt. Gordon ore with minor covellite, bornite,
chalcopyrite and enargite. The feed to the autoclave typically is 8-9% Cu. Pyrite is the dominant gangue
sulphide mineral. The ore contains various amounts of siliceous gangue.
The choice of pressure oxidation for this application was driven by necessity. Flotation of the ore to
produce high grade concentrates was trialed but was unsuccessful due to very close association between copper
and the barren pyrites in the ore. Heap leaching and atmospheric ferric sulphate leaching were trialed. Heap
leaching was rejected due to expected lower recoveries (compared to agitation leach) and concern about
oxidation of the barren pyrite with resulting formation of large excesses of acid. Atmospheric ferric sulphate
leaching was rejected due to (1) concerns about ferric regeneration and (2) the inefficiency of oxygen/air use in
atmospheric processing.

Chemistry
Chalcocite leaches in two steps in a ferric ion environment. First, chalcocite leaches to form a covellite
reaction product and then the covellite product leaches to form soluble copper and elemental sulphur. Ferric ion
is regenerated by oxygen in-situ in the autoclave.
Chalcocite Leaching Stage 1.

Cu2 S + Fe2 ( SO4 )3 CuSO4 + CuS + 2 FeSO4

Chalcocite Leaching Stage 2.

CuS + Fe2 ( SO4 )3 CuSO4 + S + 2 FeSO4

Ferric Sulphate Regeneration

4 FeSO4 + O2 + 2 H 2 SO4 2 Fe2 ( SO4 )3 + 2 H 2O

Overall Chalcocite Leaching Reaction (sum of above reactions)
3+

2+

/ Fe
Cu2 S + O2 + 2 H 2 SO4 Fe

2CuSO4 + S + 2 H 2O

Other copper minerals will also leach with oxygen in the presence of a ferric/ferrous solution. In addition
to the reactions involving the copper minerals, pyrite in the ore will also oxidize to a limited extent (2-3%). This
minor oxidation is beneficial in regenerating soluble iron and acid for the leach system.
Pyrite Oxidation
3+

2+

/ Fe
FeS 2 + 3.5O2 + H 2 O Fe

FeSO4 + H 2 SO4

The leached copper sulphate is forwarded to solvent extraction and electrowinning of copper cathode.

Plant Description
Run of mine ore is stockpiled on a pad before the primary crusher. Ore is blended into the plant to
minimize variation. The ore is crushed through a single toggle jaw crusher to a crushed ore stockpile. Ore is
reclaimed and ground in a single stage SAG mill in closed circuit with a single 500mm cyclone. Cyclone overflow
of P80 = 100 microns is thickened in a 13m high rate thickener. Slurry at 60% solids is delivered to an 1100 m3
surge tank.
Ground ore is recovered from the surge tank at a constant mass flow of leachable copper measured by an
on stream analyzer, density and flow meter. The ground, thickened slurry is dewatered on an 80m2 horizontal
filter belt to moisture of 14-18%. Filtration before leaching is important to maintain the overall leach circuit
water balance and to avoid excessive dilution of the leach liquor.

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David Dreisinger

Filter cake is re-pulped in 10g/l Fe3+, 35 g/l Fe2+, 70g/l H2SO4, 10g/l CuSO4 recycled solvent extraction (SX)
raffinate, which has been heated to 65oC by heat exchange with post autoclave leach slurry. Re-pulped slurry is
pumped into two parallel duplex SAF 2507 stainless steel autoclaves each of 180m3 total volume and 120m3
working volume. Each autoclave consists of five compartments agitated by dual impellors using bottom Rushton
turbines and upper axial flow impellors. The leach reactions are exothermic and the temperature profile in the
autoclave ranges from 77-80oC at the feed and to 85-90oC at the discharge. A quantity of unheated raffinate is
injected into the third compartment to flatten the temperature profile. The resulting control of temperature has
allowed for more efficient use of oxygen for copper leaching and hence improved autoclave leach rates.
Oxygen is supplied from two BOC VSA oxygen plants of total 80 tpd capacity at 93% O2. Oxygen is
injected into the first three compartments to maintain a total pressure of 7.7 bar and an oxygen partial pressure
of 4.2 bar.
Typical plant feed rates are 76 tph of solids at 8.8% Cu. Raffinate flows are 240 m3/hr to produce a PLS
grade of 35g/l Cu. Leach recoveries vary with feed mineralogy but are currently 91 93% to produce a total plant
recovery of 90% after allowing for subsequent wash recovery loss.
Autoclave residence time is about 60 minutes. Leach slurry is discharged from the autoclave via two small
letdown pots and then flows through to four atmospheric leach tanks each of 300 m3 working volume. A further
1-2% copper is leached in these tanks by the residual ferric sulphate in solution. The main duty of the
atmospheric leach tanks is to provide heat exchange area for cooling of the autoclave discharge. SX raffinate is
used as a coolant in three of the tanks and is heated by passing through coils immersed in each tank. The final
leach tank is cooled with re-circulating water. The re-circulating water is kept cool by connection to an
evaporative water-cooling system.
The product slurry is cooled and thickened in a hydroclassifier. The hydroclassifier underflow is filtered
and washed using a belt filter. Fine solids are removed from the hydroclassifier underflow a pinned bed clarifier.
The PLS is then treated by a 2 E 2 S copper SX system and electrowon using the ISA Process system for plating
and stripping.
Recent site improvements have included installation of a Fenix Iron Removal system for ion exchange iron
removal from copper electrowinning.
The flowsheet for the plant is seen in Figure 4 below. The capital cost of the plant was $112.7 Million AUD
(or $57.5 Million USD at 0.51 exchange rate). The operating costs are detailed in Table 4 below. The site
operating cost for ore through to metal were reported to bet $0.31 USD/lb of copper, one of the lowest cost
operations in the world [14].

Hydro-Sulfides 2004

New Developments in Hydrometallurgical Treatment of

13

Figure 4. The Mt. Gordon Copper Process Flowsheet

Table 4. Mount Gordon Copper Process Operating Costs [14]. Annualized Costs for July December, 2001. Total copper
production (annualized) is 47,866 t Cu/a. Ore feed of 628,000 tpa @ 8.85% Cu. 86% overall recovery of copper to cathode was
realized (target is 90%). 1 A$ = 0.51 US$.

Cost
Cost
A$ m/annum A$/lb

Cost
US$/lb

Breakdown by Area
Mining
Processing
Administration
Total Site Cost

$4.50
$47.30
$12.20
$64.00

0.0427
0.4492
0.1159
0.6078

$0.022
$0.229
$0.059
$0.310

Breakdown by Cost
Labour
External Services
Consumables
Other
Total Site Cost

$14.20
$9.50
$39.90
$0.04
$64.00

0.1349
0.0902
0.3789
0.0004
0.6078

$0.069
$0.046
$0.193
$0.000
$0.310

The Total Pressure Oxidation Process

The total pressure oxidation process uses high temperature and pressure oxidation conditions to oxidize
all sulphide minerals to sulphates and sulphuric acid. Conveniently, total pressure oxidation also results in iron
precipitation as hematite. The overall reaction for total oxidation may be written as follows:

CuFeS 2 + 17 / 4O2 + H 2O CuSO4 + 0.5Fe2O3 + H 2 SO4

Hydro-Sulfides 2004

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David Dreisinger

King and Dreisinger [32] studied the total oxidation of chalcopyrite concentrates and found that times of
15-30 minutes were adequate at 220 C for complete (+99%) copper extraction and sulphide oxidation. Copper
could be recovered from the oxidation solutions using SX/EW to produce LME grade copper cathode. Precious
metals, if present, could be recovered using cyanidation (with an optional lime boil treatment prior to
cyanidation if silver jarosites are present in the autoclave residue).
The use of total pressure oxidation for chalcopyrite concentrate treatment results in significant oxygen
consumption (more than 2 t of oxygen per t of copper leached) and significant acid production. Acid is produced
by the autoclave process (as shown by the reaction above). Further amounts of acid are liberated by solvent
extraction of copper. In total, approximately 3 t of H2SO4 is produced per t of Cu leached. The cost of initial
production of this acid (effectively the very high oxygen consumption) usually requires that this acid be used as a
source of makeup acid for associated leaching operations. The cost to neutralize this acid would generally be
just too high to bear. Alternately, if this acid can be used beneficially, the acid credit can be significant. For
example, at an acid cost of $80/t, the value of acid from the high temperature autoclave is effectively 3 X $80 =
$240 /t Cu leached. This equates to about $0.11 per lb of Cu, a very significant credit.
The Phelps Dodge company has now pioneered the large scale application of total pressure oxidation at
the Bagdad plant in Arizona [15]. At this facility approximately 16,000 tpa of Cu can be recovered from
concentrates that previously were sent to a smelter facility. Under total oxidation conditions, 140 short tons of
acid are produced per day for application to the stockpile leach operation at Bagdad. In this way an acid credit is
derived.
Figure 5 below shows the flow sheet adopted by Phelps Dodge for the Bagdad plant. A single autoclave is used
to leach the concentrates which then proceed to flashing (to return the slurry to atmospheric pressure), slurry
cooling, CCD washing and then copper SX/EW. The autoclave stream is merged with the stockpile leach solution
stream to provide a combined PLS feed to the SX/EW facility. The acid from the autoclave process is then
recycled in the SX raffinate back to the stockpile leach.
The washed autoclave residue is neutralized with lime in 4 stages. If precious metals were present (very
low precious metals in the Bagdad concentrate), the neutralized residue could be cyanide leached.
The total pressure oxidation process is very suitable for application where the acid from pressure leaching
can be used beneficially. The process has been commercially demonstrated at a large scale and could easily be
scaled up to larger size if required. Total pressure oxidation for copper concentrate treatment should now be
regarded as proven technology.

Hydro-Sulfides 2004

New Developments in Hydrometallurgical Treatment of

15

Figure
5. The Phelps Dodge Total Pressure Oxidation Flowsheet [15].

The Biocop Process

The BIOCOP process was developed by the BHP Billiton biotechnologies group based in Johannesburg
South Africa. The process was presented and described in a short course lecture prepared by David Dew and
John Batty of BHP Billiton [40]. The process uses thermophile bacteria to oxidize and leach copper from sulphide
concentrates. The general process flowsheet is shown in Figure 6 below. The thermophile bacteria oxidize
sulphide minerals to metal sulphates and sulphuric acid at temperatures of 65 80 C. Thermophile bacteria are
superior to mesophile bacteria in the leaching of chalcopyrite concentrates. Mesophile bacteria produce poor
copper extractions unless the chalcopyrite is finely ground prior to bioleaching (it is believed again that
passivation is a problem for leaching of coarse chalcopyrite particles).
The BIOCOP flowsheet has a number of interesting features.

Oxygen is used for bioleaching. This necessitates the provision of an oxygen plant. Previously, bioleach
plants for gold and base metal applications were operated with air blowers.
Arsenic may be removed in a separate step to produce a residue for disposal.
Copper may be recovered by SX/EW. Excess acid may be used in heap leaching if appropriate.

Hydro-Sulfides 2004

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David Dreisinger

Two
Twostage
stage
Bioleach
Bioleach

Concentrate
Concentrate
feed
feed

Liquid

Oxygen
OxygenPlant
Plant

Arsenic
Arsenic
Removal
Removal

Bioleach
Advance Electrolyte

Residue

Residue

PLS

Solvent
Solvent
Extraction
Extraction

Electrowinning
Electrowinning
Cathode

Solid

Spent Electrolyte

Raffinate

SX/EW

Neutralise (no heap leach available) or to available heap leach

Figure 6. The BIOCOP Process [40].

The Alliance Copper joint venture group (BHP Billiton and Codelco) have now commercialized the process
in Chile. A 20,000 tpa Cu plant has been built close to Chuquicamata with the long term goal of treating arsenical
concentrates from the Mansa Mina deposit. The plant is integrated with a heap leach circuit to allow for an acid
credit back to the bioleach plant. The BIOCOP process is therefore similar to the Total Pressure Oxidation
Process described above in that high copper extractions are achieved under total oxidation conditions (to
sulphates). The major difference seems to be in the availability of acid after copper solvent extraction. In the
bioleach process, acid neutralization is practiced in the two stage bioleach using limestone addition to the
bioleach slurry. This neutralization incurs an operating cost that is not present in total oxidation and effectively
reduces the available acid credit from the bioleach process. Nevertheless, for specific applications, the bioleach
approach may be favoured relative to pressure leaching. Clearly, the successful startup of the Alliance Copper
project in Chile has validated the technology at a significant scale. Bioleaching of copper concentrates is now
regarded as a proven technology.

The Sepon Copper Process

The Sepon Copper Process[41] was developed for the recovery of copper from the Sepon copper deposit
in Laos. The mineralogy of Sepon is complex. Copper is mainly as chalcocite with pyrite and a large component
of clay mineralization. The flowsheet selected is show in Figure 7 and involves atmospheric acid ferric sulphate
leaching of copper followed by residue washing (first in raffinate and then in water) and pyrite/elemental sulphur
flotation. The key development in this flowsheet is the autoclave treatment of the flotation concentrate
containing pyrite and elemental sulphur. The autoclave process produces a basic ferric sulphate product (as
opposed to the usual hematite product). The basic ferric sulphate product can then be re-leached to produce a
strong ferric sulphate solution for application to atmospheric leaching.
The autoclave operates at 220 C in the presence of 100 psig of oxygen overpressure. Pyrite oxidation
produces basic ferric sulphate according to the following reaction.

FeS 2 + 3.75O2 + 1.5H 2O Fe(OH ) SO4 + H 2 SO4

Basic ferric sulphate is stable under autoclave conditions but then on conditioning after flashing (POX
leach on the flow sheet), the basic ferric sulphate re-dissolves, producing the rich ferric solution for leaching.

2 Fe(OH ) SO4 + H 2 SO4 Fe2 ( SO4 ) 3 + 2 H 2O

Hydro-Sulfides 2004

New Developments in Hydrometallurgical Treatment of

17

CRUSHING
EXCESS
PYRITE

MILLING
POX LEACH

WASH
WATER

AUTOCLAVE

SURGE

STEAM
Fe Acid

FILTER

ADDN

DIRECT HEX

SURGE

ATM LEACH

SURGE

HEX

COOLING TWR

CLARIFICATION

SX

EW

RAF CCD
CATHODE
WASH CCD

WASH
WATER

FLOTATION

WASH CCD

Fe Acid
Cu LOSS

NEUTRALISATION

TAILINGS

Figure 7. The Sepon Copper Process [41].

The other benefit of the Sepon process is the possibility of scavenging any remaining copper minerals in
the pyrite float concentrate (that were not leached in the atmospheric leach). These copper minerals would be
expected to leach under the total oxidation conditions employed, thus increasing overall copper recovery from
the Sepon ore.
The Sepon plant is currently in construction and will start up in December 2004. The initial plant capacity
is set for 60,000 tpa of copper. The oxidation of pyrite/sulphur will provide virtually all acid and ferric sulphate
required for the copper leaching process. The process can be considered a hybrid of a copper leach and pyrite
oxidation process.

Hydro-Sulfides 2004

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David Dreisinger

The Outokumpu Hydrocopper Process

The Outokumpu Hydrocopper Process [42] is shown below in Figure 8. The process involves countercurrent
leaching of chalcopyrite using air and chlorine as oxidants (chlorine oxidizes cuprous to cupric for leaching
process). The residue from leaching contains goethite and elemental sulphur. Gold may be leached selectively
from the residue under controlled potential leaching conditions.
The copper bearing solution is purified by pH adjustment to precipitate cupric ion (for recycle to the leach),
cementation (aided by soluble mercury salt) for silver removal, base metal precipitation using sodium carbonate
and then finally an ion exchange process for polishing minor impurities (using C-467 resin from Duolite). The
purified cuprous solution is then treated with sodium hydroxide to precipitate cuprous oxide for hydrogen
reduction to metal.
The three major reagents needed for this process are chlorine, sodium hydroxide and hydrogen. These are all
produced using a standard chloro-alkali cell. The use of electrochemistry for chemical manufacture, rather than
for metal winning, is a major step forward in application of chloride technology. Chloroalkali cells are typically
operated at 3000 5000 A/m2 current density, about an order of magnitude higher than conventional metal
winning. In addition, anode to cathode distances are measured in mm, not cm, due to the absence of a metal
deposit growing in the electrode gap.
The main reactions (for chalcopyrite leaching) are shown below.
Chalcopyrite Leach

CuFeS 2 + 0.5Cl 2 + 0.75O 2 + NaCl + 0.5H 2 O NaCuCl 2 + FeO(OH) + S

Copper Precipitation

NaCuCl 2 + NaOH = 2NaCl + CuOH(s)

Copper Reduction

CuOH + 0.5 H 2 (g) = Cu + H 2 O

Chlor-Alkali Cell

NaCl + H 2 O = NaOH + 0.5Cl 2 (g) + 0.5H 2 (g)

The products from the chloro-alkali cell are exactly balanced with the requirements for leaching,
purification and copper reduction.
Outokumpu have started a 1 tpd demonstration plant in Finland for this technology.

Hydro-Sulfides 2004

New Developments in Hydrometallurgical Treatment of

Concentrate

Air

19

Leach Residue
Au

Figure 8. The Outokumpu Hydrocopper Process [42].

The Anglo American Corporation/University of British Columbia Copper Process

The Anglo American Corporation/University of British Columbia (AAC/UBC) Copper Process[43] is a
medium-temperature leaching process for chalcopyrite concentrates. The concentrate is reground to fine size
(P80 520 m) and leached under moderate pressure at 150C in an acid-sulphate system. The addition of a
surfactant disperses the molten elemental sulphur, avoiding passivation during leaching. Copper is recovered by
solvent extraction (SX) and electrowinning (EW) to produce premium copper cathode. The process is
distinguished by high copper extractions, hematite or jarosite formation for iron rejection, and elemental sulphur
as the predominant reaction product. The science of the use of surfactants for sulphur dispersion has already
been described in the introduction to this paper.
Figure 9 illustrates the importance of grind size for chalcopyrite leaching. For all except the 17.93 um particle
size, copper extraction exceeds 95%. For the coarser particle size, the leach ceases at about 80% copper
extraction due to passivation of coarse chalcopyrite particles in the feed.
The Anglo American Corporation/University of British Columbia process was evaluated in a continuous,
fully integrated pilot-plant trial [44]. The flowsheet (see Figure 10 below) comprised fine grinding of the
concentrate, pressure leaching, thickening and filtration, copper SX/EW, with a bleed circuit to recover valuable
base metal co-products. Gold was recovered from the autoclave residue by direct cyanidation. Copper and zinc
extractions above 95% and elemental sulphur yields of 60% were achieved at 150C in a 2-hour residence time.
The presence of surfactants did not affect the extraction or the phase separation in the SX process. The gold
extraction exceeded 80%. The AAC/UBC process is expected to be highly competitive with other
hydrometallurgical copper processes under commercial development.

Hydro-Sulfides 2004

20

David Dreisinger

100.00

95.00

90.00

Copper Extraction (%)

85.00

80.00
5.28 um
10.01 um

75.00

13.04 um
17.93 um

70.00

65.00

60.00

55.00

50.00
0

0.5

1.5

2.5

3.5

Time (hr)

Figure 9. Copper Extraction as a Function of Initial Particle Size for Leaching of Chalcopyrite Concentrate with
Surfactant Addition at 150 C.

Hydro-Sulfides 2004

New Developments in Hydrometallurgical Treatment of

21

Chalcopyrite concentrate

Ultrafine milling

Pressure leach

Surfactants
O2

Thickening / filtration
PLS recycle
Campaign 2

Residue washing

Copper SX1

Cu EW

Raffinate
recycle
Bleed
stream
Copper SX2

Precious metal
recovery

Copper
cathode

NaOH

Iron precipitation

Iron residue (goethite)

Zinc precipitation

Zinc residue (BZS)

Figure 10. Pilot Plant Flowsheet for the Anglo American Corporation/University of British Columbia Copper Process [44].

The Platsol Process

The PGMs, which include platinum, palladium, rhodium, ruthenium, osmium and iridium, typically occur
in nature in close association with base metals sulphides, such as those of copper and nickel. Gold, although not
traditionally included as one of the PGMs, is also frequently found in these ore bodies in varying concentrations.
These ores are normally processed by grinding and flotation to produce a sulphide concentrate, which
contains the copper cobalt and nickel as well as the PGMs. The concentrate is then smelted to separate and
upgrade the copper and nickel, which report to a matte phase, from iron sulphides and gangue minerals, which
report to a slag phase. Gold and the PGMs also report to the matte at significantly higher concentrations than
the original float concentrate. When the smelter produces sulphur-deficient mattes, a metallic phase is produced
on slow cooling which collects a substantial fraction of the PGM element value. To recover the remaining pay
metals, the matte is leached to dissolve copper and nickel, usually by a combination of atmospheric and pressure
oxidation of the sulphides, with the PGMs reporting to the small mass of leach residue (at very high
concentrations). After separation of the copper/nickel sulphate solution from the leach residue, the PGMs and
gold are leached with concentrated hydrochloric acid and chlorine gas (as the oxidant). Because of the relatively
high cost of the HCl/Cl2 leach process, it is important that the concentration of PGMs in the base metal leach
residue should be very high.
There are a number of situations in which it is undesirable or uneconomic to treat Au and PGM
concentrates by the conventional route.

Hydro-Sulfides 2004

22

David Dreisinger

The treatment of lean concentrates containing mixed base metals and relatively dilute quantities of
gold and PGMs. The complexity of separating the mixed base metals (eg. Cu Ni) and recovery of
relatively low amounts of precious metals precludes this route.
The treatment of dirty concentrates containing deleterious elements such as Bi, As, Se, Te, etc.
Smelting complexes only have a limited tolerance for deleterious elements. High levels of these
elements in concentrates may prevent treatment.
The treatment of PGM concentrates containing high concentrations of chromium and magnesium.
Chromium and magnesium have reduced solubility in smelting slags at conventional temperatures.
Accordingly it is necessary to smelt concentrates containing high concentrations of these elements
at much higher temperature in special furnace designs to affect treatment. This may prevent
treatment of such concentrates. South African concentrates (UG-2) are often very high in Cr content.
Other situations where smelting may fail to provide an acceptable economic return, are when the
size of the resource is too small to justify the capital costs of a stand-alone smelter facility, or when
the cost of transporting the concentrate to a custom smelter is prohibitive.

In these situations, direct oxidative pressure leaching of the concentrate to dissolve the base metals may
provide the best process economics. As with matte leaching, gold and the PGMs remain in the pressure leach
residue. However, in this case the leach residue contains most of the iron and gangue minerals that were present
in the original float concentrate, so the concentration of PGMs can be an order of magnitude or more lower than
in a matte leach residue. Consequently, the PGMs generally cannot be recovered economically by the HCl/Cl2
leach process that is used for matte leach residues. Thus, in most cases, conventional technology fails to provide
for the economic recovery of PGMs from ores or concentrates that cannot be smelted for one reason or another.
The PLATSOL process [45] was developed for the treatment of ore from the Northmet property (formerly
called Dunka Road) in Minnesota, USA, owned by PolyMet Mining Corp. of Denver, CO. A bulk
copper/nickel/PGM float concentrate can be produced from this resource. The concentrations of copper and
nickel in the float concentrates were somewhat lower than normal for a smelting operation, and the economic
success of the project required all base and precious metals (Cu, Ni, PGMs) to be recovered efficiently and
inexpensively. Clearly, new technology was needed.

Process Chemistry
The PLATSOL process utilizes addition of small amount of chloride salts to the total oxidation autoclave
leach to cause the precious metals to dissolve at the same time as the sulphide minerals are oxidized. Figure 11
summarizes the stability regions for Au, Pd, Pt with chloride addition. Although these diagrams were
constructed at 25 C, the general results can be applied at high temperature and pressure. The dissolution of Au,
Pd, Pt is favoured at high oxidation potential and low pH. Too low an oxidation potential will result in reprecipitation of the metal. Too high a pH will result in hydrolysis of the metal to form an oxide or hydroxide
precipitate.
The autoclave oxidation process converts metal sulphide minerals into metal sulphates and iron
hydrolysis products (primarily hematite). The chemical reactions believed to occur in the autoclave are shown
below. (Note that the mineralogy of the PGM's may be very complex, but for simplicity only the metallic species
are considered.)
Chalcopyrite Oxidation/Iron Hydrolysis:

CuFeS 2 + 17 / 4O2 + H 2O CuSO4 + 1 / 2 Fe2O3 + H 2 SO4

Pyrite Oxidation:

FeS 2 + 15 / 4O2 + 2 H 2 O 1 / 2 Fe2 O3 + 2 H 2 SO4

Pyrrhotite Oxidation

FeS + 9 / 4O2 + H 2O 1 / 2 Fe2O3 + H 2 SO4

Nickel Sulphide Oxidation:

NiS + 2O2 NiSO4

Gold Oxidation/Chlorocomplex Formation:

Hydro-Sulfides 2004

New Developments in Hydrometallurgical Treatment of

23

Au + 1 / 4O2 + 1 / 2 H 2 SO4 + 4 NaCl Na 3 AuCl 4 + 1 / 2 Na 2 SO4 + 1 / 2 H 2 O

Platinum Oxidation/Chlorocomplex Formation:

Pt + O2 + 2 H 2 SO4 + 6 NaCl Na 2 PtCl 6 + 2 Na 2 SO4 + 2 H 2 O

Palladium Oxidation/Chlorocomplex Formation:

Pd + 1 / 2O2 + H 2 SO4 + 4 NaCl Na 2 PdCl 4 + Na 2 SO4 + H 2 O

Eh (Volts)
2.0

Eh (Volts)
2.0

1.8

1.8

1.6

1.6

AuCl4-

1.4

1.4

Au(OH)3

1.2
1.0

1.0

0.8

0.8

0.6

0.4

0.2
0.0

PdO

0.6

Au

0.4

PdCl+

1.2

Pd

0.2
0

10

12

14

0.0

pH

pH

10

12

14

Eh (Volts)
2.0
1.8
1.6
1.4

PtCl6-2

1.2

PtO2

1.0
0.8
0.6
0.4

PtO

Pt

0.2
0.0

10

12

14

pH

Figure 11. (a) Eh pH Diagram for the Au-Cl system at 25 C. [Au] = 0.00001 M. [Cl] = 0.2 M., (b) Eh pH Diagram for the Pt-Cl
system at 25 C. [Pt] = 0.00001 M. [Cl] = 0.2 M., (c) Eh pH Diagram for the Pd-Cl system at 25 C. [Pd] = 0.00001 M. [Cl] = 0.2
M.

Hydro-Sulfides 2004

24

David Dreisinger

Process Testing
The process has been tested at both bench and pilot scale. The bulk concentrate from Northmet had the
assay, 15.5% Cu, 3.69% Ni, 0.15% Co, 28.7% Fe, 25.6% S, 2.8 g/t Au, 2.49 g/t Pt and 11.1 g/t Pd. The bench scale
test results are summarized in Table 6.
The tests showed the success of the addition of chloride in promoting high extraction of Au, Pt and Pd.
Test 5 showed low precious metal extraction due to incomplete oxidation at 200 C.
The pilot testing of the PLATSOL was equally successful. In a continuous autoclave operation, the total
extraction of base and precious metals was similar to batch tests from Table 6.
Au and PGM can be easily recovered from solution using NaSH addition. NaSH drops the redox potential
of the solution, resulting in reductive precipitation of the precious metals onto finely divided sulphide
precipitates. These can then be filtered and collected for further refining to pure PGM (possibly after a further
releach of excess base metal sulphides from the precipitate). Base metals can be recovered after Au and PGM
recovery using conventional technologies (SX/EW for Cu and a variety of options for Ni/Co). The simplified
flowsheet is shown in Figure 12 below.
Table 6. Benchscale testing of pressure oxidation of Northmet concentrate. Leach time 2 hours. Concentrate reground with
steel media for tests 3-5 and with ceramic media for tests 6-7.

Test
1
2
3
4
5
6
7

Feed K80
(m)
32
32
15-20
15-20
15-20
15-20
15-20

NaCl
(g/L)
0
10
10
5
10
10
10

Temp
(C)
220
220
220
220
200
220
220

Extraction (%)
Cu
Ni
99.3
97.7
99.7
93.4
99.3
95.7
99.4
94.3
98.3
90.8
99.4
93.3
99.4
94.3

Au
0
91
79
79
0
96
96

Pt
0
79
93
93
4
98
98

Pd
61
88
96
92
0
94
95

Conclusions
The hydrometallurgical treatment of copper concentrates using chemical and biological leaching has
begun to make inroads to the field traditionally dominated by smelting and refining. The field has tended to
advance thus far by necessity or unique opportunity. The Mt. Gordon and Sepon processes were developed to
recover copper from ores that were not easily amenable to conventional flotation. The total pressure oxidation
process has been commercialized by Phelps Dodge where the acid from the total oxidation autoclave can be
beneficially used in the stockpile leach process at Bagdad. The BIOCOP process has been applied to a unique
opportunity at the Chuquicamata complex in Chile. Copper concentrates containing high arsenic concentrations
(not easily treated through a smelter) will be treated through the commercial bioleach plant with by-product
weak acid solutions used for associated heap leaching operations.
The AAC-UBC and PLATSOL processes will continue to develop for selected applications. The AAC-UBC
process niche appears to be a situation where partial oxidation of sulphur to sulphate is desirable (sort of an total
oxidation lite process). This may be attractive where a modest quantity of acid can be used in an associated
heap leach operation. A small acid credit would then be applied back to the concentrate treatment process
(AAC-UBC). The PLATSOL process is entering final feasibility study for application at NorthMet. This process is
ideally suited to treatment of NorthMet bulk concentrates due to the ability to co-recover the base and precious
metals with a single leaching operation. The commercialization of total pressure oxidation at Bagdad, Arizona, is
an important step toward commercialization of the PLATSOL process. The PLATSOL process is simply total
pressure oxidation in the presence of a small addition of sodium chloride (added to allow co-leaching of precious
metals).

Hydro-Sulfides 2004

New Developments in Hydrometallurgical Treatment of

25

It is predicted that further niche applications of hydrometallurgy for concentrate treatment will continue
into the future. However, the industry is still waiting for a technology that can compete on an operating
cost/capital cost and metal recovery basis with the conventional smelting/refining process. The difficulty with all
sulphate based processes appears to be the oxidation of some elemental sulphur to sulphate during leaching.
The costs associated with the sulphur oxidation process and then the process of sulphate control (eg.
Neutralization), makes it difficult to achieve a low operating cost for copper production, except where the acid
sulphate is used to offset an existing acid consumption for an associated heap leach. The recovery of precious
metals from sulphate based process residues is also challenging (except for total oxidation or PLATSOL). The
recovery of gold and silver from a residue containing elemental sulphur by cyanidation is difficult due to
consumption of cyanide by reaction with elemental sulphur.
The chloride processes offer some promise in meeting the challenge of conventional smelting and
refining technologies. Chloride processes are attractive due to rapid copper leaching, high solution strength,
very low sulphur to sulphate oxidation and low temperature/atmospheric pressure operation. The INTEC process
continues to be developed for copper concentrate treatment. The most challenging step for INTEC is the use of
electrowinning for metal recovery. Formation and recovery of copper metal dendrites by deposition in the INTEC
electrowinning cell is difficult. The Outokumpu Hydrocopper process has the attraction of use of
electrochemistry for reagent synthesis (chlorine/hydrogen and sodium hydroxide). It will be interesting to follow
these developments into the future.
Concentrate
Oxygen
PLATSOL Leach
L
NaSH

PGM Residue to
Refinery

Neutralization

Raffinate

Barren Residue

NaSH Precip.

L
Limestone

S
Cu SX/EW

Ni/Co Recovery

Gypsum Residue
Cu Cathode

Ni/Co Products

Barren Bleed

Figure 12. Simplified PLATSOL Flowsheet

References

Hydro-Sulfides 2004

26

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Hydro-Sulfides 2004