Hydrometallurgy 140 (2013) 163–180

Contents lists available at ScienceDirect

Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Review

Chalcopyrite hydrometallurgy at atmospheric pressure: 1. Review of

acidic sulfate, sulfate–chloride and sulfate–nitrate process options
H.R. Watling
CSIRO Minerals Down Under, CSIRO Process Science and Engineering, P.O. Box 7229, Karawara, WA 6152, Australia

a r t i c l e i n f o a b s t r a c t

Article history: The need to process low-grade and/or complex chalcopyrite-containing ores that cannot be concentrated is the
Received 13 May 2013 main driver for the development of hydrometallurgical processes. The ferric sulfate–sulfuric acid system, with or
Received in revised form 19 August 2013 without the assistance of microorganisms, has been studied extensively because it comprises the most promising,
Accepted 22 September 2013
low-cost process route. Alternative oxidants to ferric ion are known but, as yet, their superior oxidation strengths
Available online 10 October 2013
have not been exploited other than at laboratory scale, probably due to their higher costs. Hybrid sulfate–chloride
Keywords:
and sulfate–nitrate systems were included because they may offer specific advantages in some instances. The
Chalcopyrite aims of this review were to summarise current knowledge in respect of these systems and highlight potentially
Leaching rewarding areas for future research.
Dissolution © 2013 Published by Elsevier B.V.
Passivation
Sulfides

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
1.1. Process options for chalcopyrite concentrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
1.2. Process options for low-grade chalcopyrite ores . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
1.3. Scope of this review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
2. Sulfuric acid–ferric sulfate systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
2.1. Chemistry of leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
2.2. Chalcopyrite surface overlayers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
2.3. Chalcopyrite surface structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
2.4. Redox control in ferric sulfate systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
2.5. Microorganisms as catalysts in ferric sulfate systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
2.5.1. Ambient- to moderate-temperature bioleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
2.5.2. Bioleaching at moderate to high temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
2.5.3. Reduced sulfur additives to increase extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
2.5.4. Separation of biological and chemical processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
2.6. Cations as catalysts in ferric sulfate systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
3. Sulfuric acid — alternative oxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
3.1. Sulfuric acid–dichromate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
3.2. Sulfuric acid–chlorate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
3.3. Sulfuric acid–permanganate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
3.4. Sulfuric acid–hydrogen peroxide–hydroxyl radical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
3.5. Sulfuric acid–ozone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
3.6. Sulfuric acid–peroxodisulfate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
4. Hybrid sulfate–chloride systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
4.1. H2SO4–NaCl–O2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
4.2. H2SO4–Fe2(SO4)3–NaCl. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
4.3. H2SO4–Fe2(SO4)3–LiCl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176

E-mail address: Helen.Watling@csiro.au.

0304-386X/$ – see front matter © 2013 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.hydromet.2013.09.013
164 H.R. Watling / Hydrometallurgy 140 (2013) 163–180

5. Hybrid sulfate–nitrate systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176

5.1. Sulfuric acid–nitric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
5.2. Sulfuric acid–sodium nitrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
6. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178

1. Introduction low-grade oxide and secondary sulfides, it is clear that the proportion
of low-grade ores containing chalcopyrite will increase in the future.
There is currently an imbalance between copper supply and world Therefore, there are imperatives to improve hydrometallurgical tech-
demand (Fig. 1). The lack of new, large, high-grade deposits to replace nologies for the extraction of copper from chalcopyrite in ores of such
those that are nearing the ends of their lives, together with the low grades that they are uneconomic to concentrate, and to augment
increased delays between discovery and production due to higher the supply by extracting copper from polymetallic ores of complex
industry standards and extensive permitting requirements, means mineralogy that cannot be concentrated and from chalcopyrite con-
that the current global imbalance between supply and demand could centrates that contain undesirable impurities such as arsenic and cannot
continue for several years. be smelted.
At the same time, there has been a decline in copper grades, often
remarked upon as a future challenge to the copper industry. As an
example, at Escondida Mine, Chile, the world's largest copper mine 1.1. Process options for chalcopyrite concentrates
and producer of 9.5% of the global copper supply, the average copper
content of mined ore fell from 1.65% in 2007–2008 to 1.14% in In recent years, many processes for the extraction of copper from
2011–2012, with measured resource, indicated resource and inferred chalcopyrite concentrates have been developed, some of them at
resource all substantially less than 1% grade (Basto, 2012). In his review atmospheric pressure. In these processes, high copper extractions
of historical trends in Australian mining, Mudd (2010) presented data could be achieved, soluble copper could be separated and purified
for copper grades mined in the last 150 years and concluded that using well-established technologies such as solvent extraction and
the decline in ore grades would continue and, in addition, that ore electrowinning, and pure, high-quality metal products were recov-
mineralogy would become more complex and make the low-grade erable (Dreisinger, 2006). Using examples from acidic sulfate-based
ores more difficult to process. Strategies to reduce the imbalance chemical systems, four strategies employed to maximise copper ex-
between supply and demand could include the processing of complex traction particularly from chalcopyrite were: (i) as high a temperature
ores, the recycling of metals from electronic and other copper- process as could be reasonably managed at atmospheric pressure (e.g.,
containing waste materials and the development of processes to extract BioCOP™ — Batty and Rorke, 2006); (ii) fine grinding to increase chal-
copper from dirty concentrates containing penalty elements or from copyrite reactivity and overcome passivation (e.g., BacTech/Mintek —
low grade ores and mine waste materials. van Staden, 1998); (iii) the use of additives (e.g., Galvanox™ — Dixon
These strategies are not new. Heap, dump, in situ and vat leaching of et al., 2008); and (iv) exploitation of innovative combinations of
whole ores are the preferred technologies for the processing of low- processing technologies, such as heap leaching of concentrates (e.g., the
grade ores. Data from 2010 showed that proven concentration and Geocoat® process — Harvey and Bath, 2007).
pyrometallurgical technologies accounted for 80% of world copper Most of the processes were taken to pilot scale and some were dem-
production while hydrometallurgical processing of low-grade ores onstrated at a larger scale. However, there are still few commercial-
containing copper oxides or secondary copper sulfides contributed scale operations and energy-intensive processes are unlikely to be
about 20% of annual copper production (Index Mundi, 2013). As economic for concentrates, except in circumstances where the
chalcopyrite (CuFeS2) is the most abundant but also the most refractory competing pyrometallurgical technologies cannot be employed. Based
of the copper sulfides, and with the current extensive exploitation of on a survey of process options for copper concentrates assisted by the
application of a ‘qualitative ranking technique’, Lunt et al. (1997)
concluded that two of the best options for the hydrometallurgical
processing of concentrates were sulfation–roast–leach and bioleach.
6
They also noted that pyrometallurgical process routes offered some
distinct advantages, not least low cost and industry acceptance and
copper production surplus or
deficit [as % of production]

4
that for any given project there were a limited number of suitable
process options. Similar points were made by Peacey et al. (2004),
2 who outlined a potential opportunity as being the hydrometallurgical
treatment of dirty copper concentrates with subsequent discharge of
0 the acidic leachate to a heap leach/SX/EW operation in circumstances
where copper concentrate was readily available but ore for heap
-2 leaching was diminishing.
Dreisinger (2006) summarised nine reasons why hydromet-
-4
allurgical processes for the treatment of copper sulfide concentrates
had failed to “achieve sustained commercial production”. They can be
distilled into: (i) Production: incomplete copper and precious metal
-6
recovery and/or poor product quality; (ii) Wastes: difficulties with
2011
[2012]
[2013]
2006

2010
2000
2001
2002
2003
2004
2005

2007
2008
2009

treatment and/or disposal of insoluble residues with particular

emphasis on sulfur and (iii) Technoeconomics: costs not competitive
Fig. 1. Imbalance between copper production and copper demand. Annual surpluses or
with pyrometallurgy and higher perceived risks associated with
deficits (data from International Copper Study Group, 2012). Square brackets indicate implementing new processes. Peacey et al. (2004) and Dreisinger
predictions. (2006) noted that successful processes tended to represent niche
 H.R. Watling / Hydrometallurgy 140 (2013) 163–180 165

90
opportunities and predicted that the field would continue to advance by Djurleite
80
way of “necessity or unique opportunity”. Other criteria for successful Bornite

Cu extracted (%)
processes could include (iv) Universality: applicable to all copper 70
concentrates and able to deal with their various impurities, for example, 60 Covellite
Zn, Pb, As, Sb, Bi, Se, Hg and F and (v) Simplicity: robust, reliable 50
pyritic chalcopyrite
technology suitable for remote locations (Jones, 1996). 40
30 porphyry chalcopyrite
20 chalcocite (+digenite)
1.2. Process options for low-grade chalcopyrite ores 10
0 chalcopyrite (+ 1500
0 5 10 15 20 25 30 35 g/t Ag)
Heap and dump technologies were developed to overcome the
Time (days)
challenges of low copper grade in vast quantities of ores. These
technologies may also be applied to less-difficult ores, not necessarily Fig. 2. Copper extraction from copper sulfide minerals (bioleaching, pH 1.8–2, 30 °C, 2 wt.%
of the lowest grade, for (i) smaller-sized ore deposits, (ii) deposits in mineral).
remote locations lacking the necessary infrastructure for, or access to, Data from Fu et al. (2012), Johnson et al. (2008), and Ruan et al. (2010).
pyrometallurgical process routes, or (iii) when pyrometallurgical
processing is marginal or uneconomic. Copper recovery rates during
leaching in acidic systems at atmospheric pressure and ambient Heap leaching of copper oxide ores and bioleaching of secondary
temperature vary greatly for different mineral phases (e.g., Table 1). copper sulfide (chalcocite) ores is widely practised (Domic, 2007).
Rates are influenced by one or more of the physico-chemical properties However, heap leaching of chalcopyrite has yet to be implemented at
of the ores: commercial scale and the extraction of copper from dumps of low-
grade chalcopyrite ores or tailings is a practical option only because
• The copper minerals present (Fig. 2). As a general rule M2S is more the slow and low copper recoveries are proportionate to the low
readily dissolved than MS and impurities also influence dissolution processing costs (Schnell, 1997). In their reviews, Watling (2006) and
rates. Pradhan et al. (2008) focused on the potential of heap leaching as a
• The mineral associations and copper mineral liberation (Fig. 3). process route for low-grade chalcopyrite ores. However, among current
For the example ore, QEMSCAN analysis indicated that only the and past heap or dump leaching operations, only one chalcopyrite heap
–0.85 mm size fraction contained substantial liberated chalcopyrite; leach operation (Straits Resources' Girilambone Copper Company,
b30% of the chalcopyrite in the larger size fractions had surface NSW) was identified and two large-scale test heaps of chalcopyrite
expression and, overall, only about 40% of the ore copper content ore were described or discussed (Schlitt, 2006; van Staden et al., 2005;
could be leached. Particle structure analysis using X −ray tomog- Watling, 2006). Watling (2006) expressed the opinion that the efficient
raphy failed to reveal particle fracturing that might have assisted in heap leaching of chalcopyrite would require greater management and
exposing further chalcopyrite grains to the leachate. control than was thus far required in oxide and secondary sulfide
• The chalcopyrite grain size. For concentrates, the need to fine grind heap leaching and van Staden et al. (2005) described some of those
chalcopyrite concentrates to obtain a reasonable (economic) copper
extraction rate during leaching is widely reported and constitutes a
key parameter in the Albion process (Hourn and Halbe, 1999; Hourn
et al., 1999) and the Mintek/BacTech process (Gericke et al., 2009;
van Staden, 1998; Wang, 2005). The same effect applies to large- Feldspar
grained chalcopyrite in ores, assuming that the grains are exposed
to the leachate (e.g., Naderi et al., 2011). K-Feldspar
• Gangue mineral dissolution consumes acid during leaching or Titanite
bioleaching and may form amorphous silica gel, thus increasing the
viscosity of leachates. Gangue mineral dissolution may increase iron
concentrations in leachates and therefore promote jarosite formation, Quartz
and may release potentially toxic elements to bioleaching solutions
(Dopson et al., 2009; Halinen et al., 2009; Watling et al., 2009).
Chalcopyrite
Table 1 Pyrite
Comparative dissolution rates in laboratory-scale tests using acidic sulfate systems for
different copper-bearing minerals found in heaps and dumps of low-grade ores.
Biotite
Required Mineral Ideal formula

Hours to days Atacamite Cu2Cl(OH)3

Chrysocolla CuSiO3·2H2O
Neotocite (Cu,Mn)2H2Si2O5(OH)4·nH2O
Tenorite CuO
Malachite Cu2(CO3)(OH)2
Quartz
Azurite Cu3(CO3)2(OH)2
Antlerite CuSO4.2Cu(OH)2
K-Feldspar
Brochantite CuSO4.3Cu(OH)2
Days to months Native Cu Cu
Cuprite Cu2O
Chalcocite Cu2S
Months to years Bornite Cu5FeS4
Covellite CuS
Fig. 3. Ore particle (N7 mm, 0.7% Cu). QEMSCAN mineral association analysis of multiple
Enargite Cu3AsS4
blocks of each size fraction of this ore revealed that chalcopyrite was primarily associated
Chalcopyrite CuFeS2
with pyrite and quartz/feldspar.
166 H.R. Watling / Hydrometallurgy 140 (2013) 163–180
requirements and how they were being achieved in a pilot heap of
chalcopyrite ore. Vat leaching, largely superseded by heap leaching, is
applied at Mantos Blancos, Chile (Schlesinger et al., 2011) for the
extraction of copper from rapid-leaching minerals such as copper
oxides or carbonates and may enjoy a revival and wider application
with the development of continuous vat technologies (Mackie and
Trask, 2009; Schlitt and Johnston, 2010).
The Geocoat® bioleaching technology is a hybrid technology. It
combines the high recoveries associated with reactor leaching of
chalcopyrite concentrate with the lower capital cost of heap leaching.
In this process, copper concentrate is coated as a thickened slurry onto
host rock particles (6–25 mm). The coated host rock particles are
then stacked and irrigated as for heap leaching (Harvey and Bath,
2007). Sulfide dissolution is catalysed by acidophilic microorganisms
appropriate to the heap temperature. The complementary Geoleach™
technology comprised a control strategy of aeration and irrigation
rates to maximise microbial activity and heat generation and/or
conservation within heaps, intended to promote faster leaching,
particularly of chalcopyrite. Though widely tested and publicised, the
technology has not been commercialised.
1.3. Scope of this review
The purposes of this review were to describe the chemistry of
chalcopyrite leaching at atmospheric pressure, in sulfate media with
different oxidants or reductants and/or other additives and treatments
and, where possible, to compare copper extractions. Not surprisingly,
most research on chalcopyrite leaching has been undertaken using
chalcopyrite concentrates, whether or not the target application was
the processing of concentrate or of low-grade ore. Such tests utilised a
simple matrix, largely free of gangue minerals that might obscure
important relationships between starting and product materials.
However, one of the difficulties of making direct comparisons between
the results of published studies has been the failure of many researchers
to include sufficient detail in methods, or test-mineral properties.
Where data are presented in different formats, or disguised for reasons
of confidentiality, comparisons between studies become even more
difficult.
The review was limited to those sulfate-based systems operated at
ambient pressure within the temperature range constrained by that
condition. Chloride, nitrate and other acidic leaching systems, and pre-
and co-treatments associated with chalcopyrite hydrometallurgy will
be reviewed separately. Sulfate systems operating at above ambient
pressure and higher temperatures were comprehensively described
and discussed by Dreisinger (2006) and McDonald and Muir (2007a,
b) and references therein, and are not discussed further. In the present
review, no account was taken of the possible economics of processing,
Table 2
Acidic sulfate processes developed for chalcopyrite or other copper sulfide concentrates or ores and operated at atmospheric pressure.
Process Temperature
(°C)
Heap leaching (e.g., Quebrada Blanca, Chile) (Domic, 2007) Ambient
ROM dump leaching (e.g., La Escondida, Chile) (Domic, 2007) Ambient
Geocoat® (Harvey and Bath, 2007) Ambient
BacTech/Mintek (Gericke et al., 2009; van Staden, 1998; Wang, 2005) 35–50
BioCOP™ (Batty and Rorke, 2006) 65–80
Sepona (Baxter et al., 2003) 80
Galvanox™ (Dixon et al., 2008) 80
Albion (Hourn and Halbe, 1999; Hourn et al., 1999) 85
Cobre Las Cruces Project (Fleury et al., 2010) 90
Cuprochlor process (Espejo et al., 2001; Herreros et al., 2006) Ambient
“Nitric acid route” (Bjorling et al., 1976) 90
a
In the Sepon process, residual pyrite is floated and then oxidised under pressure to generate acid and ferric ions for use in the secondary heap leach. C commercial; D demonstration; L
laboratory P pilot; n.d. not disclosed.
but rather the aim was to inform researchers, metallurgists and plant
operators about the wide variety of chemical systems that might be
applied in the future when copper demand is higher, ore grades
are lower and new technologies have been developed. While the
advantages or disadvantages of current technologies might be referred
to in the contexts of reported results or applications of specific systems,
a detailed account of the engineering of such technologies, their
management and/or control are outside the scope of the review.
2. Sulfuric acid–ferric sulfate systems
The most commonly employed hydrometallurgical process for the
oxidation of chalcopyrite and extraction of copper is the sulfuric acid–
ferric sulfate system. It is the system of choice for bioleaching processes
at atmospheric pressure, including stirred tank technologies for
concentrates (Batty and Rorke, 2006) and heap or dump technologies
for low-grade ores (Watling, 2006). However, whether chemical or
bio-assisted chemical leaching is undertaken, the oxidation of chal-
copyrite is slow and incomplete, possibly the consequence of the
mineral crystalline structure and changes therein (de Oliveira et al.,
2012; Klauber, 2003) but also inhibited by insoluble secondary reaction
products (elemental sulfur, ferric hydroxides or hydroxysulfates)
forming what are termed ‘passivation’ or overlayers on chalcopyrite
surfaces. There is value in examining the chemistry of ferric sulfate
and acid leaching systems, some of which are summarised in Table 2,
because they comprise the basic chemical systems against which the
use of other chemical systems would be assessed during the
development of alternative atmospheric-pressure leaching processes.
2.1. Chemistry of leaching
The generally accepted reactions for the extraction of copper from
chalcopyrite via oxidation (oxygen, ferric ions) or acid (H2SO4) leaching
are:
CuFeS2 þ 2Fe2 ðSO4 Þ3 ¼ CuSO4 þ 5FeSO4 þ 2S
0
ð1Þ
0
CuFeS2 þ O2 þ 2H2 SO4 ¼ CuSO4 þ FeSO4 þ 2S þ 2H2 O ð2Þ
4FeSO4 þ 2H2 SO4 þ O2 ¼ 2Fe2 ðSO4 Þ3 þ 2H2 O: ð3Þ
Dutrizac (1981) reviewed the literature on ferric ion leaching of
chalcopyrite (reaction (1)) and, with data from ancillary studies,
summarised existing knowledge at that time as: (i) leaching was
independent of acid above that required to keep iron in solution (and
iron need not exceed 0.1M Fe2(SO4)3 — Parker et al., 1981); (ii) leaching
Size Differentiating conditions Scale
(μm)
– Crushed ore, stacked, irrigated with dilute H2SO4 solution C
– ROM ore stacked and irrigated with dilute H2SO4 C
n.d. Sulfide concentrate supported on host rock particles; sulfate D
bioleaching in heaps
5–10 Sulfate bioleach; fine grind D
37 Sulfate leach at higher temperature using archaea as catalysts D
100 Ferric sulfate leach of chalcocite rimming pyrite (FeS2) C
53–75 Ferric sulfate leach; pyrite to chalcopyrite in 2:1 ratio P
5–10 Ferric sulfate leach; finely ground concentrate P
−150 Ferric sulfate generated from pyrite oxidation with O2; mainly Cu9S5 C
and Cu2S (6.2 wt.%), minor CuFeS2
– Sulfate–chloride leach with CaCl2 agglomeration C
n.d. Sulfate–nitric leach of chalcopyrite concentrate L
 H.R. Watling / Hydrometallurgy 140 (2013) 163–180 167

rates were proportional to chalcopyrite surface area, only slightly a

dependent on ferric ion concentrations and increased with increased
temperature; and (iii) increased sulfate ion concentration contributed
to slower leaching rates. Hiroyoshi et al. (1997) proposed that
chalcopyrite was oxidised by dissolved oxygen (reaction (2)) and that
the generated ferrous ions were oxidised to ferric ions (reaction (3)).
Their evidence for these reactions was that the pH increased with
time when ferrous sulfate was added to acid medium containing chal-
copyrite, indicating the consumption of protons. Subsequent studies
by the authors were incorporated into a two-stage reaction model to
explain ferrous-promoted chalcopyrite dissolution (Hiroyoshi et al., CuFeS2
2000 and references therein) in which (i) chalcopyrite was reduced
by ferrous ions in the presence of cupric ions to form chalcocite and
(ii) chalcocite was oxidised (more readily than chalcopyrite) by
dissolved oxygen and/or ferric ions to form cupric ions and elemental
sulfur insoluble product. From thermodynamic calculations, chalcocite b
formation only occurred when the redox potential of the solution
was lower than the critical potential (a function of the ferrous and
cupric ion activities); and the optimum oxidation–reduction potential
(ORP) for chalcopyrite leaching increased with increased copper(II)
concentrations. Conversion of the normalised redox potential to the
solution redox potential showed the optimum ORP for chalcopyrite
leaching to be a function of cupric and ferrous ion concentrations
(Hiroyoshi et al., 2008). Sandström et al. (2005) examined the reaction
products formed during the chemical leaching of chalcopyrite and
found Cu(I) species in all samples, consistent with the Hiroyoshi et al.
(2000) two-stage model. CuFeS2
Nicol and Lázaro (2003) showed that dissolution of chalcopyrite
could occur in the absence of any oxidising reagent at potentials
lower than 0.4 V versus Standard Hydrogen Electrode (SHE), with the
formation of a detectable soluble sulfur species, such as hydrogen Fig. 4. Examples of reaction products on chalcopyrite surfaces: (a) ferric hydroxysulfate
layer after 96 h exposure to ferric sulfate solution (pH 1.8); (b) elemental sulfur after 2 h
sulfide. They presented data indicating that reaction (4) was the most
exposure to HOCl (pH 4).
proton-consuming reaction and hypothesised that it was governed by
two steps: (i) rapid dissolution to establish the equilibrium between
soluble species at the chalcopyrite surface and the bulk solid and
In a critical review of the surface science investigations of what
(ii) rate-determining diffusion of the soluble species away from the
might be responsible for hindered chalcopyrite dissolution in ferric
surface. Nicol and Lázaro (2003) examined the thermodynamic
sulfate systems, Klauber (2008) clarified some of the discrepancies
feasibility of reaction (4) at 25 °C and higher temperatures using
between studies. Klauber (2008) concluded that polysulfides could be
Outukumpu HSC software and the Criss–Cobble technique.
rejected as ‘passivation candidates’ because they were too reactive
þ 2þ 2þ and oxidised to elemental sulfur on exposure to air, especially in the
CuFeS2 þ 4H →Cu þ Fe þ 2H2 S: ð4Þ
presence of moisture and metal-deficient sulfides and that the presence
of metal deficient sulfides was questionable. Overlayers of elemental
2.2. Chalcopyrite surface overlayers sulfur formed on chalcopyrite surfaces could hinder dissolution but
might subsequently be peeled off, allowing further dissolution. Overlayers
There is a general view that the slow dissolution rates of chalcopyrite of iron(III)-insoluble compounds such as jarosite were an inevitable
in ferric sulfate leaching media are, in part, a consequence of the consequence of long leach times, triggered by the formation of an
formation of secondary reaction product on the mineral surface. These intermediate ‘ferric sulfate’ compound at the chalcopyrite surface as an
secondary reaction products, ‘passivation’ or overlayers, may be of integral part of the ferric ion leaching mechanism.
such depth and sufficiently compact (Fig. 4) as to hinder the diffusion More recently, Debernardi and Carlesi (2012) presented a review of
of reagents to the chalcopyrite surface and/or the diffusion of ions chalcopyrite passivation in which they outlined the capabilities and
away from the surface, or they may have low electrical conductivity. limitations of electrochemical and surface analysis techniques in
Reaction products thought to be implicated in chalcopyrite passivation resolving the nature of chalcopyrite passivation. As part of their review,
included: in which they summarised many of the papers discussed by Klauber
• Complex films of sulfides, polysulfides and/or elemental sulfur (2008), Debernardi and Carlesi (2012) questioned whether the current
(reaction (1)), or an unreactive, copper-rich layer on partially- techniques in electrochemistry and surface analysis could provide
oxidised chalcopyrite surfaces (Fu et al., 2012; Hackl et al., 1995; reliable data on surface phenomena and whether those data were
Linge, 1976; Nicol and Lázaro, 2003; Warren et al., 1982); being interpreted correctly. They identified potential research topics
• Iron oxides, hydroxides, iron hydroxysulfates and/or jarosite that might assist in the future interpretation of data obtained using
(reaction ((5)) (Córdoba et al., 2008a,b; Gómez et al., 1996; Parker sophisticated instrumentation.
et al., 2003; Sandström et al., 2005; Stott et al., 2001).
2.3. Chalcopyrite surface structure
3þ 2– þ þ
3Fe þ 2SO4 þ 6H2 O þ M →MFe3 ðSO4 Þ2 ðOHÞ6 þ 6H ð5Þ
In their initial study, using X-ray photoelectron spectroscopy (XPS),
Klauber et al. (2001) proposed that a disulfide phase was among
where M = K+, Na+, NH+ +
4 or H . the reaction products on leached chalcopyrite surfaces (Fig. 5). The
168 H.R. Watling / Hydrometallurgy 140 (2013) 163–180
Fig. 5. X-ray photoelectron spectrum of a chalcopyrite surface after treatment with 0.1 M ferric sulfate solution at pH 1.8. Deconvolution of the spectrum to reveal the underlying sulfide,
and the disulfide, elemental sulfur and sulfate species on the surface (Klauber et al., 2001).
synthesis of model polysulfides and their subsequent examination using
XPS indicated that polysulfides did not play a role in inhibiting
chalcopyrite dissolution, leading to the conclusion that chalcopyrite
dissolution occurred via the oxidation of the disulfide phase (Parker
et al., 2003). In a subsequent detailed study of a freshly-cleaved
chalcopyrite surface prepared in an inert atmosphere, Klauber (2003)
again identified a disulfide phase and presented a well-constructed
argument for the formation of a two-layer surface phase containing
pyritic FeS2 at 50% of the density of bulk pyrite. He proposed a model
that described the physical and redox mechanisms of the reconstruction
and concluded that it would lead to a lower-energy chalcopyrite
surface.
de Oliveira and Duarte (2010) used density functional theory within
plane wave framework to analyse the reconstruction of the chalcopyrite
(001) surface and its reactivity, at the molecular level. The calculations
predicted that the sulfur-terminated (001) surface underwent a
reconstruction in which disulfide groups formed on the surface,
consistent with the XPS results of Klauber (2003), with the concomitant
reduction of iron(III) to iron(II) oxidation state.
Subsequently de Oliveira et al. (2012) applied plane wave density
functional calculations to a comparative study of the (001), (100),
(111), (112), (101) and (110) chalcopyrite surfaces including both
sulfur- and metal-terminated cleavages of the first three (Fig. 6).
Three different surface reconstructions emerged from the calculations
of de Oliveira et al. (2012) which they described as follows: (i) on
surfaces which have relatively close sulfur atoms in the first atomic
Fig. 6. Chalcopyrite surface reconstructions which may partially impact on leaching kinetics.
Reprinted with permission from de Oliveira, C., de Lima G.F., de Abreu, H.A. and Duarte, H.A. (2012), Journal of Physical Chemistry C 116, 6357–6366. Copyright 2012 American Chemical
Society.
layer with lower coordination number than in the bulk chalcopyrite
(the (001)-S, (100)-S, and (112) surfaces), the formation of disulfide
groups via an oxidative process with concomitant reduction of Fe(III)
to Fe(II) or, for the sulfur-terminated (111)-S face, the formation of the
S2−
4 group; (ii) on surfaces terminated in metal atoms (the (001)-M,
(100)-M and (111)-M surfaces), the formation of metal–metal bonds
resulting in alloy-like structures beneath a layer of exposed sulfur
atoms, and (iii) the relaxation of metal atoms with downward migration
(the (101), (110) and part of the (112) surfaces). The experimental
detection of the disulfide groups has been reported (e.g., Klauber,
2003) but the predicted formation of the proposed metal– metal, alloy-
like groups and/or metal migration requires greater investigation in
respect of elucidating the slow dissolution kinetics of chalcopyrite.
de Lima et al. (2011) directed their study towards water adsorption
on the reconstructed (001)-S and (001)-M chalcopyrite surfaces. Their
calculations predicted that (i) an iron atom was the most favourable
site for a water molecule to adsorb on the reconstructed (001)-S surface,
(ii) dissociation of the water molecule was not favoured, and (iii) water
adsorption on the (001)-M surface was also unfavourable, suggesting
that the (001)-M surface would exhibit hydrophobic characteristics
that might influence surface reactivity. In an extension of that study,
the calculations of de Lima et al. (2012) revealed additional insights
relevant to chalcopyrite leaching. Their calculations predicted that
(iv) water molecules and chloride ions, with their similar adsorption
energies, competed for iron sites on (001)-S chalcopyrite surfaces,
(v) that sulfate and bisulfate ions were more strongly bound to the
 H.R. Watling / Hydrometallurgy 140 (2013) 163–180
surface than water or chloride ion, that binding was bidentate, replacing
two water molecules, and that bisulfate was bound more strongly than
sulfate, and (vi) that high acidity would lead to the protonation of the
disulfides on the surface, probably weakening the disulfide bond. It is
anticipated that future contributions from this research group should
advance our understanding of the slow kinetics of chalcopyrite leaching,
especially where predicted surface changes and interactions lend
themselves to experimental validation.
Recently, Li et al. (2013) conducted a comprehensive review of the
literature on the leaching of chalcopyrite, specifically the nature and
roles of secondary product overlayers, the reconstruction of the bulk
sulfide crystal when fractured or otherwise exposed as a surface and
the consequences of reconstruction in different leaching systems, and
the participation of redox reactions (both oxidation and reduction)
during leaching. While they reviewed many of the publications
discussed by Klauber (2008) and Debernardi and Carlesi (2012), Li
et al. (2013) adopted a broader approach, taking account of research
using oxidants other than ferric ion and a consideration of the above
modelling predictions. Li et al. (2013) concluded that three important
questions remained to be answered in order to explain the chalcopyrite
leaching mechanism(s), relating to: (i) the interaction between
chalcopyrite surfaces and oxidants; (ii) the relationships between
oxidants and secondary surface reaction products and (iii) elucidation
of the key factor that determines whether a chalcopyrite surface will
become passivated.
2.4. Redox control in ferric sulfate systems
The acceleration of copper extraction from chalcopyrite in acidic
ferric/ferrous sulfate media at low ORP in the temperature range of
20–50 °C (e.g., Fig. 7), is well established. As a consequence, different
strategies for ORP control were implemented in fundamental studies
and process developments. Bruynestein et al. (1986) established a
slurry potential of 540–660 mV versus SHE via the initial addition of
thiosulfate and cupric ions in a process that was specifically designed
to promote the extraction of copper from chalcopyrite and the partial
oxidation of the sulfide to elemental sulfur (not sulfate). Kametani
and Aoki (1985) maintained a bioleaching suspension at the relatively
low ORP of 635 mV (versus SHE) by controlled additions of potassium
permanganate solution, to maximise copper extraction from a
chalcopyrite concentrate. Sandström et al. (2005) maintained an ORP
of 635 mV (versus SHE) during the chemical leaching of a chalcopyrite
concentrate using potassium permanganate, but reduced the airflow
(oxygen) and added sodium sulfite to maintain a similarly low ORP
100
bacterial ORP control
80
copper extraction (%)
bacterial
60
40
chemical ORP control
20
chemical
0
0 5 10 15 20
leach duration (days)
Fig. 7. Enhanced copper extraction at 50 °C from chalcopyrite with bacteria and redox
control (re-drawn from Ahmadi et al., 2010). Electrochemical control of ORP at
400–450 mV versus Ag/AgCl reference electrode.
169
during bioleaching. Third et al. (2002) and Gericke et al. (2010) also
used oxygen limitation to control ORP during bioleaching, the former
by temporarily arresting the air supply to the reactor when the ORP
was greater than a designated set point, and the latter by adjusting
impeller speed to control oxygen mass transfer. Ahmadi et al. (2010)
exercised electrochemical control of ORP by applying a direct current
into the ore suspension with/without bacteria.
Viramontes-Gamboa et al. (2007) studied the oxidative dissolution
of chalcopyrite in acidified ferric/ferrous sulfate media in the tem-
perature range of 25–80 °C and concluded that chalcopyrite displayed
the active–passive behaviour of passivating metals. They showed that
the predicted electrochemical passivation potentials (E-pp) obtained
using electrochemical techniques were consistent with the results
from leaching experiments and reported that E-pp increased from
680 mV (versus SHE) at 25 °C to 755 mV at 80 °C. In their systematic
study of the effect of acidity in the range of 2–100 g H2SO4 L−1, they
also showed that E-pp were insensitive to acidity in the temperature
ranges of 25–40 °C and 60–80 °C but that between 40 and 60 °C, an
acid-dependent transition of E-pp occurred from 680 to 755mV (versus
SHE). Subsequently, Viramontes-Gamboa et al. (2010) collated data
from studies in which chalcopyrite leaching kinetics were investigated
under conditions of controlled ORP and found that chalcopyrite
passivation was reported to occur at one of two potentials, either
greater than about 680 mV or greater than about 750 mV (versus SHE)
for samples from different locations and with different impurities.
They then demonstrated electrochemically that transitions from active
to passive and vice versa did not take place at the same potential; at
temperatures of 50 °C or higher and conditions of increasing potential,
chalcopyrite passivated at about 750–755 mV (versus SHE) but if the
chalcopyrite was already passivated and the potential was decreased,
the chalcopyrite only became active at about 680 mV (versus SHE).
Viramontes-Gamboa et al. (2010) noted that this result offered a
possible explanation for the apparent discrepancies between published
controlled-ORP leaching studies but did not elucidate the factors that
determined whether chalcopyrite would be active or passive during
leaching in the potential range of 680–755 mV (versus SHE).
The benefits of enhanced chalcopyrite dissolution under conditions
of controlled ORP were sufficiently important to have prompted patent
applications relating to stirred tank and heap technologies. The patent
of Bruynestein et al. (1986) was noted above. In the patent of Dixon
and Tshilombo (2005), the chemical leaching of chalcopyrite in acidic
sulfate medium, with added pyrite as catalyst, was conducted “under
conditions whereby the pyrite is not materially oxidised, for example
by maintaining the operating solution potential at a suitable level”.
Redox-control during chalcopyrite bioleaching was also a key claim in
patents by van der Merwe et al. (1998), Pinches et al. (2001a, b) and
Lastra and Budden (2002). Pinches et al. (2001a) proposed to bioleach
chalcopyrite in stirred tanks by controlling air, oxygen and/or carbon
dioxide concentrations to limit the efficiency of iron(II)-oxidation by
the microbial community, specifically to control the ORP in the range
575–675 mV (versus SHE) “thereby to promote the rate and extent of
chalcopyrite oxidation”. Pinches et al. (2001b) claimed that the above
methodology could also be applied in a heap leaching process “in
which the leach solution was conditioned to provide the said surface
potential”. This latter claim was supported by the results of comparative
column leaching tests in which the iron(III)–H2SO4 feed solutions were
produced in a separate bacterial ferric-ion-generator and could thus be
controlled at “high” redox (775 mV versus SHE) or “low” redox
(637 mV), as required. The authors noted that in a ‘normal’ heap leach
system, the presence of the natural bacterial community would make
control of ORP extremely difficult. Lastra and Budden (2002) proposed
25
two methods of controlling the ORP in heap bioleaching of chalcopyrite.
In their invention, they described (i) the direct method: the im-
provement of “maintaining the reduction potential at below or around
EH b 550 mV” (reference electrode not specified but probably SCE or
Ag/AgCl), a condition in which it was proposed could be achieved by
170
limiting the concentrations of oxygen in a heap operated at N 50 °C; and
(ii) the indirect method, in which they proposed that biological
oxidation of ferrous ions would be achieved in a separate reactor and
that oxygen would be excluded from the heap, so as to prevent ferrous
ion oxidation in situ. Key claims in the patent of Hunter (2006) were
that a chalcopyrite heap would be inoculated with a “sulfide-oxidising”
bacterial culture that was either inefficient at oxidising iron(II) or did
not have that specific ability, and that the process water being fed to
the heap would be maintained at ORP lower than 695 mV (versus
SHE), “such that the prevailing chemical conditions are conducive
to leaching chalcopyrite while being non-conducive to surface
passivation”. As heaps are open systems, the maintenance of low-ORP
would be difficult should adventitious colonisation of the ore by native
iron(II)-oxidising microorganisms occur.
2.5. Microorganisms as catalysts in ferric sulfate systems
Bioleaching can be considered as a chemical system catalysed by
microorganisms. The bioleaching of sulfide minerals with emphasis on
copper sulfide leaching using low-temperature heap technology was
reviewed (Watling, 2006 and references therein). Briefly, sulfide
minerals in pristine (but exposed) deposits, mine waste dumps
and tailings, and/or managed heaps represent complex habitats for
acidophilic microorganisms but very few of the microorganisms have
been cultured, isolated or identified.
2.5.1. Ambient- to moderate-temperature bioleaching
Microorganisms participate in the dissolution of sulfide minerals in
two main ways: (i) by catalysing the oxidation of ferrous ions to ferric
ions (reaction (3)) more rapidly than occurs in chemical systems and
(ii) by oxidising sulfur to sulfate, helping to remove sulfur overlayers
and generating additional acid (reaction (6)). The costs associated
with the maintenance of sulfide bioleaching microorganisms are
minimal because they gain energy from the redox reactions (3) and
(6) (oxygen is usually supplied by air), acquire carbon for growth
from the carbon dioxide in air and obtain phosphorus, nitrogen,
potassium and micronutrients from the ore environment. Microbial
attachment to mineral surfaces is mediated by the properties of the
extracellular polymeric substances produced by the cells and
attachment is mineral and site specific and may change the properties
of the underlying mineral surface (Watling, 2006 and references
therein). In some cases the addition of organic compounds may enhance
copper extraction (e.g., Hiroyoshi et al., 1995; Li and Li, 2010; Mallick
and Dasgupta, 1997) but, more generally, the presence of organic
compounds is deleterious to microbial growth, iron(II)- and/or sulfur
120
100
copper extracted (%)
80
in 96 hours
60
40
mesophiles
20
0
25 30
inoculated tests
Fig. 8. Temperature dependence of chalcopyrite dissolution. Copper extraction from a chalcopyrite concentrate of composition 64% chalcopyrite, 6.6% pyrite, 3.3% pyrrhotite and 25%
quartz, with mean particle size 27 μm, P80 −66 μm and surface area 0.36 m2 g−1 (5-point BET analysis). Tests (96 h) inoculated with single species or mixed cultures; 25–35 °C, mesophiles;
45–55 °C, moderate thermophiles; and 60–82 °C, thermophiles (archaea). Abiotic tests were not inoculated.
H.R. Watling / Hydrometallurgy 140 (2013) 163–180
oxidation (e.g., Mazuelos et al., 1999; Okibe and Johnson, 2002; Torma
and Itzkovitch, 1976).
0
2S þ 3O2 þ 2H2 O → 2H2 SO4 : ð6Þ
2.5.2. Bioleaching at moderate to high temperature
Given the strong temperature dependence of chalcopyrite dis-
solution (Fig. 8), the bioleaching of chalcopyrite at temperatures
60–90 °C is an attractive R&D goal (e.g., Córdoba et al., 2008d; Gericke
et al., 2001; Rodríguez et al., 2003) but not yet a full-scale, commercial
process (e.g., Batty and Rorke, 2006). The iron(II)-(reaction (3)) and
sulfur-oxidising (reaction (6)) capabilities of archaeal members of
Acidianus, Metallosphaera and Sulfolobus and possibly other genera are
exploited in higher-temperature bioleaching. Some recent key findings,
most often arising from studies using individual species but applicable
to other archaea, are summarised: Archaeal species contribute to stable
leach environments in continuous pilot plants operated at 12–20%
solids loadings (Gericke and Pinches, 1999; Sandström and Petersson,
1997). Limitations resulting from reduced gas solubilities in tanks
operated at high temperatures (60–80 °C) can be minimised by
supplying oxygen and/or carbon dioxide to the reactors (Batty and
Rorke, 2006; Dew et al., 2001). Microbial sensitivity to shear from
agitators results in an upper limit for solids loading of about 12.5% at
demonstration scale (Batty and Rorke, 2006). Archaea exhibit different
sensitivities to soluble metals arising from the leaching of impure
concentrates or complex ores, but in the case of copper, archaeal
cultures tolerate up to 35 g Cu L−1 (Batty and Rorke, 2006). While
redox-controlled bioleaching of chalcopyrite at temperatures 20–50 °C
results in enhanced copper extraction, redox-control is less beneficial
in the temperature range of 60–80°C (Gericke et al., 2010). The addition
of iron(II) (0.5 g L−1) promotes cell growth, high ORP and increased
chalcopyrite dissolution rates but the presence of iron at N5 g L–1
promotes jarosite formation on chalcopyrite surfaces that hinders
further dissolution (Córdoba et al., 2008d; Sandström et al., 2005).
Thus operating conditions should be optimised to minimise the
formation of iron-rich overlayers, possibly requiring strategies for iron
control. Cell attachment to surfaces is rapid (within 20 min) (Konishi
et al., 1999, 2001). As long as a fraction of the population can attach
to the chalcopyrite surface, copper extraction is efficient, but the
population may not grow if cells are prevented from approaching the
chalcopyrite surface (Gautier et al., 2008). Attached cells oxidise
elemental sulfur on particle surfaces (Liang et al., 2012) and planktonic
cells oxidise the soluble reduced sulfur or iron(II) species that accu-
mulate in solution (Jordan et al., 2006). The joint activity of attached
cells and planktonic cells has been termed ‘cooperative leaching’
archaea
moderate
thermophiles
35 45 50 55 60 65 70 75 82
temperature (degrees Celsius)
abiotic tests
 H.R. Watling / Hydrometallurgy 140 (2013) 163–180
(Rodríguez et al., 2003). Archaeal activity does not change the
underlying mechanism of chalcopyrite dissolution by ferric ions.
However, surface-attached archaea may increase the corrosion
potential and corrosion current density of chalcopyrite and may also
reduce the polarisation resistance of chalcopyrite during bioleaching
(Li and Huang, 2011).
2.5.3. Reduced sulfur additives to increase extraction
The addition of elemental sulfur to sulfide bioleach operations is a
strategy that can be used to meet three needs: (i) an alternative
means of providing the acid required to extract the target metals
(reaction (6)); (ii) the generation of heat to increase copper extraction
rates; and (iii) a means of promoting microbial colonisation in a low-
grade sulfide ore.
In the usual method of heap leaching, sulfide oxidation occurs in
acidic ferric sulfate solutions, so the presence of acid is essential.
However, for heaps of low-grade ore, greater than 99% of the bulk ore
is comprised of gangue minerals which also consume acid, to a greater
or lesser extent, with time. This acid consumption during gangue
mineral dissolution constitutes a reagent loss because it does not
contribute to the target-metal extraction. For the majority of ores
processed using heap technology, acid consumption is a major
operating cost. It is not surprising, therefore, that the biological
production of sulfuric acid through the oxidation of sulfides or
elemental sulfur has been described. Young et al. (2003) patented a
method for microbiological production of acid in which two
applications (processes) were described, one having many of the
characteristics of a heap leach of sulfide minerals and the other
employing reactor technology, such as an agitated tank. In both, the
aim was to oxidise elemental sulfur or mineral sulfides to produce
sulfuric acid using sulfur-oxidising acidophilic microorganisms that
tolerate the high sulfate and metal concentrations occurring in process
solutions. In the patent described by Duyvesteyn et al. (2002), a primary
claim was that the process described would lessen or eliminate the need
to supply commercially-purchased or chemically-produced sulfuric
acid (such as from an on-site acid production plant). The proposed
technology/application was broad; the sulfur-amended ore could be in
the form of a slurry, a heap, or a charge in a vat, with or without prior
agglomeration. Bouffard et al. (2009) listed the benefits of sulfur
addition directly to a bioleaching heap as being reduced acid con-
sumption by gangue minerals, faster mineral leaching kinetics, and
heat generation. However, they also noted the disadvantages of adding
commercially-available sulfur, which is sold and transported in prill,
slate or pellet form. In these commercial products, particle sizes
range from 1 to 13 mm and, as such, have low surface areas. Sulfur is
virtually insoluble in water, the solubility of rhombic sulfur being
1.9 ± 0.6 × 10−8 mol S8 kg−1 (Boulegue, 1978). Therefore the thrust of
the Bouffard et al. (2009) study was the addition of lignosulfonate to
improve the wettability of sulfur particles during a wet-grinding
process. In laboratory tests, Salo-Zieman et al. (2006) studied the
bioleaching of a pyrrhotite-rich, acid-consuming nickel–copper ore
and reported that the addition of elemental sulfur reduced the need
for acid supplementation during bioleaching with mesophiles.
Kohr et al. (2004) described a process for heating a heap rapidly to
temperatures at least 50 °C by augmenting the ‘fuel’ content of the ore
to at least 10 kg of exposed sulfide per tonne of ore, via the addition of
sulfide minerals. They further defined the process as the addition
preferably of small particle sizes of sulfur-containing materials that
would generate a large amount of heat when oxidised. The details of
the process were as already described in a family of patents on the
GEOCOAT® process (Harvey and Bath, 2007), in which host rock was
coated with fine particles of material rich in sulfide, and leached in a
heap. Essentially the same process was described in their more recent
patent (Kohr et al., 2011). Of the patents examined thus far, the process
described by Hunter and Williams (2006) was the only one in which the
addition of elemental sulfur was specifically proposed, compared with
171
others in which ‘sulfur addition’ was subsequently defined to mean
the addition of mineral sulfides. This patent differed also in that the
primary purpose of the addition was to achieve a sufficient sulfur
content (between 2 and 20% w/w) to promote a rapid increase in the
internal temperature of a chalcopyrite heap, such that thermophilic
microorganisms could grow and function. The concomitant production
of acid in the heap from microbial sulfur oxidation was noted as
beneficial.
In a laboratory study, augmentation of a chalcopyrite concentrate
with elemental sulfur was intended to selectively promote the growth
of sulfur-oxidising microorganisms in an iron- and sulfur-oxidising,
mixed-mesophilic culture during bioleaching, the rationale being that
sulfur overlayers formed on chalcopyrite surfaces could become rate
limiting if not removed efficiently. However, Xia et al. (2012) found
that the strategy conferred an advantage on Acidithiobacillus thiooxidans
at the expense of Leptospirillum ferriphilum to such an extent that
iron-oxidation was inhibited and copper extraction was reduced.
Optimisation of the conditions should correct the imbalance between
sulfur- and iron-oxidation. This is essentially the underlying concept
of the Bioheap™ process (Hunter, 2002a,b) in which a sulfur-oxidising
culture inefficient at iron oxidation was used to inoculate a heap of
chalcopyrite-containing ore. The process also provided for iron control
by passage of process solution through a second heap of largely barren
and inert ore, thus reducing the possible formation of passivating
iron(III) oxides/hydroxides/ hydroxysulfates on chalcopyrite surfaces.
Uhrie et al. (2012) proposed the use of elemental sulfur to promote
microbiological growth in a separate bioreactor for the purpose of
generating an inoculum for a heap leaching process.
2.5.4. Separation of biological and chemical processes
The benefits of implementing an indirect bioleaching process are:
(i) the independent optimisation of the biological and chemical
processes, (ii) restricted access of microorganisms to sulfur reaction
products, minimising sulfur oxidation to sulfate (reaction (6)) and, in
some reactor configurations, (iii) lower oxygen requirement during
leaching, (iv) a degree of acid and iron control through iron hydrolysis
and jarosite formation (reaction ((5)) and (v) lower exposure of
microorganisms to potentially toxic components in concentrates or
ores.
The separation of biological and chemical processes during
bioleaching was briefly mentioned above in the context of ORP control
and is generally referred to in the literature as ‘indirect bioleaching’. It
depends upon the propensity of acidophilic microorganisms to become
attached to inert substrates and form biofilms, within which bacterial
oxidation of ferrous ion occurs (reaction (3)) and from which the
circulating ferric-ion rich medium is fed to a chemical leaching reactor.
Ferrous ion oxidation can be achieved with different types of reactors
furnished with different inert support materials for the biofilm. Most
applications apply packed beds, fluidised beds or rotating biological
contactors furnished with a variety of support materials (e.g., resin,
glass or alginate beads, activated carbon, ground silica, jarosite, poly-
ethylene, polyvinyl chloride, polystyrene). Relatively small (economic)
reactors can be used because ferric ion productivity is generally high. A
number of two-stage processes have been developed and implemented,
most providing suitable growth conditions for At. ferrooxidans, the species
thought to be most prevalent in bioleaching at the time of those studies.
Acronyms used to describe three examples are BACFOX (bacterial film
oxidation — Karavaiko, 1985), BFIG (bacterial ferric ion generator — Van
Staden, 1998) and IBES (indirect bioleaching with effects separation —
Carranza et al., 1993).
2.6. Cations as catalysts in ferric sulfate systems
Several studies have been conducted in which selected cations were
added to sulfuric acid–ferric sulfate leach systems and the enhancement
(or not) of copper extraction from chalcopyrite reported. Barriga
172 H.R. Watling / Hydrometallurgy 140 (2013) 163–180

Mateos et al. (1987) compared a number of elements and showed that
the precipitation of silver sulfide onto fresh chalcopyrite surfaces, or
onto already-passivated surfaces, reactivated chalcopyrite. In other
comparative tests, silver ions were the most efficient at promoting
chalcopyrite dissolution (Ballester et al., 1990, 1992; Escudero et al.,
1993; Muñoz et al., 2007a). Johnson et al. (2008) reported that
concentrates containing high silver contents were amenable to
bioleaching at low temperatures with mesophiles but that concentrates
with lower silver contents required higher temperatures and moderate
thermophiles.
The beneficial action of silver (Ag+) was thought to proceed through
reaction with the chalcopyrite surface with the formation of silver
sulfide (Ag2S) on the sulfide mineral surface (reaction (7)) followed
by the oxidation of Ag2S by ferric ions (reaction (8)) (Miller and
Portillo, 1979). However, this simple mechanism does not account for
all the observations made then and subsequently. For example, it was
shown that ferric ion oxidation of Ag2S (reaction (8)) required
temperatures greater than 100 °C (Dutrizac, 1994) and elemental sulfur
was not detected on a chalcopyrite surface post silver-catalysed
leaching (reactions (8)and (9)) (Parker et al., 2003). Hypotheses
about the formation of a small amount of silver (Muñoz et al., 1998;
Price and Warren, 1986) included reactions (9)–((11)] (Kolodziej and
Adamski, 1984; Price and Warren, 1986). In addition, the formation of
Ag2SO4 in the presence of a large excess of Ag+ (Warren et al., 1984)
was attributed to high oxidation potentials and excess Ag+ near the
Ag2S surface (Price and Warren, 1986), a reaction that would deplete
Ag+ concentrations and result in lower (catalysed) copper extraction,
as was also reported by Córdoba et al. (2008c, 2009). In the reaction
mechanism proposed by Hiroyoshi et al., 2002 for systems operated at
low solution potential, chalcopyrite was reduced to chalcocite and silver
ions reacted with hydrogen sulfide (overall reaction (12)) and
chalcocite was oxidised by ferric ions more readily than chalcopyrite
(reaction (13)). Hiroyoshi et al. (2007) reported that Ag+ caused the
critical potential (that potential below which chalcopyrite leaching
occurs faster) to rise.
þ 2þ
CuFeS2 þ 4Ag ¼ 2Ag2 Sðon chalcopyrite surfaceÞ þ Cu
3þ þ 0 2þ
2Fe þ Ag2 S ¼ 2Ag ðregenerated catalystÞ þ S þ 2Fe
The benefits of pre-treating pyrite with silver and then using the
treated pyrite in the Galvanox™ process were described by Nazari
et al. (2012). In that process, in the absence of silver-treated pyrite,
the surface layer of sulfur that forms on chalcopyrite particles is non-
conductive and limits electrical contact between the pyrite and
chalcopyrite particles. However copper extraction in the Galvanox™
process is enhanced when silver-treated pyrite is used. Nazari et al.
(2012) proposed that the mechanism of silver-enhanced extraction
involved a small part of the added silver reacting with the sulfur layer
to increase its conductivity and facilitate the transfer of electrons
between chalcopyrite and pyrite particles. The pyrite (plus added silver)
is recycled in the Galvanox™ process.
Bismuth has received less attention than silver as a copper leaching
catalyst. Hiroyoshi et al. (2007) ranked bismuth second, and Escudero
et al. (1993) ranked bismuth fourth most-effective catalyst of the
metal ions tested. In contrast, Muñoz et al. (2007a) reported that
bismuth did not enhance the leaching of copper from a sulfide ore and
Gómez et al. (1999) reported only a small positive effect. Mier et al.
(1994) suggested that the mechanism involved the reaction of
bismuth with the phosphate added as part of the bioleaching medium
and precipitation of bismuth phosphate, preventing ferric ions from
complexing with the phosphate and thus increasing the oxidising
potential of the Fe(III)/Fe(II) couple.
3. Sulfuric acid — alternative oxidants
The sulfuric acid–ferric sulfate system for the oxidative leaching of
chalcopyrite has been studied widely, and the redox chemistry, reaction
products, and consequences of adopting certain controlled conditions
are well understood. The reagents are inexpensive and, with biological
assistance, can be regenerated during processing. However, the
oxidising potential of ferric ion is not particularly high and several
stronger oxidants have been tested for their ability to extract copper
from chalcopyrite. Half reactions with standard reduction potentials
are summarised for selected oxidants (Table 3) and copper extraction
data compared in Fig. 9. It should be noted that the cupric/cuprous
2þ
þ Fe ð7Þ couple does not play a role in sulfate systems as concentrated as those
used in oxidative hydrometallurgy, as sulfate anions do not complex
and thus stabilise the cuprous ion, which is rapidly oxidised in
ð8Þ oxygenated or ferric ion systems.

þ 2þ 2þ 0 0 3.1. Sulfuric acid–dichromate

CuFeS2 þ 4Ag → Cu þ Fe þ 4Ag þ 2S ð9Þ

The dissolution of a chalcopyrite concentrate in medium containing

þ 2þ 0 3þ
Ag þ Fe → Ag þ Fe ð10Þ 0.2 M dichromate and 0.5 M sulfuric acid showed strong temperature
dependence in the range of 30–80 °C (Antonijevic et al., 1994). In
0
2AgCl → Ag þ Cl2 ðphotochemical decompositionÞ ð11Þ those tests, the consumption of dichromate was greater than would
be expected if elemental sulfur was the sole product of sulfide oxidation
þ 2þ 0 (reaction (14)) indicating that some of the sulfide was oxidised to
2CuFeS2 þ 4Ag → Cu2 S þ 2Fe þ 2Ag2 S þ S ð12Þ

3þ 2þ 2þ 0
Cu2 S þ 4Fe → 2Cu þ 4Fe þS : ð13Þ
Table 3
In tests using ore particles in columns, simulating heap leaching, the Selected oxidants, half reactions and standard reduction potentials.
benefit of silver catalysis was less clear. Silver addition resulted in a Handbook of Chemistry and Physics, 89th edition, CRC Press, 2008.

sharp but transient increased copper extraction rate from chalcopyrite Oxidant Half reaction Standard reduction
contained within in a complex ore (Ahonen and Tuovinen, 1990) but potential
resulted in improved copper recoveries from low-grade chalcopyrite (E0) [V]

ore in 300-day tests (Muñoz et al., 2007b). In those process develop- Cupric ion Cu2+ + e− → Cu+ 0.153
ments where silver catalysis was shown to be effective, there remained Ferric ion Fe3+ + e− ⇆ Fe2+ 0.771
−
Dichromate Cr2O2− +
7 + 14H + 6e → 2Cr
3+
+ 7H2O 1.232
a concern about the economics of adding silver to full scale operations.
Chlorate ClO− + −
3 + 6H + 6e → 3H2O + Cl
−
1.451
Hu et al. (2002) suggested the use of silver-bearing concentrates as MnO− + − 2+
Permanganate 4 + 8H + 5e → Mn + 4H2O 1.507
a cost-effective strategy. In the IBES process (Carranza et al., 1997; Hydrogen peroxide H2O2 + 2H+ + 2e− → 2H2O 1.776
Palencia et al., 1998) and the BRISA process (Romero et al., 2003), the Ozone O3 + 2H+ + 2e− → O2 + H2O 2.076
−
flow sheets included a methodology to recover and recycle silver from Peroxodisulfate S2O2− +
8 + 2H + 2e ⇆ 2HSO−4 2.123
−•
S2O2−
8 + initiator ⇆ 2SO4 2.6
the leached residues.
 H.R. Watling / Hydrometallurgy 140 (2013) 163–180 173

90 0.1 M Fe(III) in H2SO4; 80C

80 0.1 M Fe(III); 0.18 M H2SO4; 90C
70 1 M Fe(III); 0.25 M H2SO4; 90C

Cu (% extracted)
60 0.2 M Cr2O7; 0.5 M H2SO4; 70C
50 0.1 M Cr2O7; 0.4 M H2SO4; 70C

40 0.5 M ClO3; 1 M HCl; 65C

30 20% H2O2; 0.1 M H2SO4; 70C

2 M H2O2; 3 M H2SO4; 40C
20
3 M H2O2; 1 M H2SO4; 25C
10
2.5% O3; 0.5 M H2SO4; 22C
0
0 10 20 30 40 50 60 0.2 M S2O8; 0.01 M Fe(III); 0.1 M H2SO4; 23C
time (hours)

Fig. 9. Example copper extraction data for chalcopyrite concentrates of similar particle sizes: ferric sulfate systems (Ferreira and Burkin, 1976; Jones and Peters, 1976; Munoz et al., 1979),
dichromate (Antonijevic et al., 1994; Aydogan et al., 2006), sodium chlorate (Xian et al., 2012), hydrogen peroxide (Adebayo et al., 2003; Antonijevic et al., 2004; Olubambi et al., 2006),
ozone (Havlik and Skrobian, 1990); peroxodisulfate (Dakubo et al., 2012).

sulfate (reaction (15)). The results were consistent with those of earlier
studies (Murr and Hiskey, 1981; Shantz and Morris, 1974). The
concentration of dichromate did not affect the dissolution rate and it
was concluded that the chalcopyrite surface was covered by Cr(VI)
(Antonijevic et al., 1994; Murr and Hiskey, 1981). Dichromate activity
increased with increasing acid concentration in the range 0.25–2.0 M
H2SO4 but there was minimal additional benefit when acid con-
centrations N 2M were used. The presence of chloride ions in the system
decreased copper recovery, an effect that was attributed to the
displacement of Cr(VI) ions with Cl− ions on the chalcopyrite surface.
Concentrations of ferric ions (up to 0.09 M) and copper ions (up to
0.08 M) had negligible effects on reaction rates.
6CuFeS2 þ 5K2 Cr2 O7 þ 35H2 SO4 → 6CuSO4 þ 3Fe2 ðSO4 Þ3 þ 5K2 SO4
0
þ12S þ 5Cr2 ðSO4 Þ3 þ 35H2 O
6CuFeS2 þ 17K2 Cr2 O7 þ 71H2 SO4 → 6CuSO4 þ 3Fe2 ðSO4 Þ3 þ 17K2 SO4
3.3. Sulfuric acid–permanganate
Permanganate ion has been used to maintain solution ORP in the
acid leaching of chalcopyrite and pyrite but not as the primary oxidant.
Kametani and Aoki (1985) and Sandström et al. (2005) used potassium
permanganate to control ORP during ferric sulfate chemical leaching of
finely-ground chalcopyrite concentrates at 90 and 65 °C, respectively.
From their results, Sandström et al. (2005) concluded that the
permanganate oxidised ferrous ions to ferric ions (reaction (17)), rather
than oxidising the chalcopyrite directly. They noted that a disadvantage
of using potassium permanganate was the loss of ferric ions from
solution via reaction with potassium and sulfate ions to form jarosite
(reaction ((5)) resulting in lower copper extraction. Potassium perman-
ganate was also a suitable oxidant for controlling ORP during the ferric
ð14Þ sulfate leaching of pyrite, and the mass of potassium permanganate
solution required to maintain an ORP set point was a reliable indicator
of leaching progress (Bouffard et al., 2006).

þ17Cr2 ðSO4 Þ3 þ 71H2 O: ð15Þ

2þ – þ 3þ 2þ
5Fe þ MnO4 þ 8H → 5Fe þ Mn þ 4H2 O: ð17Þ
In the study by Aydogan et al. (2006), dissolution of a chalcopyrite
concentrate in H2SO4 (0.1–0.5 M) and K2Cr2O7 (0.01–0.15 M) media 3.4. Sulfuric acid–hydrogen peroxide–hydroxyl radical
was temperature dependent, the greatest extraction being achieved at
97 °C, the top temperature tested. At 70 °C, about 70% copper was Hydrogen peroxide is a strong oxidising agent in acidic medium
extracted in 150 min in medium containing 0.4 M H2SO4 and 0.1 M (Adebayo et al., 2003). It has been used as a leaching agent for uranium
dichromate. While dissolution with dichromate was faster than with ores (Eary and Cathles, 1983) and various studies on the use of peroxide
ferric ions, it was nevertheless controlled by diffusion through a porous with zinc–lead concentrate, pyrite and sphalerite have also been
sulfur layer (reaction (14)). conducted (e.g., Antonijevic et al., 1994; Olubambi et al., 2006). A
suggested oxidation mechanism in dilute aqueous solutions of
3.2. Sulfuric acid–chlorate hydrogen peroxide involved dissociation to form the hydroxyl radical
(reaction (18), catalysed by ferrous ions) that oxidised the sulfide
Chlorate ion is a strong oxidising agent (Table 3) that has been used moiety of minerals (reaction (19)) (Adebayo et al., 2003; Lin and
to enhance chalcopyrite leaching in both hydrochloric acid and sulfuric Luong, 2004).
acid systems. Kariuki et al. (2009) studied chalcopyrite oxidation by
mixing 2 g concentrate with up to 3 g sodium chlorate and 30 mL 2þ · – 3þ
H2 O2 þ Fe → HO þ OH þ Fe ð18Þ
of 10 g L−1 H2SO4 and heating in sealed Teflon-lined vessels in the
temperature range of 45–200 °C. The results showed that chalcopyrite
oxidation (reaction ((16)) increased with increased temperature up to · 2– 0
2HO þ 2S ðsÞ → 2S ðsÞ þ H2 O þ 0:5O2 : ð19Þ
approximately 165 °C.

6CuFeS2 þ 17NaClO3 þ 3H2 SO4 →3Fe2 ðSO4 Þ3 þ 6CuSO4
þ17NaCl þ 3H2 O:
Sodium chlorate concentrations up to 1 M were tested at 45 °C with
stirring in batch reactors (Xian et al., 2012). In these tests, the leaching
rate accelerated with increased acid up to 1.5 M. At 0.5 M and 1 M HCl,
respectively, 45% and 65% Cu were extracted in 300 min.
ð16Þ Both Adebayo et al. (2003) and Antonijevic et al. (2004) used
chalcopyrite concentrates in their studies, while Olubambi and
Potgieter (2009) conducted an electrochemical study focused on the
mechanism of chalcopyrite oxidation with acidic peroxide solution.
Olubambi and Potgieter (2009) noted that chalcopyrite leaching with
sulfuric acid alone was slow (reaction (2)) but that, when hydrogen
peroxide was added to the system, copper extraction was rapid
174 H.R. Watling / Hydrometallurgy 140 (2013) 163–180

and that the sulfide was oxidised to elemental sulfur and sulfate solution and it has a high oxidising potential (Table 3). Havlik and
(reactions (20) and (21)). Skrobian (1990) studied the oxidation of a chalcopyrite concentrate
using an isothermal reactor containing 3 g sample and 1 L of 0.5 M
0
2CuFeS2 þ 5H2 O2 þ 5H2 SO4 → 2CuSO4 þ Fe2 ðSO4 Þ3 þ 4S þ 10H2 O H2SO4 into which ozone was introduced using a gas impeller. The
ð20Þ maximum ozone concentration was 3 vol.% in the gaseous stream
being sparged into the leachate. Copper extraction was efficient at
20 °C but decreased at higher temperatures, an effect attributed to the
2CuFeS2 þ 17H2 O2 þ H2 SO4 → 2CuSO4 þ Fe2 ðSO4 Þ3 þ 18H2 O: ð21Þ
lower ozone solubility. Because no elemental sulfur was detected in
any experiment and the ratio of Fe:Cu was 1:1, Havlik and Skrobian
Leaching rates were strongly dependent on temperature in a range
(1990) concluded that the reaction, comprising several possible
of 30–80 °C; with maximum copper extractions of 5% to 60% after
intermediate steps, proceeded according to overall reaction (23).
60 min. However, rates slowed after 60–80 min at temperatures
Using results obtained at different temperatures and visualisation of
60–80 °C, attributed to increased peroxide at higher temperatures
leached surfaces, they proposed that the rate limiting step was the
(Adebayo et al., 2003). These authors also reported that best results
diffusion of ozone from the acidic medium to the chalcopyrite surface.
were obtained using 30% H2O2 v/v with H2SO4 and moderate agitation,
They also noted the possibility of using powerful ozonisers, which are
and suggested that high peroxide concentrations and strong agitation
used to prepare drinking water, in future mineral processing flowsheets.
during leaching both caused accelerated hydrogen peroxide decom-
In subsequent research, Havlik et al. (1999) examined ways of making
position. Antonijevic et al. (2004) reported increased leaching rates in
the process more efficient, particularly in respect of the contact times
the range 0.1–5 M H2O2 in 2 M H2SO4 at 40 °C. In both studies, higher
between gas bubbles and the mineral particles.
sulfuric acid concentrations resulted in higher dissolution rates (tests
conducted in the range 0.1–6 M H2SO4). More recently, Adebayo
(2006) showed that copper extraction from a low-grade chalcopyrite 3CuFeS2 þ 8O3 → 3CuSO4 þ 3FeSO4 : ð23Þ
ore was faster when leached in a solution (pH 4.3) containing ammo-
nium sulfate (72 g L−1) with 45% v/v H2O2.
Carillo-Pedroza et al. (2010) studied the use of ozone as a strong
The addition of ethylene glycol to batch reactors containing finely
oxidant in an acidic ferric sulfate system applied to copper extraction
ground chalcopyrite in 1 M H2SO4–0.26 M H2O2 medium at 65 °C
from an ore. They conducted isothermal agitated tests in which the
hindered peroxide decomposition, resulting in improved copper
solution was heated prior to ore addition (300 g in 1 L solution), and
extraction from 20% to 60% in 240 min (Mahajan et al., 2007). Similarly,
the oxygen/ozone mixture was injected into the base of the reactor
copper extraction of 65% was achieved in 60 min when ethylene glycol
(υO3 0.5 or 1 g h−1). The tests were carried out at 25 °C, using a low-
was added to a 1.25M H2SO4–2.1M H2O2 solution but no further copper
grade, ground ore (0.7%Cu) split into different size fractions and leached
was extracted up to 300 min (Solis-Marcíal and Lapidus, 2013).
in solutions of sulfuric acid (0.1–0.5 M) and ferric ions (0–0.5 M). Not
Olubambi et al. (2006) reported copper extraction of 74% in 180 min
surprisingly, best copper extractions were obtained using the smallest
from a ground, complex ore leached in 1 M H2O2–1 M H2SO4 solution
size fraction and highest ferric and acid concentrations, with 0.5 g h−1
and attributed the increased dissolution rate with high peroxide
O3 inflow. Overall, the results showed that ozone reduced the leaching
concentration to the formation of Caro's acid (reaction ((22)).
time and allowed the use of lower ferric ion and acid concentrations
when compared with a typical ferric sulfate leach system. It is also
H2 O2 þ H2 SO4 → H2 SO5 þ H2 O: ð22Þ
worth noting that gangue minerals in the low grade ore apparently
did not consume ozone. However, the enhanced chalcopyrite leaching
Olubambi et al. (2006) suggested that optimisation of a system with
was less effective with larger particle sizes, from which result it was
1 M H2SO4 and peroxide concentrations up to 1 M could yield an
concluded that the presence of a single oxidant was sufficient to
economical process because the reagent costs were low and the overall
promote copper extraction from samples with low chalcopyrite surface
process would not be particularly corrosive in respect of materials of
areas. In their subsequent, broader study, Carillo-Pedroza et al. (2012)
construction. While the test was encouraging in that the peroxide was
summarised their results on the use of ozone as an alternative oxidant
active when an ‘ore’ was used, this ‘ore’ was atypical, comprising
for sulfide ores as follows: “Results show that the extraction of gold
massive chalcopyrite (66%) with minor pyrite (11%) and silica (7%). In
and silver is increased by at least 15%, with lower cyanide consumption;
an investigation of the kinetics of peroxide decomposition in the
the extraction of copper increased by 16% and in less time; and in the
presence of ground pyrite crystals in hydrochloric acid, Chiriţ (2007)
case of coal, sulfur is removed above 70%”. They concluded that the
reported that peroxide decomposition was catalysed by both the iron
oxidation using ozone was a promising clean technology for processing
sites on pyrite surfaces and by aqueous ferric ions. Increases in pyrite
of sulfide ores.
surface area, temperature, peroxide concentration and acid con-
centration all resulted in increased peroxide decomposition rates. The
highest losses of peroxide by decomposition into molecular oxygen 3.6. Sulfuric acid–peroxodisulfate
and water were observed at moderate temperature (45 °C) and initial
solution pH 2. In the presence of ferric ion ligands, only the mechanism The advantages of peroxodisulfate (S2O2−8 ) as an oxidising agent
of decomposition catalysed by the iron sites on the pyrite surface were reported to be that it could be made from sulfuric acid using an
contributed and thus overall decomposition was lower. The dissolution electrochemical cell (Canizares et al., 2005; Radimer and McCarthy,
of chalcopyrite involves the production of ferrous ions which would 1979) at low energy cost ($0.20 kg−1) (Kimizuka et al., 2001).
be oxidised to ferric ions in leach solutions (reactions (20) and (21)). Peroxodisulfate undergoes decomposition or hydrolysis, depending
The additional ferric ions entering the solution would increase the upon the prevalent conditions (reactions (24) and (25)) but may also
decomposition rate of hydrogen peroxide (Garten, 1962; Kolthoff form reactive species and radicals (Table 3). In the leaching of chal-
et al., 1973), constituting a further reagent loss. copyrite using peroxodisulfate, the main activator for the formation of
sulfate radicals is expected to be the ferrous ion released from the
3.5. Sulfuric acid–ozone mineral during dissolution (Dakubo et al., 2012). In contaminated
aquifer remediation using ferrous ion-activated peroxodisulfate, the
Potential advantages of the use of ozone as an oxidising agent for decomposition rate of peroxodisulfate was 10–20% per week (Brown,
chalcopyrite are that it does not introduce additional ions into the 2003). Once the peroxodisulfate has been converted to sulfate ions,
 H.R. Watling / Hydrometallurgy 140 (2013) 163–180
it can be regenerated electrochemically, minimising sulfuric acid
consumption.
2Na2 S2 O8 þ 2H2 O → O2 þ 2H2 SO4 þ 2Na2 SO4 ð24Þ
Na2 S2 O8 þ H2 O → NaHSO4 þ NaHSO5 : ð25Þ
Dakubo et al. (2012) leached chalcopyrite concentrate or ore in
stirred reactors or small columns at 23 °C. When ground massive
chalcopyrite samples were leached in columns with solutions (pH 2)
containing sulfuric acid or peroxodisulfate (10 g L−1) in sulfuric acid,
copper extraction with peroxodisulfate was 500 times greater than
without (% extraction not shown but roughly calculated to be
approximately 10% extraction in 75 h). In tests using stirred batch
reactors containing either 1.5 g of chalcopyrite concentrate or 20 g of
ground, low-grade ore in 1 L H2SO4 (pH 2), dissolved oxygen enhanced
copper extraction but the pre-addition of ferrous ions to the reactors
had little effect. Up to 30% of the contained copper was extracted in
90 h when the ground ore was leached with 10 g L−1 Na2S2O8 at pH 2.
Up to 50% Cu was recovered from concentrate at 45 °C using 50 g L−1
Na2S2O8 at pH 2. Particle size influenced extraction; extractions were
70% (25 μm particle size) and 25% (125 μm particle size), under similar
leaching conditions. Dakubo et al. (2012) estimated a molar ratio of
S2O2−
8 added to Cu extracted as 8.8:1, for a 96-hour test with 50 g L−1
Na2S2O8 (i.e., not reagent limited).
4. Hybrid sulfate–chloride systems
4.1. H2SO4–NaCl–O2
The advantage of using sulfuric acid and sodium chloride to create a
pseudo-chloride lixiviant is that these reagents are cheaper than ferric
chloride or cupric chloride. The addition of chloride to a sulfate system
radically changes the solution speciation, as both iron and copper ions
can form complex species with chloride ions which may assist leaching.
The oxidant in this system is oxygen. There should be no need to add
ferric ions to the system initially; ferrous ions produced during
chalcopyrite leaching will be oxidised to ferric ions (reactions (2) and
(3)) and will subsequently contribute to overall copper extraction.
With careful selection of leaching conditions, most of the iron and
some sulfate can be precipitated as sodium jarosite (reaction ((5)).
The addition of chloride to a sulfate system changes the speciation of
both copper and iron through the formation of Cu- and Fe-complex
chloride ions in concentrations reflecting the overall solution compo-
sition. However, there is as yet no consensus on which complex species
are beneficial to copper extraction under different conditions. Li et al.
(2010) examined the extraction rates of copper from a chalcopyrite
concentrate for a suite of leach systems and concluded that Fe3+ activity
was a key parameter. In tests conducted at 75 °C, they measured faster
kinetics for the NaCl (0.25 M)–H2SO4 system at pH 2 (97% Cu extraction
in 170 h) than at pH 1 (58% Cu extraction in 170 h). The slower rate at
pH 1 was attributed to the increased solubility of iron-containing
secondary minerals due to the formation of FeCl2+ solution species
and the consequent lower Fe3+ activities in the presence of chloride.
Ruiz et al. (2011) reported that leaching of a finely-ground chalcopyrite
concentrate in sulfate–chloride solutions was rapid, 90% of the copper
being extracted in 180 min at 100 °C. The presence of 0.5 M chloride
ions (29 g L−1 NaCl) enhanced the leaching rate significantly but the
addition of 3 g L−1 Fe3+ caused both an increase in the ORP and a
large decrease in the leaching rate. Muñoz-Ribadeneira and Gomberg
(1970, 1971) attributed the increased copper extraction from
chalcopyrite when as little as 0.1 M HCl was added to a sulfuric acid
leach to the in situ generation of the oxidant CuCl2−4 from the mixed
acid. Subramanian and Ferrajuolo (1976) leached a complex sulfide
ore in sulfuric acid with O2 over pressure (100 °C) and reported that
the presence of chloride ion (0.5–10gL−1) resulted in slightly enhanced
175
copper extraction from chalcopyrite, reduced the amount of sulfate
formation and reduced the concentration of iron in solution. Similarly,
Deng et al. (2001) reported that the addition of small amounts of
chloride to a sulfuric acid–O2 leach system enhanced copper extraction
from the copper residue produced from the oxidative leaching of nickel
matte.
In 1983 the Broken Hill Associated Smelters patented a process for
the recovery of copper from a copper–lead matte using oxygenated
acidic sulfate–chloride solutions (Sawyer and Shaw, 1983). According
to Lu et al. (2000), this was possibly the only low-pressure sulfide
leach process to have been commercialised. Lu et al. (2000) applied
the ‘copper matte’ process to the dissolution of finely-ground chal-
copyrite concentrate in solutions of pH b 0.8 (0.8 M H2SO4) containing
1 M NaCl in the temperature range of 60–95 °C. They achieved up to
97% copper extraction in 9-hour tests. Based on their results showing
that chloride concentrations N0.5 M did not enhance the leaching rate
of chalcopyrite (consistent with the results of Palmer et al., 1981), Lu
et al. (2000) concluded that it was important only that there were
sufficient chloride ions present rather than an excess. This finding has
commercial implications for geographical areas lacking in freshwater
but with a supply of brackish water or seawater; seawater contains
approximately 0.5M chloride ions. From an examination of the residues,
Lu et al. (2000) concluded that the sulfur reaction product obtained in
the presence of 1 M NaCl was crystalline and porous, allowing reactants
to diffuse through the surface product layer to the unreacted mineral
surface. O'Brien et al. (1999) piloted a similar process involving oxygen
sparging of an agitated leach at 80–95 °C. Ground chalcopyrite–pyrite
ore (4% Cu) was used for the tests of duration less than 24 h. The pyrite
in the ore promoted chalcopyrite oxidation via galvanic interaction and
up to 95% of the chalcopyrite was oxidised, compared with only 17% of
the marcasite/pyrite content.
The Cuprochlor process (Espejo et al., 2001) has been used to extract
copper from copper oxide and mixed copper oxide/secondary sulfide ores
containing chalcocite, bornite and covellite (Herreros et al., 2006). In part,
the process consisted of fine crushing of the ore and agglomeration with
the addition of first a calcium chloride solution (12 kg CaCl2 t−1 ore) and
then sulfuric acid. This strategy resulted in the formation of competent
agglomerates bound by gypsum, as described by Vračar et al. (2000), as
well as high chloride concentrations in solution. After curing, the heaped
ore was leached with high-chloride solution (90 g L−1) containing
copper (5 g L−1). At the Michilla mine in Chile (Antofagasta Minerals),
65% of the contained copper was extracted in 50 days of leaching and
90% in 110 days. The process was considered to be ‘competitive with
bioleaching’ (Herreros et al., 2006). A modification of the Cuprochlor
process to facilitate the leaching of copper sulfide concentrates (including
chalcopyrite) in heaps incorporated the calcium chloride agglomeration
strategy (Rauld Faine et al., 2005a), by which it was differentiated from
other processes for the leaching of concentrates in heaps.
In a separate development, Aroca Alfaro and Rauld Faine (2004)
used a reactive chloride–sulfate gel mixed with copper concentrate to
form a high viscosity paste which was poured into an open mould
that allowed the ingress of oxygen. The mixture was allowed to settle
and react, with the periodic addition of water to counter evaporation
and sulfuric acid to maintain sulfate activity. Copper was recovered
easily from the resulting dry paste, which contained the copper salts
as chloride and sulfate compounds. A similar process to leach copper
from copper concentrates under pressure but at ambient temperature
using a reactive chloride–sulfate gel was described by Rauld Faine
et al. (2005b); the authors specifically included chalcopyrite as one of
the target minerals.
4.2. H2SO4–Fe2(SO4)3–NaCl.
The systems discussed in this section are similar to the above but are
differentiated by the inclusion of ferric ions in leach media, rather
than reliance on their production during chalcopyrite oxidation. The
176 H.R. Watling / Hydrometallurgy 140 (2013) 163–180
influence of sodium chloride on ferric sulfate oxidation of chalcopyrite
was studied at 95 °C and atmospheric pressure using a finely-ground
chalcopyrite concentrate (Carneiro and Leão, 2007). Solutions were
prepared by dissolving ferric sulfate and sodium chloride and adjusting
the solution to pH0.15 with concentrated sulfuric acid. Using a 5% solids
loading, up to 90% of the copper was extracted with added sodium
chloride (58 g L−1; 0.5 M) compared with 45% of the copper in the
absence of sodium chloride (Carneiro and Leão, 2007). In that study,
sodium chloride addition was reported to enhance chalcopyrite dissolu-
tion by reducing the total iron and ferric iron concentrations via jarosite
precipitation (reaction ((5)), forming cuprous chloride complex ions
and enabling the participation of the Cu(I)/Cu(II) redox couple in
leaching, and increasing the surface area and porosity of the sulfur
reaction product. In another study (Kinnunen and Puhakka, 2004), a
much lower concentration of sodium chloride (5 g L−1) resulted in
enhanced chalcopyrite (bio)leaching in ferric sulfate media; copper
extractions of about 100% and 80% were achieved at 87 °C in 20 days
with and without added sodium chloride, respectively. However, the
enhancement in copper extraction with sodium chloride was much
less in similar 20-day tests at 68 °C. In the tests with added sodium
chloride, solutions were pH b1 compared with pHs 1.2–1.3 in the
absence of sodium chloride, a factor influencing the soluble iron(III)
concentrations (higher with sodium chloride) and amounts of jarosite
formed (higher without sodium chloride). The results of the above
recent studies were consistent with those of Dutrizac (1981) who
reported that the addition of chloride ion to a ferric sulfate–sulfuric
acid system progressively accelerated the leaching of chalcopyrite and
promoted copper extraction significantly.
Dutrizac and MacDonald (1971) investigated the addition of sodium
chloride on the rate of chalcopyrite dissolution from low-grade (3% Cu)
copper sulfide lump ore at low temperatures over prolonged periods,
in a simulation of dump leaching conditions. In those tests, ore was
crushed to −6 mm and loaded into 25 mm-diameter columns to give a
1 m bed depth. The ore was leached with 0.1 M Fe3+ in 0.1 M H2SO4
with/without 0.1 M NaCl without solution recycle. Extractions ranged
from 1 to 8% Cu in tests conducted in the temperature range of
25–40 °C but, more importantly, the presence of sodium chloride
inhibited chalcopyrite dissolution. Dutrizac and MacDonald (1971)
concluded that, as dump leach temperatures are generally below 50 °C,
large chloride additions would not be beneficial. Nevertheless, in some
arid regions where freshwater supplies are restricted and water use in
mineral processing must be efficient, seawater was substituted for
freshwater in a few unit processes, including heap leaching of copper
ores. Clearly, the main benefit to the mine was related to water efficiency
and there are few published data on the chemistry of the hybrid sulfate–
chloride system. Philippe et al. (2010) reviewed those operations using
seawater and noted that the majority had to overcome specific issues
related to water quality, corrosion management and process efficiency.
4.3. H2SO4–Fe2(SO4)3–LiCl
In tests using relatively dilute sulfate solutions, Dutrizac (1981) noted
that the addition of lithium chloride in the concentration range of 1–4 M
converted the sulfate system (0.1 M Fe2(SO4)3; 0.3 M H2SO4; 90 °C) to a
pseudo-chloride system. In that study, the addition of lithium chloride
was a means of increasing the chloride concentration without promoting
the formation of jarosite-like compounds, as happened when sodium or
potassium chlorides were added into sulfate systems. The addition of
chloride ion caused a gradual increase in the leaching rate, up to 2.6
times at a concentration of 4 M chloride ion; however, greater chloride
concentrations resulted in the precipitation of lithium sulfate.
5. Hybrid sulfate–nitrate systems
Nitric acid is both a strong acid and a strong oxidising agent. The
potential use of nitric acid in copper processing has been studied over
many years (Bardt, 1919–1922; Bjorling, 1968; Brennecke et al., 1981;
Davies et al., 1981; Habashi, 1973; Prater et al., 1973; Westby, 1918),
but the only process to have been operated at commercial scale is
the Nitrogen-Species-Catalysed (NSC) sulfuric acid pressure leach
(Anderson, 1999, 2000). The advantage of nitric acid at moderate
temperature is the absence of corrosion of stainless steel equipment.
Disadvantages are that the industry has had relatively little experience
of the system and that nitrate in leach solutions may present problems
for SX systems because the nitrogen species may degrade extractants.
5.1. Sulfuric acid–nitric acid
Queneau and Prater (1974) patented a process in which a sulfide
material (including copper sulfide) was subjected to leaching in nitric
acid solution under conditions controlled to ensure the formation of
easily filterable hydrogen jarosite or other insoluble iron compounds.
Elemental sulfur was formed and reported with the residues and the
precipitated iron compounds in the filter cake. Unreacted sulfide
particles could be separated by froth flotation after removal of the
elemental sulfur and recycled to the leach system. The testwork
associated with this development was described by Prater et al.
(1973), who suggested that the dissolution proceeded according to
reaction (26). It was noted that acid concentration was an important
parameter, strongly influencing the ratio of NO/NO2 generated from
nitric acid; the NO species is the more reactive and dominates solutions
b25% HNO3. Both temperature and nitric acid concentrations influenced
the amount of elemental sulfur formed (Prater et al. (1973)). The
complexity of this system would necessitate careful testwork to
optimise copper extraction and elemental sulfur production.
6CuFeS2 þ 22HNO3 þ 9H2 SO4 → 6CuSO4 þ 3Fe2 ðSO4 Þ3 þ 22NO ð26Þ
0
þ6S þ 20H2 O:
Bjorling et al. (1976) aimed to develop a process for the treatment of
chalcopyrite concentrate that met the criteria: (i) a closed circuit from
which products can be utilised or disposed in an environmentally
friendly manner; (ii) air as the primary oxidant because of its
availability and low cost; and (iii) minimised construction costs by
using simple equipment. The further condition, that the sulfide moiety
of the chalcopyrite must be oxidised to elemental sulfur (not sulfate)
by controlling ORP required a secondary oxidant for the oxidation step
that could be regenerated using air. They described the system as
oxidation of chalcopyrite by oxygen (air) in sulfuric acid in the presence
of a small amount of nitric acid, which acted as a catalyst (reaction (27)).
Nitric acid is an efficient oxidant, becoming reduced to nitric oxide
(reaction (28), in which the protons are supplied by the sulfuric acid);
nitric oxide can be re-oxidised to nitric acid in the presence of oxygen
and water (reaction (29)).
4CuFeS2 þ 5O2 þ 20H → 4Cu
þ 2þ 3þ
þ 4Fe þ 10H2 O þ 8S
0
ð27Þ
 
– þ – 0
NO3 þ4H þ3e → NO þ 2H2 O E ¼ 0:957V ð28Þ
4NO þ 3O2 þ 2H2 O → 4HNO3 : ð29Þ
In the process developed by Bjorling et al. (1976), nitric acid and
hydrogen ions had to be supplied continuously at the same rates as
they were consumed (pH 0.9) in order for the critical ORP to be
maintained. Under such conditions the formation of sulfate could be
minimised and other parameters optimised. The nitric oxide could be
re-converted to nitric acid outside the reaction vessel (reaction (29)).
In this process, a retention time of 2.5 h resulted in almost complete
chalcopyrite dissolution at 95 °C and, as in the Queneau and Prater
(1974) process, the unreacted sulfides were recovered by flotation
and recycled to the leach system.
 H.R. Watling / Hydrometallurgy 140 (2013) 163–180 177

0
Researchers at Kennecott Copper in Utah built a pilot plant for S þ 3NO2 þ H2 O ¼ H2 SO4 þ 3NO ð36Þ
treating copper concentrate with a nitric–sulfuric acid mixture and
concluded that the process was feasible but not economical because of NO þ 2NaNO3 þ H2 SO4 ¼ 3NO2 þ Na2 SO4 þ H2 O ð37Þ
the formation of a small amount (0.5%) of nitrous oxide which cannot
be reconverted to nitric acid and thus represents a loss of reagent in 3NO2 þ H2 O ¼ 2HNO3 þ NO: ð38Þ
this process (Habashi, 1999). A further requirement with economic
consequences was that nitrous oxide must not be released to the
6. Summary
atmosphere unless first reduced catalytically to nitrogen. Nitric acid is
expensive because it is produced from the oxidation of ammonia but if
A number of drivers exist for the development of different hydro-
it could be produced more cheaply from sodium nitrate, this might
metallurgical technologies for the extraction of copper from chalcopyrite.
influence the economics in favour of a nitrate oxidative process for
They include the current imbalance between copper supply and demand,
chalcopyrite dissolution.
the overall decline in ore grades and the extensive exploitation of
low-grade oxide and secondary sulfide ores that leave vast quantities of
low-grade chalcopyrite ores as a major, but thus far uneconomic, source
5.2. Sulfuric acid–sodium nitrate
of copper. Other sources of copper are polymetallic ores of complex
mineralogy that cannot be concentrated and chalcopyrite concentrates
Sokic et al. (2009) examined the leaching of chalcopyrite in the
that contain impurities such as arsenic and cannot be smelted.
sulfuric acid–sodium nitrate system. They chose leach conditions after
The primary focus of the review is on the chemistry of leaching in
consideration of the thermodynamics of the main chemical reactions
sulfate systems at atmospheric pressure. The use of chalcopyrite
in the temperature range of 25–90 °C. The matrix of tests involved as
concentrates for the majority of fundamental studies gives confidence
variables: stirring rate, temperature, leaching time, particle size, and
that the chalcopyrite is entirely ‘liberated’ and therefore exposed to
H2SO4 and NaNO3 concentrations. Solids loading in the tests was 20 g
the lixiviant/oxidant, provides a simple test matrix largely free of
concentrate in 1.2 L solution. Using conditions 80 °C, −37 μm particle
other phases that could mask the reaction chemistry, and accentuates
size fraction and 1.5 M H2SO4, copper extraction in 240 min was 40%
the impact of chalcopyrite grain size and surface area on leaching rates.
at 0.15M NaNO3; 60% at 0.3M NaNO3; and 75% at 0.9M NaNO3 addition.
There are many fundamental studies in which electrochemical
As Bredenhann and Van Vuuren (1996) had shown that sodium nitrate
and spectroscopic techniques have been used to probe chalcopyrite
oxidised millerite more rapidly than did ferric sulfate, Sokic et al. (2009)
surfaces, describe the leaching mechanism and identify the surface
did not make a similar comparison with ferric sulfate in their study of
species responsible for the ‘passivation’ of chalcopyrite during leaching.
chalcopyrite dissolution. In a subsequent study, it was shown that
Attempts have been made in three recent substantial reviews to
elemental sulfur was formed during the reactions of chalcopyrite with
reconcile reported results, despite significant differences between the
sodium nitrate (reactions (30)–(33)) and that its presence on particle
conditions under which those results were obtained. One of the
surfaces slowed leaching (Sokic et al., 2010).
difficulties of that reconciliation is highlighted by the recent prediction
of three different chalcopyrite surface structures that may leach via
3CuFeS2 þ 4NaNO3 þ 8H2 SO4 ¼ 3CuSO4 þ 3FeSO4 þ 2Na2 SO4
0 different mechanisms at different rates. No reports on chalcopyrite
þ 6S þ 4NO þ 8H2 O ð30Þ leaching were found in which the surface orientation of the chalcopyrite
was identified prior to leaching, creating a future opportunity for focused
CuFeS2 þ 4NaNO3 þ 4H2 SO4 ¼ CuSO4 þ FeSO4 þ 2Na2 SO4 research on chalcopyrite surfaces of known crystallographic orientation.
0
þ 2S þ 4NO2 þ 4H2 O ð31Þ The range of solution chemistry parameters that influence bulk
chalcopyrite dissolution in acidic ferric sulfate systems have been
studied comprehensively but often as independent variables. Many
6CuFeS2 þ 10NaNO3 þ 20H2 SO4 ¼ 6CuSO4 þ 3Fe2 ðSO4 Þ3 þ 5Na2 SO4
studies have generated results consistent with leaching rates being:
0
þ12S þ 10NO þ 20H2 O
ð32Þ • largely independent of acid concentration above that required to
maintain a sufficient ferric ion concentration (which need not exceed
2CuFeS2 þ 10NaNO3 þ 10H2 SO4 ¼ 2CuSO4 þ Fe2 ðSO4 Þ3 þ 5Na2 SO4 0.1 M Fe2(SO4)3),
0 • dependent on sulfate concentration and solution ORP (with optimum
þ4S þ 10NO2 þ 10H2 O:
ORP being dependent on ferric–ferrous and cupric–cuprous ion
ð33Þ concentrations), and
The leaching of chalcocite in a sodium nitrate–sulfuric acid system • enhanced by microorganisms (biological catalysts) or the addition of a
was studied by Vračar et al. (2003). For a system with conditions: 20 g chloride salt, under some conditions. Processes with the addition of
Cu2S in 1.2 L solution with stirring, temperature 80 °C and duration of nitric acid or a nitrate salt are less well developed and the benefits
leach 3–30 min and sulfuric acid 1 M, copper extraction increased less convincing.
with increased NaNO3 concentration from 30% at 0.15 M NaNO3 to
In studies using concentrates, chalcopyrite surfaces may become
95% at 0.6 M NaNO3. The system was as complex as the chalcopyrite–
covered in ‘overlayers’ of elemental sulfur or ferric oxy-hydroxy-sulfate
nitrate system in respect of chemical reactions. Both Vračar et al.
compounds such as jarosite. These bulk precipitates have often been
(2003) and Sokic et al. (2009) gave comprehensive accounts of the
blamed for the slower dissolution rates obtained after an initial period
reaction chemistry. The negative Gibbs free energy calculated for the
of relatively rapid copper extraction during leaching or bioleaching.
reactions (30)–(34), (1), and (35)–(37) showed that they were all
The effects may be overcome by changing the leaching mechanism
thermodynamically feasible at atmospheric pressure in the temperature
using a catalyst (e.g., Ag+) or by exploiting galvanic interaction with
range of 25–90°C. Only reaction (38) had a positive Gibbs Energy value.
another mineral (e.g., pyrite). Overlayers are unlikely to present a
6FeSO4 þ 2NaNO3 þ 4H2 SO4 ¼ 3Fe2 ðSO4 Þ3 þ Na2 SO4 þ 2NO þ 4H2 O significant problem in most whole-ore (heap) leaching systems unless
the amounts of iron(III) delivered through gangue dissolution are
ð34Þ
excessive. Studies in which multiple variables are jointly optimised and
controls put in place to maintain optimum conditions, may be rewarded
0
S þ 2NaNO3 –Na2 SO4 þ 2NO ð35Þ with increased copper extraction from chalcopyrite. While exercising
178 H.R. Watling / Hydrometallurgy 140 (2013) 163–180
that degree of control in heaps is difficult but not impossible, other
reactor types should also be considered. In any style of reactor, a primary
requirement of whole ore leaching is the exposure of the chalcopyrite
grains to the selected lixiviant and oxidant. This may require special
ore preparation and/or, may exclude heap leaching as a process option.
The development of processes using sulfuric acid as lixiviant and
oxidants other than ferric ions is an interesting research area that has
yet to be taken beyond laboratory scale. The main disadvantage is that
the alternative oxidants are more expensive than ferric ion. Countering
the cost, the alternative oxidants are stronger oxidising agents
than ferric ions and copper extractions are much faster. Few studies
have been undertaken using ores rather than concentrates. Thus the
interactions of these reagents with gangue minerals have not been
described. Assuming one or more reagents can be found that are
selective for sulfide minerals and sufficiently aggressive to extract
copper from chalcopyrite, then a goal of future research may be to
develop a process in which a strong alternative oxidant can be
regenerated and recycled, thus minimising reagent costs.
Acknowledgements
The financial support of the Australian Government through CSIRO
Minerals Down Under Flagship is gratefully acknowledged.
References
Adebayo, A.O., 2006. Dissolution of some sulphide minerals in the presence of hydrogen
peroxide solution and extraction of the base metals. PhD Thesis Federal University
of Technology, Akure, Nigeria.
Adebayo, A.O., Ipinmoroti, K.O., Ajayi, O.O., 2003. Dissolution kinetics of chalcopyrite with
hydrogen peroxide in sulphuric acid medium. Chem. Biochem. Eng. Q. 17, 213–218.
Ahmadi, A., Schaffie, M., Manafi, Z., Ranjbar, M., 2010. Electrochemical bioleaching of high
grade chalcopyrite flotation concentrates in a stirred bioreactor. Hydrometallurgy
104, 99–105.
Ahonen, L., Tuovinen, O.H., 1990. Silver catalysis of the bacterial leaching of chalcopyrite
containing ore material in column reactors. Miner. Eng. 3, 437–445.
Anderson, C.G., 1999. The treatment of chalcopyrite concentrates with nitrogen species
catalysed oxidative pressure leaching. In: Young, S.K., Dreisinger, D.B., Hackl, R.P.,
Dixon, D.G. (Eds.), Proceedings of Copper99–Cobre99 International Conference.
Hydrometallurgy of Copper, vol. IV. TMS, Warrendale, pp. 139–149.
Anderson, C.G., 2000. The industrial hydrometallurgical production of copper from
concentrates with nitrogen species catalysed pressure leaching, solvent extraction
and electrowinning. ALTA SX/IX Forum. ALTA Metallurgical Services, Melbourne.
Antonijevic, M.M., Jankovic, Z.D., Dimitrijevic, M.D., 1994. Investigation of the kinetics of
chalcopyrite oxidation by potassium dichromate. Hydrometallurgy 35, 187–201.
Antonijevic, M.M., Jankovic, Z.D., Dimitrijevic, M.D., 2004. Kinetics of chalcopyrite
dissolution by hydrogen peroxide in sulphuric acid. Hydrometallurgy 73, 329–334.
Aroca Alfaro, F., Rauld Faine, J., 2004. Procedure to leach copper concentrates, under
pressure and at ambient temperature, by forming a reactive gel in a sulfate–chloride
medium. European patent EP 1559799 (priority date 29 January 2004).
Aydogan, S., Ucar, G., Canbazoglu, M., 2006. Dissolution kinetics of chalcopyrite in acidic
potassium dichromate solution. Hydrometallurgy 81, 45–51.
Ballester, A., González, F., Blázquez, M.L., Mier, J.J., 1990. The influence of various ions in
the bioleaching of metal sulphides. Hydrometallurgy 23, 221–235.
Ballester, A., González, F., Blázquez, M.L., Gómez, C., Mier, J.L., 1992. The use of catalytic
ions in bioleaching. Hydrometallurgy 29, 145–160.
Bardt, H., 1919–1922. Recovering metals contained in metalliferous ore, waste residues
and alloys. German Patent 353,795.
Barriga Mateos, F., Palencia Perez, I., Carranza Mora, F., 1987. The passivation of
chalcopyrite subjected to ferric sulfate leaching and its reactivation with metal
sulfides. Hydrometallurgy 19, 159–167.
Basto, E., 2012. Escondida site tour. Source: http://www.bhpbilliton.com/home/investors/
reports/Documents/2012/121001_Escondida%20Site%20Visit%20Presentation.pdf.
Batty, J.D., Rorke, G.V., 2006. Development and commercial demonstration of the BioCOP™
thermophile process. Hydrometallurgy 83, 83–89.
Baxter, K., Dreisinger, D.B., Pratt, G., 2003. The Sepon copper project: Development of a
flowsheet. In: Young, C.A., Alfantazi, A.M., Anderson, C.G., Dreisinger, D.B., Harris, B.,
James, A. (Eds.), Hydrometallurgy. TMS, Warrendale, pp. 1487–1502.
Bjorling, G., 1968. Hydrometallurgical production of copper from activated chalcopyrite.
AIME Annual Meeting, New York, February 1968.
Bjorling, G., Faldt, I., Lindgren, E., Toromanov, I., 1976. A nitric acid route in combination
with solvent extraction for hydrometallurgical treatment of chalcopyrite. In:
Yannopoulos, J.C., Agarwal, J.C. (Eds.), Extractive Metallurgy of Copper, vol. II. AIME,
NY, pp. 725–737.
Bouffard, S.C., Rivera-Vasquez, B.F., Dixon, D.G., 2006. Leaching kinetics and stoichiometry
of pyrite oxidation from a pyrite–marcasite concentrate in acid ferric sulfate media.
Hydrometallurgy 84, 225–238.
Bouffard, S.C., Tshilombo, A., West-Sells, P.G., 2009. Use of lignosulfate for elemental sulfur
biooxidation and copper leaching. Miner. Eng. 22, 100–103.
Boulegue, J., 1978. Solubility of elemental sulfur in water at 298 K. Phosphorus Sulfur 5,
127–128.
Bredenhann, R., Van Vuuren, C.P.J., 1996. The leaching behaviour of a nickel concentrate in
an oxidative sulphuric acid solution. Miner. Eng. 12, 687–692.
Brennecke, H.M., Bergmann, O., Ellefson, R.R., Davies, D.S., Lueders, R.E., Spitz, R.A., 1981.
Nitric–sulfuric leach process for recovery of copper from concentrate. Min. Eng. 33,
1259–1266.
Brown, R.A., 2003. In situ chemical oxidation: performance, practice and pitfalls. Paper
Presented at the Air Force Center for Engineering and the Environment Technology
Transfer Workshop (Source: http://clu-in.org/download/techfocus/chemox/4_brown.
pdf).
Bruynestein, A., Hackl, R.P., Lawrence, R.W., Vizsolyi, A.I., 1986. Biological acid leach
process. U.S. Patent 4,571,387 (18 February 1986).
Canizares, P., Larrondo, F., Lobato, J., Rodrigo, M.A., Saez, C., 2005. Electrochemical
synthesis of peroxodisulfate using boron-doped diamond anodes. J. Electrochem.
Soc. 152, D191–D196.
Carillo-Pedroza, F.R., Sánchez-Castillo, M.A., Soria-Aguilar, M.J., Martínez-Luévanos, A.,
Gutiérrez, E.C., 2010. Evaluation of acid leaching of low grade chalcopyrite using
ozone by statistical analysis. Can. Metall. Q. 49, 219–226.
Carillo-Pedroza, F.R., Soria-Aguilar, M.J., Pecina Trevino, T., Sánchez-Castillo, M.A.,
Martínez-Luévanos, A., 2012. Treatment of sulfide minerals by oxidative leaching
with ozone. Miner. Process. Extr. Metall. Rev. 33, 269–279.
Carneiro, M.F.C., Leão, V.A., 2007. The role of sodium chloride on surface properties of
chalcopyrite leached by ferric sulphate. Hydrometallurgy 87, 73–82.
Carranza, F., Iglesias, N., Romero, R., Palencia, I., 1993. Kinetics improvement of high-grade
sulphides bioleaching by effects separation. FEMS Microbiol. Rev. 11, 129–138.
Carranza, F., Palencia, I., Romero, R., 1997. Silver-catalyzed IBES process: application to a
Spanish copper–zinc sulphide concentrate. Hydrometallurgy 44, 29–42.
Chiriţ , P., 2007. A kinetic study of hydrogen peroxide decomposition in presence of
pyrite. Chem. Biochem. Eng. Q. 21, 257–264.
Córdoba, E.M., Muñoz, J.A., Blázquez, M.L., González, F., Ballester, A., 2008a. Leaching of
chalcopyrite with ferric ion. Part I: general aspects. Hydrometallurgy 93, 81–87.
Córdoba, E.M., Muñoz, J.A., Blázquez, M.L., González, F., Ballester, A., 2008b. Leaching of
chalcopyrite with ferric ion. Part II: effect of redox potential. Hydrometallurgy 93, 88–96.
Córdoba, E.M., Muñoz, J.A., Blázquez, M.L., González, F., Ballester, A., 2008c. Leaching of
chalcopyrite with ferric ion. Part III: effect of redox potential on the silver-catalyzed
process. Hydrometallurgy 93, 97–105.
Córdoba, E.M., Muñoz, J.A., Blázquez, M.L., González, F., Ballester, A., 2008d. Leaching of
chalcopyrite with ferric ion. Part IV: the role of redox potential in the presence of
mesophilic and thermophilic bacteria. Hydrometallurgy 93, 106–115.
Córdoba, E.M., Muñoz, J.A., Blázquez, M.L., González, F., Ballester, A., 2009. Comparative kinetic
study of the silver-catalyzed chalcopyrite leaching. Int. J. Miner. Process. 92, 137–143.
Dakubo, F., Baygents, J.C., Farrell, J., 2012. Peroxodisulfate assisted leaching of
chalcopyrite. Hydrometallurgy 121–124, 68–73.
Davies, D.S., Lueders, R.E., Spitz, R.A., Frankiewicz, T.C., 1981. Nitric–sulfuric leach process
improvements. Min. Eng. 33, 1252–1259.
de Lima, G.F., de Oliveira, C., de Abreu, H.A., Duarte, H.A., 2011. Water adsorption on the
reconstructed (001) chalcopyrite surface. J. Phys. Chem. 115, 10709–10717.
de Lima, G.F., de Oliveira, C., de Abreu, H.A., Duarte, H.A., 2012. Sulfuric and hydrochloric
acid adsorption on the reconstructed sulfur terminated (001) chalcopyrite surface.
Int. J. Quantum Chem. 112, 3216–3222.
de Oliveira, C., Duarte, H.A., 2010. Disulphide and metal sulphide formation on the
reconstructed (001) surface of chalcopyrite: a DFT study. Appl. Surf. Sci. 257, 1319–1324.
de Oliveira, C., de Lima, G.F., de Abreu, H.A., Duarte, H.A., 2012. Reconstruction of the
chalcopyrite surfaces — a DFT study. J. Phys. Chem. C 116, 6357–6366.
Debernardi, G., Carlesi, C., 2012. Chemical–electrochemical approaches to the study of
passivation of chalcopyrite. Miner. Process. Extr. Metall. Rev. 34, 10–41.
Deng, T., Lu, Y., Wen, Z., Liu, D., 2001. Oxygenated chloride-assisted leaching of copper
residue. Hydrometallurgy 62, 23–30.
Dew, D.W., Basson, P. and Miller, D.M., 2001. Recovery of copper from copper bearing
sulphide minerals by bioleaching with controlled oxygen feed. World Patent WO
01/18269 (15 March 2001).
Dixon, D.G., Tshilombo, A.F., 2005. Leaching process for copper concentrates. U.S. Patent
Application 269208-A1 (8 December 2005).
Dixon, D.G., Mayne, D.D., Baxter, K.G., 2008. Galvanox™ — a novel galvanically-assisted
atmospheric leaching technology for copper concentrates. Can. Metall. Q. 47, 327–336.
Domic, E.M., 2007. A review of the development and current status of copper bioleaching
operations in Chile: 25 years of successful commercial implementation. In: Rawlings,
D.E., Johnson, D.B. (Eds.), Biomining. Springer, Berlin, pp. 81–95.
Dopson, M., Lövgren, L., Boström, D., 2009. Silicate mineral dissolution in the presence of
acidophilic microorganisms: implications for heap bioleaching. Hydrometallurgy 96,
288–293.
Dreisinger, D., 2006. Copper leaching from primary sulfides: options for biological and
chemical extraction of copper. Hydrometallurgy 83, 10–20.
Dutrizac, J.E., 1981. The dissolution of chalcopyrite in ferric sulfate and ferric chloride
media. Metall. Trans. B 12, 371–378.
Dutrizac, J.E., 1994. The leaching of silver sulfide in ferric ion media. Hydrometallurgy 35,
275–292.
Dutrizac, J.E., MacDonald, R.J.C., 1971. The effect of sodium chloride on the dissolution of
chalcopyrite under simulated dump leaching conditions. Metall. Trans. 2, 2310–2312.
Duyvesteyn, W.P.C., Budden, J.R. and Lastra, M.R., 2002. Recovery of metals from ore. U.S.
Patent 6,387,239 (14 May 2002).
Eary, L.E., Cathles, M., 1983. The kinetics of uranium dioxide dissolution in acidic
hydrogen peroxide solutions. Metall. Trans. B 14, 325–334.
 H.R. Watling / Hydrometallurgy 140 (2013) 163–180
Escudero, M.E., González, F., Blázquez, M.L., Ballester, A., Gómez, C., 1993. The catalytic
effect of some cations on the biological leaching of a Spanish complex sulphide.
Hydrometallurgy 34, 151–169.
Espejo, R. Y., Arriagada F., D'amico, J., Jo, M., Rojas, J., Neuberg, H., Ruiz, M., Yanez, H.,
Reyes, R., Bustos, S., Montealegre, R., Rauld, J., 2001. Procedimiento para aglomerar
minerales de cobre chancados fino, mediante la adicion de cloruro de calcio y acido
sulfurico y procedimiento de lixiviacion previa aglomeracion del mineral. Chilean
Patent Application No. 40891 (19 May 1997; granted 2001).
Ferreira, R.C.H., Burkin, A.R., 1976. Acid leaching of chalcopyrite. In: Burkin, A.R. (Ed.),
Leaching and reduction in hydrometallurgy. IMM, London, pp. 54–66.
Fleury, F., Delgado, E., Collao, N., 2010. A new technology for processing hydro-
metallurgical copper ore, Cobre Las Cruces Project. Proceedings of Copper 2010
(Hamburg, Germany). Hydrometallurgy, vol. 5. GDMB, Clausthal-Zellerfeld,
pp. 1871–1897.
Fu, K.B., Lin, H., Wang, H., Wen, H.W., Wen, Z.L., 2012. Comparative study on the
passivation layers of copper sulphide minerals during bioleaching. Int. J. Miner.
Metall. Mater. 19 (10), 886–892.
Garten, V.A., 1962. The decomposition of hydrogen peroxide by ferric ion. Aust. J. Chem.
15, 719–728.
Gautier, V., Escobar, B., Vargas, T., 2008. Cooperative action of attached and planktonic
cells during bioleaching of chalcopyrite with Sulfolobus metallicus at 70 °C.
Hydrometallurgy 94, 121–126.
Gericke, M., Pinches, A., 1999. Bioleaching of copper sulphide concentrate using extreme
thermophilic bacteria. Miner. Eng. 12, 893–904.
Gericke, M., Pinches, A., van Rooyen, J.V., 2001. Bioleaching of a chalcopyrite concentrate
using an extremely thermophilic culture. Int. J. Miner. Process. 62, 243–255.
Gericke, M., Neale, J.W., van Staden, P.J., 2009. A Mintek perspective of the past 25 years in
minerals bioleaching. J. South. Afr. Inst. Min. Metall. 109, 567–585.
Gericke, M., Govender, Y., Pinches, A., 2010. Tank bioleaching of low-grade chalcopyrite
concentrates using redox control. Hydrometallurgy 104, 414–419.
Gómez, C., Figueroa, M., Muñoz, J., Blázquez, M.L., Ballester, A., 1996. Electrochemistry of
chalcopyrite. Hydrometallurgy 43, 331–344.
Gómez, E., Ballester, A., González, F., Blázquez, M.L., 1999. Leaching capacity of a new
extremely thermophilic microorganism, Sulfolobus rivotincti. Hydrometallurgy 52,
349–366.
Habashi, F., 1973. The action of nitric acid on chalcopyrite. Trans. AIME 254, 224–228.
Habashi, F., 1999. Nitric acid in the hydrometallurgy of sulfides. In: Mishra, B. (Ed.),
Proceedings of the EPD Congress 1999. TMS–AIME, Warrendale, PA, pp. 25–32.
Hackl, R.P., Dreisinger, D.B., Peters, E., King, J.A., 1995. Passivation of chalcopyrite during
oxidative leaching in sulfate media. Hydrometallurgy 39, 25–48.
Halinen, A.K., Rahunen, N., Kaksonen, A.H., Puhakka, J.A., 2009. Heap bioleaching of a
complex sulfide ore. Part I: effect of pH on metal extraction and microbial
composition in pH controlled columns. Hydrometallurgy 98, 92–100.
Harvey, T.J., Bath, M., 2007. The GeoBiotics GEOCOAT® technology — progress and challenges.
In: Rawlings, D.E., Johnson, D.B. (Eds.), Biomining. Springer, Berlin, pp. 97–112.
Havlik, T., Skrobian, M., 1990. Acid leaching of chalcopyrite in the presence of ozone. Can.
Metall. Q. 29, 133–139.
Havlik, T., Dvorscikova, J., Ivanova, Z., Kammel, R., 1999. Sulphuric acid chalcopyrite
leaching using ozone as oxidant. Métallurgie (Berl.) 53, 57–60.
Herreros, O., Quiroz, R., Longueira, H., Fuentes, G., Viñals, J., 2006. Leaching of djurleite in
Cu2+/Cl− media. Hydrometallurgy 82, 32–39.
Hiroyoshi, N., Nakamura, T., Tsunekawa, M., Hirajima, T., Ito, M., 1995. Enhancement in
bacterial leaching of chalcopyrite by polyoxyethylene sorbitan monolaurate addition.
J. Min. Mater. Process. (Jpn) 111, 943–948.
Hiroyoshi, N., Hirota, M., Hirajima, T., Tsunekawa, M., 1997. A case of ferrous sulfate
addition enhancing chalcopyrite leaching. Hydrometallurgy 47, 37–45.
Hiroyoshi, N., Miki, H., Hirajima, T., Tsunekawa, M., 2000. A model for ferrous-promoted
chalcopyrite leaching. Hydrometallurgy 57, 31–38.
Hiroyoshi, N., Arai, M., Miki, H., Tsunekawa, M., Hirajima, T., 2002. A new reaction model
for the catalytic effect of silver ions on chalcopyrite leaching in sulfuric acid solutions.
Hydrometallurgy 63, 257–267.
Hiroyoshi, N., Kuroiwa, S., Miki, H., Tsunekawa, M., Hirajima, T., 2007. Effects of coexisting
metal ions on the redox potential dependence of chalcopyrite leaching in sulfuric acid
solutions. Hydrometallurgy 87, 1–10.
Hiroyoshi, N., Kitagawa, H., Tsunekawa, M., 2008. Effect of solution composition on the
optimum redox potential for chalcopyrite leaching in sulfuric acid solutions.
Hydrometallurgy 91, 144–149.
Hourn, M., Halbe, D., 1999. The NENATECH Process: Results on Frieda River copper gold
concentrates. Randol Copper Hydromet Roundtable. Randol International, Golden
Colorado, pp. 97–102.
Hourn, M.M., Turner, D.W., Holzberger, I.R., 1999. Atmospheric mineral leaching process.
U.S. Patent 5,993,635 (30 November 1999).
Hu, Y., Qiu, G., Wang, J., Wang, D., 2002. The effect of silver-bearing catalysts on
bioleaching of chalcopyrite. Hydrometallurgy 64, 81–88.
Hunter, C.J., 2002a. Bioheap™ leaching of a primary nickel–copper sulphide ore. ALTA
Nickel/Cobalt 2002 (Perth). ALTA Metallurgical Services, Melbourne (11 pp.).
Hunter, C.J., 2002b. Method for the bacterially assisted heap leaching of chalcopyrite.
World Patent 02/070757 A1 (12 September 2002).
Hunter, C.J., 2006. Method for the bacterially assisted heap leaching of chalcopyrite. U.S.
Patent 7,022,504 (4 April 2006).
Hunter, C.J., Williams, T.L., 2006. Heap leach. U.S. Patent 2006/0248983 A1 (9 November
2006).
Index Mundi, 2013. Copper: World Production by Country. Source: www.indexmundi.
com/en/commodities/minerals/copper/copper_t20.html.
International Copper Study Group, 2012. World Copper Factbook 2012. 54 (Source:
www.icsg.org/index.php/component/jdownloads/finish/170/1188).
179
Johnson, D.B., Okibe, N., Wakeman, K., Liu, Y., 2008. Effect of temperature on the
bioleaching of chalcopyrite concentrates containing different concentrations of silver.
Hydrometallurgy 94, 42–47.
Jones, D.L., 1996. CESL copper process. ALTA Copper Hydrometallurgical Forum
(Brisbane). ALTA Metallurgical Services, Melbourne.
Jones, D.L. and Peters, E., 1976. The leaching of chalcopyrite with ferric sulfate and ferric
chloride. In: Yannopoulos, J.C. and Agarwal, J.C., 1986 (Eds.), Extractive Metallurgy
of Copper, Volume 2. AIME, New York, pp. 633– 653.
Jordan, H., Sanhueza, A., Gautier, V., Escobar, B., Vargas, T., 2006. Electrochemical study of
the catalytic influence of Sulfolobus metallicus in the bioleaching of chalcopyrite at
70 °C. Hydrometallurgy 83, 55–62.
Kametani, H., Aoki, A., 1985. Effect of suspension potential on the oxidation rate of copper
concentrate in a sulfuric acid solution. Metall. Trans. B 16, 695–705.
Karavaiko, G.I., 1985. Microbiological processes for the leaching of metals from ores. In:
Torma, A.E. (Ed.), United Nations Environment Programme. USSR Commission for
UNEP, Moscow, pp. 1–69.
Kariuki, S., Moore, C., McDonald, A.M., 2009. Chlorate-based oxidative hydrometallurgical
extraction of copper and zinc from copper concentrate sulfide ores using mild acidic
conditions. Hydrometallurgy 96, 72–76.
Kimizuka, K., Kajiwara, S. and Tsuruga, T., 2001. Process for producing persulfate. U.S.
Patent 6,214,197-B1 (10 April 2001).
Kinnunen, P.H.-M., Puhakka, J.A., 2004. Chloride-promoted leaching of chalcopyrite concen-
trate by biologically-produced ferric sulfate. J. Chem. Technol. Biotechnol. 79, 830–834.
Klauber, C., 2003. Fracture-induced reconstruction of a chalcopyrite (CuFeS2) surface.
Surf. Interface Anal. 35, 415–428 (and Klauber, C., 2003. Erratum, op. cit. 35, 770).
Klauber, C., 2008. A critical review of the surface chemistry of acidic ferric sulphate dissolu-
tion of chalcopyrite with regards to hindered dissolution. Int. J. Miner. Process. 86, 1–17.
Klauber, C., Parker, A., van Bronswijk, W., Watling, H.R., 2001. Sulphur speciation of
leached chalcopyrite surfaces as determined by X-ray photoelectron spectroscopy.
Int. J. Miner. Process. 62, 65–94.
Kohr, W.J., Shrader, V., Johansson, C., 2004. High temperature heap bioleaching process.
U.S. Patent 6,8028,88 B2 (12 October 2004).
Kohr, W.J., Shrader, V. and Johansson, C., 2011. High temperature heap leaching process.
U.S. Patent 8,012,238 (6 September 2011).
Kolodziej, B., Adamski, Z., 1984. A ferric chloride hydrometallurgical process for recovery
of silver from electronic scrap materials. Hydrometallurgy 12, 117–127.
Kolthoff, I.M., Meehan, E.J., Kimura, M., 1973. Hydrogen peroxide formation upon
oxidation of oxalic acid in presence and absence of oxygen and of manganese(II)–
III. Iron(III) and copper(II) as retarders. Talanta 20, 81–87.
Konishi, Y., Asai, S., Tokushige, M., Suzuki, T., 1999. Kinetics of the bioleaching of
chalcopyrite concentrate by acidophilic thermophile Acidianus brierleyi. Biotechnol.
Prog. 15, 681–688.
Konishi, Y., Tokushige, M., Asai, S., Suzuki, T., 2001. Copper recovery from chalcopyrite
concentrate by acidophilic thermophile Acidianus brierleyi in batch and continuous-
flow stirred tank reactors. Hydrometallurgy 59, 271–282.
Lastra, M.R. and Budden, J.R., 2002. Improved high yield bioheap leaching of chalcopyrite
copper ores. World Patent WO 02/070758 A1 (12 September 2002).
Li, A., Huang, S., 2011. Comparison of the electrochemical mechanism of chalcopyrite
dissolution in the absence or presence of Sulfolobus metallicus at 70 °C. Miner. Eng.
24, 1520–1522.
Li, D., Li, D., 2010. Citric catalysis on the microbiological leaching of chalcopyrite fine
grained tailings in shake flask. Res. J. Biotechnol. 5, 64–67.
Li, J., Kawashima, N., Kaplun, K., Absolon, V.J., Gerson, A.J., 2010. Chalcopyrite leaching: the
rate controlling factors. Geochim. Cosmochim. Acta 74, 2881–2893.
Li, Y., Kawashima, N., Li, J., Chandra, A.P., Gerson, A.P., 2013. A review of the structure and
fundamental mechanisms and kinetics of the leaching of chalcopyrite. Adv. Colloid
Interf. Sci. 197–198, 1–32.
Liang, C.L., Xia, J.L., Nie, Z.Y., Yang, Y., Ma, C.Y., 2012. Effect of sodium chloride on sulfur
speciation of chalcopyrite bioleached by the extreme thermophile Acidianus
manzaensis. Bioresour. Technol. 110, 462–467.
Lin, H.K., Luong, H.V., 2004. Column leaching for simulating heap and in-situ soil
remediation with metallic Fenton reaction. J. Miner. Mater. Charact. Eng. 3, 33–39.
Linge, H.G., 1976. A study of chalcopyrite dissolution in acidic ferric nitrate by
potentiometric titration. Hydrometallurgy 2, 51–64.
Lu, Z.Y., Jeffrey, M.I., Lawson, F., 2000. The effect of chloride ions on the dissolution of
chalcopyrite in acidic solutions. Hydrometallurgy 56, 189–202.
Lunt, D., Poulter, S., Canterford, J., 1997. Hydrometallurgical treatment of copper
concentrates: what are the “real” process options? ALTA 1997 Copper Hydro-
metallurgy Forum (Brisbane). ALTA Metallurgical Services, Melbourne (24 pp.).
Mackie, D., Trask, F., 2009. Continuous vat leaching — first copper pilot trials. ALTA
Copper-X. ALTA Metallurgical Services, Melbourne.
Mahajan, V., Misra, M., Zhong, K., Fuerstenau, M.C., 2007. Enhanced leaching of copper
from chalcopyrite in hydrogen peroxide–glycol system. Miner. Eng. 20, 670–674.
Mallick, S.A., Dasgupta, A.K., 1997. Bioleaching of copper from chalcopyrite ores coated
with polyaniline film. Curr. Sci. 72, 201–205.
Mazuelos, A., Iglesias, N., Carranza, F., 1999. Inhibition of bioleaching processes by
organics from solvent extraction. Process Biochem. 35, 425–431.
McDonald, R.G., Muir, D.M., 2007a. Pressure oxidation leaching of chalcopyrite. Part 1.
Comparison of high and low temperature reaction kinetics and products.
Hydrometallurgy 86, 191–205.
McDonald, R.G., Muir, D.M., 2007b. Pressure oxidation leaching of chalcopyrite. Part 2.
Comparison of medium temperature kinetics and products and effect of chloride
ion. Hydrometallurgy 86, 206–220.
Mier, J.L., Gomez, C., Ballester, A., Blazquez, M.L., Gonzalez, F., 1994. The effects of silver
and bismuth on bioleaching of copper sulphide concentrates with thermophilic
microorganisms. Hydrometallurgy '94. IMM, Chapman and Hall, London, pp. 369–383.
180 H.R. Watling / Hydrometallurgy 140 (2013) 163–180
Miller, J.D., Portillo, H.Q., 1979. Silver catalysis in ferric sulfate leaching of chalcopyrite. In:
Laskowski, J. (Ed.), Proceedings of the XIII Mineral Processing Congress. Elsevier,
Amsterdam, pp. 851–901.
Mudd, G.M., 2010. The environmental sustainability of mining in Australia: key mega-
trends and looming constraints. Resour. Policy 35, 98–115.
Munoz, P.B., Miller, J.D., Wadsworth, M.E., 1979. Reaction mechanism for the acid ferric
sulfate leaching of chalcopyrite. Metall. Trans. B 10, 149–158.
Muñoz, J.A., Gόmez, C., Ballester, A., Blazquez, M.L., Gonzalez, F., 1998. Electrochemical
behaviour of chalcopyrite in the presence of silver and Sulfolobus bacteria. J. Appl.
Electrochem. 28, 49–56.
Muñoz, J.A., Dreisinger, D.B., Cooper, W.C., Young, S.K., 2007a. Silver catalyzed bioleaching
of low-grade copper ores. Part I: shake flask tests. Hydrometallurgy 88, 3–18.
Muñoz, J.A., Dreisinger, D.B., Cooper, W.C., Young, S.K., 2007b. Silver catalysed bioleaching
of low-grade copper ores. Part III. Column reactors. Hydrometallurgy 88, 35–51.
Muñoz-Ribadeneira, F.J., Gomberg, H.J., 1970. Possibilities of recovering copper from
chalcopyrite by underground leaching in situ. Trans. Am. Nucl. Soc. 13, 636–637.
Muñoz-Ribadeneira, F.J., Gomberg, H.J., 1971. Leaching of chalcopyrite (CuFeS2) with
sodium chloride sulfuric acid solutions. Nucl. Technol. 11 (3), 367–371.
Murr, L.E., Hiskey, G.B., 1981. Kinetic effect of particle size and crystal dislocation density
on the dichromate leaching of chalcopyrite. Metall. Trans. B 12, 255–267.
Naderi, H., Abdollahy, M., Mostoufi, N., Koleini, M.J., Shojaosadati, S.A., Manafi, Z., 2011.
Kinetics of chemical leaching of chalcopyrite from low grade copper ore: behaviour
of different size fractions. Int. J. Miner. Metall. Mater. 18, 638–645.
Nazari, G., Dixon, D.G., Dreisinger, D.B., 2012. The mechanism of chalcopyrite leaching in
the presence of silver-enhanced pyrite in the Galvanox™ process. Hydrometallurgy
113–114, 122–130.
Nicol, M.J., Lázaro, I., 2003. The role of non-oxidative processes in the leaching of
chalcopyrite. In: Riveros, P.A., Dixon, D., Dreisinger, D.B., Menacho, J. (Eds.), Copper
2003–Cobre 2003, vol. VI. Canadian Institute of Mining, Metallurgy and Petroleum,
Montreal, pp. 367–381 (Book 1).
O'Brien, R.T., MacDonald, C.A., Meadows, N.E., 1999. Chloride–sulphate leaching from
chalcopyrite ores from Sabah. ALTA Copper Sulphides Symposium and Copper
Hydrometallurgy Forum (Gold Coast, QLD). ALTA Metallurgical Services, Melbourne.
Okibe, N. And, Johnson, D.B., 2002. Toxicity of flotation reagents to moderately
thermophilic bioleaching microorganisms. Biotechnol. Lett. 24, 2011–2016.
Olubambi, P.A., Potgieter, J.H., 2009. Investigations on the mechanisms of sulfuric acid
leaching of chalcopyrite in the presence of hydrogen peroxide. Miner. Process. Extr.
Metall. Rev. 30, 327–345.
Olubambi, P.A., Borode, J.O., Ndlovu, S., 2006. Sulphuric acid leaching of zinc and copper
from Nigerian complex sulphide ore in the presence of hydrogen peroxide. J. S. Afr.
Inst. Min. Metall. 106, 765–770.
Palencia, I., Romero, R., Carranza, E., 1998. Silver-catalyzed IBES process: application to a
Spanish copper–zinc sulphide concentrate. Part 2. Biooxidation of the ferrous iron
and catalyst recovery. Hydrometallurgy 48, 101–112.
Palmer, B.R., Nebo, C.O., Rau, M.F., Fuerstenau, M.C., 1981. Rate phenomena involved in
the dissolution of chalcopyrite in chloride-bearing lixiviants. Metall. Trans. B 12,
595–601.
Parker, A.J., Paul, R.L., Power, G.P., 1981. Electrochemistry of the oxidative leaching of
copper from chalcopyrite. J. Electroanal. Chem. Interfacial Electrochem. 118, 305–316.
Parker, A., Klauber, C., Kougianos, A., Watling, H.R., van Bronswijk, W., 2003. An X-ray
photoelectron spectroscopy study of the mechanism of oxidative dissolution of
chalcopyrite. Hydrometallurgy 71, 265–276.
Peacey, J., Guo, X., Robles, E., 2004. Copper hydrometallurgy — current status, preliminary
economics, future direction and positioning versus smelting. Trans. Nonferrous Met.
Soc. China 14, 560–568.
Philippe, R., Dixon, R., Dal Pozzo, S., 2010. Sal or Desal. Seawater supply options for the mining
industry. Paper presented at water in mining. II International Congress on Water
Management in the Mining Industry (Santiago, Chile). Gecamin, Santiago, pp. 13–20.
Pinches, A., Myburgh, P.J., van der Merwe, C., 2001b. Process for the rapid leaching of
chalcopyrite in the absence of catalysts. U.S. Patent 6,277,341 (21 August 2001).
Pinches, A., Gericke, M., and van Rooyen, J.V., 2001a. A method of operating a bioleach
process with control of redox potential. World Patent 01/31072 A1 (3 May 2001).
Pradhan, N., Nathsarma, K.C., Srinivasa Rao, K., Sukla, L.B., Mishra, B.K., 2008. Heap
bioleaching of chalcopyrite: a review. Miner. Eng. 21, 355–365.
Prater, J.D., Queneau, P.B., Hudson, T.J., 1973. Nitric acid route to processing copper
concentrate. Trans. AIME 254, 117–122.
Price, D.W., Warren, G.W., 1986. The influence of silver ion on the electrochemical
response of chalcopyrite and other mineral sulfide electrodes in sulfuric acid.
Hydrometallurgy 15, 303–324.
Queneau, P.B. and Prater, J.D., 1974. Nitric acid process for recovering metal values from
sulfide ore materials containing iron sulfide. U.S. Patent 3,793,429 (19 February 1974).
Radimer, K.J. and McCarthy, M.J., 1979. Electrolytic production of sodium persulfate. U.S.
Patent 4,144,144 (13 March 1979).
Rauld Faine, J., Aroca Alfaro, F., Montealegre Jullian, R., Backit Gutierrez, A., 2005a.
Non-biochemical method to heap leach copper concentrates. U.S. Patent 6,926,753
(9 August 2005).
Rauld Faine, J., Aroca Alfaro, F., Montealegre Jullian, R., Backit Gutierrez, A., 2005b.
Procedure to leach copper concentrates, under pressure and at ambient temperature,
by forming a reactive gel in a sulfate–chloride medium. US Patent 2005/0169823 A1
(process also described in European Patent EP 1559799).
Rodríguez, Y., Ballester, A., Blázquez, M.L., González, F., Muñoz, J.A., 2003. New in-
formation on the chalcopyrite bioleaching mechanism at low and high temperature.
Hydrometallurgy 71, 47–56.
Romero, R., Mazuelos, A., Palencia, I., Carranza, F., 2003. Copper recovery from
chalcopyrite concentrates by the BRISA process. Hydrometallurgy 70, 205–215.
Ruan, R., Zhou, E., Liu, X., Wu, B., Zhou, G., Wen, J., 2010. Comparison on the leaching
kinetics of chalcopyrite and pyrite with or without bacteria. Rare Metals 29, 552–556.
Ruiz, M.C., Montes, K.S., Padilla, R., 2011. Chalcopyrite leaching in sulfate–chloride media
at ambient pressure. Hydrometallurgy 109, 37–42.
Salo-Zieman, V.L.A., Kinnunen, P.H.M., Puhakka, J.A., 2006. Bioleaching of acid-consuming
low-grade nickel ore with elemental sulfur addition and subsequent acid generation.
J. Chem. Technol. Biotechnol. 81, 34–40.
Sandström, Å., Petersson, S., 1997. Bioleaching of a complex sulphide ore with moderate
thermophilic and extreme thermophilic microorganisms. Hydrometallurgy 46, 181–190.
Sandström, Å., Shchukarev, A., Paul, J., 2005. XPS characterisation of chalcopyrite
chemically and bio-leached at high and low redox potential. Miner. Eng. 18, 505–515.
Sawyer, H.D., Shaw, R.W., 1983. Hydrometallurgical recovery of copper. Australian Patent
Au-B-17181/83.
Schlesinger, M.E., King, M.J., Sole, K.C., Davenport, W.G.I., 2011. Hydrometallurgical copper
extraction: Introduction and leaching, In: Schlesinger, M.E., King, M.J., Sole, K.C.,
Davenport, W.G. (Eds.), Extractive Metallurgy of Copper, Fifth ed. Elsevier, Oxford,
pp. 281–322.
Schlitt, W.J., 2006. Kennecott's million-ton test heap — the active leach program. Miner.
Metall. Process. 23 (1), 1–16.
Schlitt, J., Johnston, A., 2010. The Marcobre vat leach system: a new look at an old process.
Proceedings of Copper 2010. Hydrometallurgy, vol. 5. GDMB, Clausthal-Zellerfeld,
pp. 2039–2057.
Schnell, H., 1997. Bioleaching of copper. In: Rawlings, D.E. (Ed.), Biomining: Theory,
Microbes and Industrial Processes. Springer Verlag, Berlin, pp. 21–43.
Shantz, R., Morris, T.M., 1974. Dichromate process demonstrated for leaching of copper
sulphide concentrates. Eng. Min. J. 175, 71–72.
Sokic, M.D., Markovic, B., Zivkovic, D., 2009. Kinetics of chalcopyrite leaching by sodium
nitrate in sulphuric acid. Hydrometallurgy 95, 273–279.
Sokic, M.D., Matkovic, V.L., Markovic, B.R., Strbac, N.D., Zivkovic, D.T., 2010. Passivation of
chalcopyrite during the leaching with sulphuric acid solution in presence of sodium
nitrate. Hem. Ind. 64, 343–350.
Solis-Marcíal, O.J., Lapidus, G.T., 2013. Improvement of chalcopyrite dissolution in acid
media using polar organic solvents. Hydrometallurgy 131–132, 120–126.
Stott, M.B., Sutton, D.C., Watling, H.R., Franzmann, P.D., 2001. The effect of solution
chemistry on jarosite deposition during the leaching of chalcopyrite by the
thermophilic archaeon Sulfolobus metallicus. Process Metall. 11A, 207–215.
Subramanian, K.N., Ferrajuolo, R., 1976. Oxygen pressure leaching of Fe–Ni–Cu sulfide
concentrates at 110 °C — effect of low chloride addition. Hydrometallurgy 2, 117–126.
Third, K.A., Cord-Ruwisch, R., Watling, H.R., 2002. Control of redox potential by oxygen
limitation improves bacterial leaching of chalcopyrite. Biotechnol. Bioeng. 78, 433–441.
Torma, A.E., Itzkovitch, I.J., 1976. Influence of organic solvents on chalcopyrite oxidation
ability of Thiobacillus ferrooxidans. Appl. Environ. Microbiol. 32, 102–107.
Uhrie, J.L., Bowman, G., Caro Matus, C.A., Mayta, P., Hoenecke, S., Chavez, M., 2012.
Methods and systems for leaching a metal-bearing ore for the recovery of a metal
value. U.S. Patent 8,118,907 (21 February, 2012).
van der Merwe, C., Pinches, A., Myburgh, P.J., 1998. A process for the leaching of
chalcopyrite. World Patent WO9839491 (11 September 1998); also published as
Australian Patent 2224697 and subsequently as Pinches et al., 2001b.
van Staden, P.J., 1998. The Mintek/Bactech copper bioleach process. ALTA 1998 Copper
Sulphides Symposium (Brisbane). ALTA Metallurgical Services, Melbourne.
van Staden, P.J., Shaidaee, B., Yazdani, M., 2005. A collaborative plan towards heap
bioleaching of low grade chalcopyritic ore from a new Iranian mine. In: Harrison,
S.T.L., Rawlings, D.E., Petersen, J. (Eds.), Proceedings of the 16th International
Biohydrometallurgy Symposium (Cape Town), 16th International Biohydrometallurgy
Symposium, Cape Town, pp. 115–123.
Viramontes-Gamboa, G., Rivera-Vasquez, B.F., Dixon, D.G., 2007. The active–passive
behavior of chalcopyrite — comparative study between electrochemical and leaching
responses. J. Electrochem. Soc. 154, C299–C311.
Viramontes-Gamboa, G., Peña-Gomar, M.M., Dixon, D.G., 2010. Electrochemical hysteresis
and bistability in chalcopyrite passivation. Hydrometallurgy 105, 140–147.
Vračar, R.Z., Parezanović, I.S., Cerović, K.P., 2000. Leaching of copper(I) sulfide in chloride
solution. Hydrometallurgy 58, 261–267.
Vračar, R.Z., Vucković, N., Kamerović, Z., 2003. Leaching of copper(I) sulphide by sulphuric
acid solution with addition of sodium nitrate. Hydrometallurgy 70, 143–151.
Wang, S., 2005. Copper leaching from chalcopyrite concentrates. J. Met. 57 (7), 48–51.
Warren, G.W., Wadsworth, M.E., El-Raghy, S.M., 1982. Passive and transpassive anodic
behaviour of chalcopyrite in acid solutions. Metall. Trans. B 13, 571–579.
Warren, G.W., Drouven, B., Price, D.W., 1984. Relationships between the Pourbaix
diagram for Ag–S–H2O and electrochemical oxidation and reduction of Ag2S. Metall.
Trans. B 15, 235–242.
Watling, H.R., 2006. The bioleaching of sulphide minerals with emphasis on copper
sulphides — a review. Hydrometallurgy 84, 81–108.
Watling, H.R., Elliot, A.D., Maley, M., van Bronswijk, W., Hunter, C., 2009. Leaching of a
low-grade, copper–nickel sulfide ore. 1. Key parameters impacting on Cu recovery
during column bioleaching. Hydrometallurgy 97, 204–212.
Westby, G.C., 1918. Nitric acid and copper ores. Metall. Chem. Eng. 18, 290–296.
Xia, L., Tang, L., Xia, J., Yin, C., Cai, L., Zhao, X., Nie, Z., Liu, J., Qiu, G., 2012. Relationships
among bioleaching performance, additional sulfur, microbial population dynamics
and its energy metabolism in bioleaching of chalcopyrite. Trans. Nonferrous Met.
Soc. China 22, 192–198.
Xian, Y.J., Wen, S.M., Deng, J.S., Liu, J., Nie, Q., 2012. Leaching chalcopyrite with sodium
chlorate in hydrochloric acid solution. Can. Metall. Q. 52, 133–140.
Young, T.L., Greene, M.G., Rice, D.R., Karlage, K.L., Premeau, S.P., Cassells, J.M., 2003.
Method for the microbiological production of sulfuric acid. U.S. Patent 6,610,268
(26 August 2003).