Accepted Manuscript

The effect of thermal pre-treatment on the dissolution of

chalcopyrite (CuFeS2) in sulfuric acid media

Nebeal Faris, Rahul Ram, Miao Chen, James Tardio, Mark I.

Pownceby, Lathe Jones, Scott McMaster, Nathan A.S. Webster,
Suresh Bhargava

PII: S0304-386X(16)30963-X
DOI: doi: 10.1016/j.hydromet.2016.12.006
Reference: HYDROM 4484
To appear in: Hydrometallurgy
Received date: 4 November 2015
Revised date: 22 August 2016
Accepted date: 12 December 2016

Please cite this article as: Nebeal Faris, Rahul Ram, Miao Chen, James Tardio, Mark I.
Pownceby, Lathe Jones, Scott McMaster, Nathan A.S. Webster, Suresh Bhargava , The
effect of thermal pre-treatment on the dissolution of chalcopyrite (CuFeS2) in sulfuric acid
media. The address for the corresponding author was captured as affiliation for all authors.
Please check if appropriate. Hydrom(2016), doi: 10.1016/j.hydromet.2016.12.006

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 ACCEPTED MANUSCRIPT

The effect of thermal pre-treatment on the dissolution of chalcopyrite

(CuFeS2) in sulfuric acid media

Nebeal Faris1, Rahul Ram1, Miao Chen1,2, James Tardio1, Mark I. Pownceby2†, Lathe
Jones1, Scott McMaster1, Nathan A.S. Webster2 and Suresh Bhargava1†
1
Advanced Materials and Industrial Chemistry Centre: School of Applied Sciences RMIT
University GPO Box 2476, Melbourne, Vic, 3001, Australia

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2
CSIRO Mineral Resources, Private Bag 10, Clayton South, Victoria 3169, Australia

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Key words – chalcopyrite; thermal pre-treatment; copper dissolution
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HIGHLIGHTS-
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 Impact of reducing and inert thermal pre-treatment on Chalcopyrite

 Structural and chemical modifications due to thermal pre-treatment


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Sulfuric acid leaching of pre-treated Chalcopyrite

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† Corresponding author Email: mark.pownceby@csiro.au; suresh.bhargava@rmit.edu.au

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ABSTRACT
Chalcopyrite ore was roasted at 200, 550 and 800ºC in reducing (5%H2/95%Ar) and inert (N2)
atmospheres to examine the effects of the thermal pre-treatment on the phase mineralogy and on
subsequent copper extraction using sulfuric acid media. No mineralogical changes occurred in the
pre-leached samples heated to 200°C under both inert and reducing conditions while at 550ºC
partial decomposition of chalcopyrite resulted forming bornite and metal-rich derivatives talnakhite
and mooihoekite. Further heating to 800°C saw differences in chalcopyrite decomposition
according to the atmosphere. In the inert atmosphere chalcopyrite decomposed to the metal-rich
derivatives and minor bornite and geerite while in the reduced atmosphere copper metal, bornite,
troilite, cubanite and chalcocite formed. Leaching at 50°C of the chalcopyrite pre-treated in an inert
atmosphere saw a slight increase in %Cu extraction with increasing temperature of treatment. A
maximum copper extraction of 16%Cu was measured in the sample treated at 800°C. Leaching of

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the chalcopyrite pre-treated in a reduced atmosphere led to modest increases in copper extraction
between the 200°C and 550°C samples with 21%Cu and 24%Cu leached. Treatment at 800°C
resulted in a significant increase reaching 78%Cu extraction.

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1. INTRODUCTION
The majority of the world’s copper is extracted from sulfide ores with chalcopyrite, CuFeS2, being
the dominant mineral in most copper-rich ore bodies (approximately 70% of the world’s copper
reserves is in the form of CuFeS2 (Córdoba et al., 2008a; Nazari et al., 2011)). The dominant
method for recovery of copper from chalcopyrite ores is by froth flotation to produce a copper-rich
concentrate followed by pyrometallurgical treatment in reverbatory/flash smelters (Córdoba et al.,
2008a; Prasad and Pandey, 1998). Approximately 80-85% of the world’s copper is produced
through flotation/pyrometallurgical processes (Li et al., 2013). Although capable of achieving high
copper recoveries, significant disadvantages are associated with a pyrometallurgical route to copper
production. These include: pollution of the environment through production of sulfur dioxide (Li et
al., 2013; Munoz et al., 1979; Prasad and Pandey, 1998); smelting is only appropriate for high grade
concentrates with mineral beneficiation and smelting processes being uneconomical for low grade

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ores, finely disseminated ores and complex sulfide ores (Munoz et al., 1979; Prasad and Pandey,
1998), and; pyrometallurgical processes are more capital intensive than hydrometallurgical
processes and have difficulty recovering base and precious metal by-products associated with

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copper ores (Dreisinger, 2006). With average mineral grades declining due to high grade ore bodies
becoming depleted, interest has focussed on using hydrometallurgy as an alternative route to

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extracting copper from chalcopyrite concentrates (Córdoba et al., 2008b; Li et al., 2013; Munoz et
al., 1979). Hydrometallurgical processes are typically less energy intensive, more suitable for low
grade and complex ore types and present a lower environmental impact due to lower fuel
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requirements and lack of SO2 generation.

Leaching of chalcopyrite is usually conducted in an oxidising environment using lixiviant involving

sulfates, chlorides, ammonia and nitrates (Hackl et al., 1995). Of these acidic ferric sulfate lixiviant
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has received the most attention due to factors including; low cost, operational simplicity, reduced
corrosion problems and the ability to regenerate the lixiviant (Munoz et al., 1979).

Chalcopyrite dissolution in acidic ferric sulfate media is an electrochemical process (Nazari and
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Asselin, 2009) with the overall reaction for the oxidation and dissolution of chalcopyrite given by:
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CuFeS2 (s) + 2 Fe2(SO4)3 (aq) = CuSO4 (aq) + 5 FeSO4 (aq) + 2 So (s) [1]
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Reaction [1] can also be described by the half-cell anodic and cathodic reactions:
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Anodic reaction CuFeS2 (s) = Cu2+ (aq) + Fe2+ (aq) + 2 So (s) + 4e- [2]

Cathodic reaction 4 Fe3+ (aq) + 4 e- = 4 Fe2+ (aq) [3]

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A number of ferric sulfate processes have been trialled (Dutrizac, 1981; Munoz et al., 1979)
however to date, commercial application of chalcopyrite hydrometallurgy has been confined to heap
leaching of low grade ores and waste rock by a combination of acidic ferric sulfate and bacteria,
with subsequent copper recovery by solvent extraction and electrowinning (Dutrizac, 1981; Li et al.,
2013; Liang et al., 2010; Prasad and Pandey, 1998; Venkatachalam, 1991). Alternative processes
whereby chalcopyrite concentrates are oxidised in air to convert the sulfides to oxides or sulfates
have also been proposed. In this approach, the sulfates are subsequently leached and the copper
recovered by conventional electrowinning (Prasad and Pandey, 1998; Venkatachalam, 1991).

Despite the benefits of hydrometallurgy for the recovery of copper from chalcopyrite, processing
via a hydrometallurgical route has had little commercial success. The reason for the lack of
acceptance of hydrometallurgical processes is that chalcopyrite becomes refractory during oxidative
leaching due to the formation of stable passivation layers on the mineral surface (Córdoba et al.,
2009; Córdoba et al., 2008a; Nazari and Asselin, 2009). The surface transformations which form the
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passivating layers result in slow dissolution rates. A number of species within the passivating layer
have been reported including; elemental sulfur, So, (Nazari and Asselin, 2009; Nazari et al., 2012b),
bimetallic sulfide (Burkin, 1969), copper polysulfides (Sn2-) with a deficit of iron with respect to
chalcopyrite (Córdoba et al., 2009; Nazari and Asselin, 2009) and iron hydrolysis products such as
jarosite (Córdoba et al., 2009). Córdoba et al. (2008a) suggested that the passivation layers either
act as diffusion layers or electrical insulators however in a recent review Li et al. (2013) concluded
that the chemistry and nature of the passivation layers is not well understood and the role of the new
surface species which form is still unknown.

Enhancing chalcopyrite dissolution rates in ferric sulfate media has been a key focus of previous
research. Liang et al. (2010); Nakazawa et al. (1998) studied the bioleaching of chalcopyrite in
ferric sulfate media with the addition of activated carbon. Both studies concluded that activated

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carbon resulted in an increase in copper recovery and enhanced dissolution rates. Chalcopyrite
dissolution in ferric sulfate media has also been enhanced through the addition of pyrite in a process
known as GalvanoxTM (Dixon et al., 2008). The presence of pyrite in electrical contact with

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chalcopyrite results in enhanced copper leaching due to the pyrite providing a catalytic surface for
ferric iron reduction to take place(Dixon et al., 2008).The effect of silver addition on the leaching of
chalcopyrite in ferric sulfate media has also received considerable attention. Córdoba et al. (2008c)

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showed that the addition of silver ions resulted in an increase in copper dissolution. The proposed
mechanism was that the silver prevented nucleation of Fe3+ hydrolysis products on the chalcopyrite
surface which would normally inhibit leaching. Furthermore, the presence of excess silver was
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believed to result in a transformation of the chalcopyrite surface into covellite, CuS, and geerite,
Cu8S5. In a similar study, Nazari et al. (2011; 2012a; 2012b) studied the leaching of chalcopyrite in
ferric sulfate media in the presence of pyrite which was pre-treated with silver. These studies found
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that the presence of silver resulted in a dramatic increase in copper leaching rate that was attributed
to the formation of silver sulfide, AgS2, by reaction of silver with the sulfur layer surrounding
individual chalcopyrite particles. The formation of AgS2 resulted in an increase in electrical
conductivity of the sulfur layer and hence an increase in dissolution rate of chalcopyrite. Other
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methods of enhancing chalcopyrite dissolution in ferric sulfate media have included addition of
ferrous sulfate (Hiroyoshi et al., 1997; Hiroyoshi et al., 2001) and conducting chalcopyrite
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dissolution at high redox potential (Córdoba et al., 2008b).

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Thermal activation of chalcopyrite under an inert or reducing atmosphere has also been suggested
as a potential method of enhancing the leaching kinetics and extent of copper recovery
(Venkatachalam, 1991). Such treatments have the potential of avoiding sulfur dioxide production
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which is associated with the roasting of complex sulfide ores. Sherritt Gordon Mines Limited and
Cominco Limited patented a process for treating chalcopyrite concentrates by thermal activation
under oxidising and reducing atmospheres to remove labile sulfur and activate the sulfide mineral.
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This pre-treatment was followed by sulfuric acid leaching to remove soluble iron to produce a
higher grade copper sulfide concentrate for sale or further processing (Swinkels and Maschmeyer,
1980). Similarly, Gaballah et al. (1994) investigated the thermal treatment of complex sulfide ores
containing pyrite, chalcopyrite, galena and sphalerite in nitrogen and hydrogen atmospheres.
Gaballah et al. (1994) reported that thermal pre-treatment of a chalcopyrite/pyrite concentrate under
nitrogen resulted in thermal decomposition of chalcopyrite at about 450ºC via a two-step process to
produce cubanite (CuFe2S3), bornite (Cu5FeS4) and pyrrhotite (Fe(1-x)S) as shown in equations 4 and
5.

4 CuFeS2 = 2 CuFe2S3 + Cu2S + So [4]

2 CuFe2S3 + Cu2S = 0.8 Cu5FeS4 + 3.2 Fe(1-x)S + 0.6 So [5]

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In comparison, thermal pre-treatment of the chalcopyrite/pyrite concentrate under a hydrogen
atmosphere resulted in transformation of chalcopyrite to cubanite (CuFe 2S3) at about 350ºC and
then reduction of cubanite to metallic copper at about 600ºC according to:

2 CuFeS2 + H2 = CuFe2S3 + Cuo + H2S [6]

CuFe2S3 + 3 H2 = 2 Feo + Cuo + 3H2S [7]

Leaching experiments conducted on untreated concentrate and that subjected to thermal activation
have shown that copper extraction is considerably improved after the concentrate has undergone
thermal treatment (Venkatachalam, 1991).

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In this study, we briefly review the chemistry that takes place when chalcopyrite is subjected to
high temperatures under different atmospheres before investigating the influence of thermal pre-
treatment of chalcopyrite under both reducing and inert atmospheres on the extent of copper

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dissolution in sulfuric acid media in the absence of an external oxidant (eg. ferric iron, hydrogen
peroxide or air). Leach studies were conducted at 30°C and 50°C with the addition of pyrite to
assist chalcopyrite dissolution via galvanic interaction(Dixon et al., 2008). Detailed characterisation

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studies were conducted on the chalcopyrite samples pre- and post-leaching.

2. HIGH TEMPERATURE PHASE CHEMISTRY OF CHALCOPYRITE

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The phase chemistry of chalcopyrite at high temperature has been the subject of numerous
investigations (e.g.Yund and Kullerud (1966); Kullerud (1970); Cabri (1973); Tsujimura and
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Kitakaze (2004); Kravchenko and Nenasheva (2012)). At elevated temperatures a number of ternary
Cu-Fe-S phases form within a broad composition range, varrying between pyrrhotite (Fe(1-x)S) on
the Fe-S binary and high digenite-bornite (Cu7.2-xS4-Cu5FeS4)ss solid solution on, or extending
from, the Cu-S binary (Figure 1a). At high temperatures, chalcopyrite has a narrow solid solution
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extending from stoichiometric CuFeS2 to Cu0.9Fe1.1S2 along a line with metal:S atomic ration of
approximately 1. Nearby in Cu-Fe-S ternary space, but at lower overall S contents, lies an isometric
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(cubic) solid solution, denoted iss, comprising the metal-excess chalcopyrite-like minerals;
talnakhite, Cu9Fe8S16, mooihoekite, Cu9Fe9S16, and haycockite, Cu4Fe5S8 (Cabri and Hall, 1972).
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These phases, known as stuffed derivatives of chalcopyrite, have additional metal atoms located in
interstitial sites and typically form as high-temperature breakdown products from chalcopyrite when
the temperature exceeds ~557ºC (Pankratz and King (1970). Upon cooling from high temperatures,
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MacLean et al. (1972) noted that a network of chalcopyrite lamellae within a talnahkite matrix
forms indicating exsolution. The matrix, having lost some S during heating, is now enriched in Fe
and metal-rich with respect to S. Additional phases that may form in the Cu-Fe-S ternary from
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chalcopyrite decomposition (depending on parameters such as pO2 and pS2) include; cubanite,
pyrite, pyrrhotite, bornite and chalcocite.

A study by Kullerud (1970) yielded the high temperature phase relations in the Cu-Fe-S system
between 700°C and 1100ºC. In a more recent study, Tsujimura and Kitakaze (2004) refined the
earlier Kullerud (1970) study and measured in detail the phase relations at 800°C. Their results are
shown in Figure 1b. In addition to the expanded iss, bornitess and pyrrhotitess phase fields, in the
central part of the diagram is a region of liquid phase formation where chalcopyrite is no longer
stable having been transformed to a ternary phase assemblage comprising liq+iss+S.

Electrochemical and x-ray photoelectron spectroscopy (XPS) studies of the metal-stuffed

derivatives talnakhite, mooihoekite and haycockite show marked differences in oxidation rates
compared to stoichiometric chalcopyrite (Vaughan et al., 1995). This is to be expected if solid state
diffusion is the rate controlling mechanism: the additional interstitial site metals in the stuffed
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derivatives are more active and mobile. The relative rates of oxidation are in the order haycockite >
mooihoekite > talnakhite > chalcopyrite for reaction in acid solutions using perchloric and
hydrochloric acids (Vaughan et al., 1995). Similar studies have not been conducted using acid
sulfate solutions.

3. MATERIALS AND METHODS

3.1. Materials

Naturally occurring chalcopyrite (CuFeS2) concentrate (Cpy conc.) and pyrite (FeS2) concentrate
(Py conc.) were used in the leach tests. Both were sourced from the Mt Lyell mine in Tasmania and

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concentrated by flotation to 99wt% purity. Analysis by x-ray diffraction (XRD) confirmed the
concentrates were single phase while average elemental composition data determined by ICP-MS
for the chalcopyrite and pyrite concentrates gave calculated compositions of CuFe1.1S2 and FeS1.9,

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respectively.

3.2. Chalcopyrite thermal treatment

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Both the Cpy conc. and Py conc. samples were ground using a mortar and pestle and then sieved to
produce a sample within the -63+38 μm size fraction. This size fraction was used throughout the
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testing for the pre-treatment heating studies and subsequent leaching studies.

The Cpy conc. was divided into six fractions for the pre-treatment process. The fractions were
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heated in platinum-lined alumina boats in a temperature programmed Lindburg tube furnace at

200°C, 550°C and 800°C under either a reducing (Ar/H2 - 95%/5%) or an inert (N2) atmosphere. All
samples were heated at a ramp rate of 20°C per minute and held at temperature for a period of 5 hrs
before being cooled within the furnace to room temperature.
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3.3. Dissolution studies

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The following reagents were used as received in the leaching tests; sulfuric acid [H2SO4] (1M
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solution) and nitric acid [HNO3] (70% w/w AR grade. Milli-Q water was used to prepare all
solutions.
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Dissolution experiments were conducted in a three-neck, 250 ml round bottom flask fitted with an
overhead mechanical stirrer and pH and oxidation reduction potential (ORP) probes (glass electrode
and platinum vs. Ag/AgCl electrode, respectively). For the dissolution tests, 0.5 g of Cpy conc. and
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1.5 g of Py conc. (1:3) were weighed and mixed with 150 mL of milli-Q water to generate a slurry.
The slurry was then stirred while being heated to temperature using a heating mantle controlled by
an electronic temperature controller. Once the required temperature was reached 1M H2SO4 was
added to maintain pH at 1.8. The addition of the acid was designated as time zero. Slurry samples
were collected at pre-determined time intervals. These were filtered through a 0.45 μm nylon filter
and 0.25 ml of the filtered solution was acidified with concentrated nitric acid, diluted and then
analysed for Cu using ICP-MS.

3.4. Characterisation methods

3.4.1. Elemental composition (ICP-MS)

The following chemicals were used as received for preparing and analysing the leach residues via
ICP-MS: sulfuric acid [H2SO4] (98% AR grade, Merck Ltd), nitric acid [HNO3] (70% AR grade,
Merck Ltd), hydrochloric acid [HCl] (33% AR grade, Merck Ltd), hydrofluoric acid [HF] (50% AR
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grade, Ajax Chemicals), 30% hydrogen peroxide [H2O2] (30% AR grade, Merck Ltd). MilliQ water
was used in the preparation of all solutions.

To prepare the samples for ICP-MS analysis, a multi acid digestion procedure was used. 0.1g of
crushed sample was weighed into a teflon vessel followed by slow addition of 6 mL concentrated
HCl, 2 mL concentrated HNO3, 2 mL concentrated H2SO4 and 3 mL concentrated HF. The teflon
vessel was then placed on an aluminium heating block and heated at 110°C until incipient dryness
and then raised to 160°C to bring the sample to complete dryness. Once dry, an additional 1 mL of
concentrated HNO3 and two drops of H2O2 were added until dryness. Finally 1 mL concentrated
HNO3 and 19 mL of 2% HNO3 were added and capped in a sealed vessel at 110°C for 2 hours. Full
quantitative analysis was completed using a multi elemental environmental standard on an Agilent
HP 7700 series ICP-MS. An internal standard containing Sc, Ge, Rh, In, Tb, Lu, Bi, was added to

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all calibration and test samples. The error for the elemental composition analysis was calculated to
be ±3%.

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3.4.2. X-ray diffraction (XRD)
The pre-leached, thermally treated samples and leach residues were analysed by x-ray diffraction.
XRD data were collected from 5-140° 2θ using a PANalytical MPD instrument fitted with a cobalt

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long-fine-focus X-ray tube operated at 40 kV and 40 mA. The incident beam path was defined
using 0.04 radian Soller slits, a 20 mm mask, a 0.5° fixed divergence slit, and a 1° anti scatter slit.
The diffracted beam incorporated a second set of Soller slits, a graphite monochromator to
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eliminate unwanted wavelengths and a 4.6 mm anti-scatter slit. An X’Celerator detector was used in
scanning line (1D) mode with an active length of 2.122° 2θ. Qualitative phase analysis was carried
out on all samples using HighScore Plus (Version 4.1) software.
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For selected samples, a Rietveld refinement-based approach to quantitative phase analysis (QPA)
was performed using TOPAS (Version 5 – Bruker, 2014). Analyses are considered accurate to
±5wt%. The crystal structure information in Hall and Stewart (1973), Hall and Gabe (1972), Koto
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and Morimoto (1975), Bayliss (1977), Rettig and Trotter (1987), Skála et al. (2006), Goble and
Robinson (1980), Wyckoff (1963), Burdick and Ellis (1917) and Hall and Rowland (1973) was
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used for chalcopyrite (tetragonal), talnakhite, bornite, pyrite, sulfur, troilite, geerite, copper,
chalcopyrite (cubic) and mooihoekite, respectively.
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3.4.3. Scanning Electron Microscopy/ Energy Dispersive X-ray Analysis

The thermally treated samples plus the residues after leaching were prepared for SEM analysis by
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dispersing grains in epoxy resin and mounting into 2.5 cm round blocks. Scanning electron
microscopy was performed using an FEI Quanta FEG 400 Environmental Scanning Electron
Microscope (ESEM) instrument equipped with a single Bruker XFlash® silicon drift detector for
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conducting energy dispersive x-ray spectroscopy (EDX) and Esprit v.1.9 analytical software. The
ESEM was operated at an accelerating voltage of 15 kV, a probe current of ~0.7 nA and a vacuum
of <2x10-6 Torr.

3.4.4. Electron Probe Microanalysis (EPMA)

Two types of EPMA information were obtained. Initially all thermally treated samples and leached
residues were mapped using a high resolution Field Emission Gun (FEG) equipped EPMA (JEOL
8500F Hyperprobe). This was done in order to examine the chemical homogeneity of individual
grains, and to examine textural differences between the pre- and post-leached samples. Operating
conditions for the microprobe during mapping of the pre-leached samples were an accelerating
voltage of 12 kV, a beam current of 40 nA, a step size of 0.5 m (in x and y), and a counting time
of 20 ms per step. For the leach residues, the step size was reduced to 0.3 m based on a visual
examination of the samples which revealed the presence of fine, sub-micron textural features. The
element distribution data obtained by mapping were manipulated using the software package
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CHIMAGE (Harrowfield et al., 1993) which incorporates an automated clustering algorithm that
identifies chemically alike phases (Wilson and MacRae, 2005). These phases were then overlaid
onto the mapped region to provide a “phase-patched” map showing the distribution of all
chemical/mineral phases and associated textures within the mapped area.

Following mapping by FEG-EPMA, selected samples were examined by quantitative EPMA

techniques using a JEOL 8900 Superprobe to assess the distribution of major and minor elements
within the different phases. The suite of elements analysed included Cu, Fe, S, As and Zn.
Standards used were synthetic versions of NiAS, ZnS, FeS2 and CuFeS2. For the quantitative
analyses, the microprobe was operated at 12 kV and 40 nA and the electron beam focused to ~1 μm.
Counting times were 30 s on the main peak and 30 s on the background (i.e 15 s either side of the
main peak analysed).

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4. RESULTS AND DISCUSSION

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4.1. Characterisation of the starting materials

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The purity of the starting Cpy and Py concentrates used in the thermal treatment and leaching
experiments was confirmed by quantitative electron probe microanalysis (Table 1). Average
elemental composition data determined by EPMA for the chalcopyrite and pyrite concentrates gave
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calculated compositions of Cu0.99FeS2 and FeS2.05, respectively, in good agreement with the ICP-
MS results.
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4.2. Characterisation of thermally treated samples (pre-leach)

Results from the XRD analysis of the heat-treated samples are provided in Table 2. In samples
heated to 200°C under both inert and reducing conditions, there was no observable change in the
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sample with the chalcopyrite present in the tetrahedral form. At 550°C in both atmospheres, the
chalcopyrite began to decompose into talnakhite and a minor amount of bornite, consistent with the
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phase diagram at 600°C (Figure 1a) which indicated high temperature breakdown of chalcopyrite to
a bornite solid solution and metal-rich derivatives. The EPMA map results on both samples at
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550°C were inconclusive and suggested that the chalcopyrite remained unchanged. This was most
likely due to the inability of the rapid EPMA mapping procedure used to distinguish the subtle
chemical differences between chalcopyrite, talnakhite and bornite which were most likely present as
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complex intergrowths. Quantitative EPMA results on the sample heated to 550°C under reducing
conditions indicated a phase with slight enrichment in Cu and Fe and depletion in S relative to the
Cpy starting material (Table 1). This material may represent a fine-grained intergrowth of Cpy and
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iss phase which, according to the XRD results in Table 2, was most likely talnakhite.

Further heating of the chalcopyrite to 800°C saw differences in the decomposition phases present
according to the atmosphere. Heating under an inert atmosphere resulted in the complete
disappearance of chalcopyrite with the final assemblage being composed of the metal-rich phases
talnakhite and mooihoekite along with minor bornite and geerite. According to Putnis and
McConnell (1976), upon cooling rapid ordering associated with a decrease in free energy results in
the preservation of these ordered or partially ordered phases that have only minor variations in
structure with relation to composition. This indicates they are likely to be preserved upon cooling
and is consistent with the observation that all three phases talnakhite, mooihoekite and haycockite
occur as natural minerals (Cabri and Hall, 1972).

Under reduced conditions at 800°C, the decomposition of chalcopyrite was extensive. The metal-
rich derivatives were no longer stable with the major phases present being bornite (orthorhombic
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form), cubanite, chalcocite and troilite. A small amount of geerite and metallic copper also formed.
The EPMA map from the 800°C H2 reduced sample is shown in Figure 2. Textures within the
reduced chalcopyrite grains are complex and appear to be composed of mixtures of bornite with
exsolved chalcocite (Figure 2b). An example of the complex textures present with individual grains
is shown in Figure 3. The fine-grained intergrowth texture made it difficult to obtain quantitative
EPMA results on many of the Cu-Fe-S phases and therefore data was only obtained for the coarser-
grained troilite, chalcocite and copper metal phases. These are provided in Table 1.

4.3. Dissolution studies

The effect of the thermal treatment temperature and atmosphere on the leaching of copper from
chalcopyrite was examined at 30°C and 50°C in leach experiments conducted over seven days.

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Leach conditions, Cpy conc. (1:3 vs. Pyr conc.), pH (1.8), and particle size (P80- 65-38µm), were
kept constant for all tests. All experimental data are listed in Table 3.

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4.3.1. Influence of thermal treatment on dissolution of chalcopyrite concentrate.
Results showing the effect of the thermal treatment temperature (200°C, 550°C and 800°C) and gas
atmosphere (reducing versus inert) on the %Cu extraction at 50°C is shown in Figure 4.

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The treatment of the Cpy conc. under an inert N2 atmosphere resulted in only a slight increase in
%Cu extraction with increasing thermal treatment (Figure 4a). Leaching of the untreated
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concentrate gave a %Cu extraction of ~12.5% Cu after seven days. The amount of copper extracted
systematically increased with treatment temperature rising to ~14.6% Cu (200°C), ~15.3% Cu
(550°C) and ~15.8% (800°C). These results are consistent with the thermal treatment under
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nitrogen producing phase assemblages that contain more readily oxidised and leachable species
such as talnakhite and mooihoekite (Vaughan et al., 1995) although it appears that these mineral
phases are refractory and are only marginally more easily oxidised relative to pure chalcopyrite, at
least in sulfuric acid solutions.
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The thermal treatment under a reducing atmosphere followed by leaching at 50°C (Figure 3b) saw
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modest increases in copper extraction at 200°C and 550°C with ~21 %Cu and ~24 %Cu extraction,
respectively. However, this was greater than that observed under equivalent experiments conducted
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under inert nitrogen atmosphere at 200°C and 550°C with ~14 %Cu and ~15 %Cu extraction
respectively. This is likely due to the smaller hydrogen molecule being able to penetrate fractures
and pores leading to an increase in surface area for the leachant to attack and also the increased
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amount of talnakite formed during the pre-treatment. Heating under a reducing atmosphere at the
higher temperature of 800°C however resulted in a significant increase in the %Cu extraction,
reaching 78% extraction over the seven days. This dramatic increase is associated with the
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significant changes in mineral phase assemblage observed in the 800ºC sample with the formation
of readily leachable geerite, chalcocite, and copper phases forming. It was also noted that two
different leach rates were observed for the 800ºC sample (Figure 4b). Initially there was a rapid rate
of Cu extraction over the first ~10-12 hours of leaching which was likely associated with the
leaching of metallic copper, chalcocite and geerite. This was then followed by a decline in the
extraction rate associated with the leaching of bornite and cubanite.

4.3.2. Influence of leach temperature

The influence of leach temperature on the extraction of copper from the thermally treated
chalcopyrite concentrates was also investigated. The Cpy conc. treated at 200°C and 800°C under
reducing conditions was leached at 30°C and 50°C and compared with non-treated concentrate in
order to determine the activation energy of chalcopyrite leaching under the conditions studied. The
tests were conducted for a period of seven days with all other conditions maintained to be constant;
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including pyrite concentration (3:1 vs. Cpy conc.); pH 1.8; P80- 65-38µm; Eh 360 mV vs. Ag/AgCl.
Results are illustrated in Figure 5.

The change in leaching temperature had minimal impact on both the %Cu extraction for the non-
treated samples with the increase in temperature from 30°C to 50°C resulting in a change from only
~12% Cu extraction to ~13% Cu extraction, respectively. A similar, but slightly greater %Cu
extraction trend was observed for leaching of the 200°C thermally treated samples where there was
an increase from ~21% Cu extraction at 30ºC to ~22% Cu extraction at 50°C. The effect of
temperature was more pronounced in the sample thermally treated in a reducing atmosphere at
800C. For this sample ~71% Cu extraction was obtained at a leach temperature of 30°C compared
to ~78% Cu extraction observed at 50°C. Based on these results leaching temperature has an
influence when the concentrate has been subjected to extensive chemical and physical modifications

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by the thermal pre-treatment.

4.4. Leach Residue Characterisation

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Results from the XRD analysis of the residues from the leached, heat-treated samples are provided
in Table 4 and Figure 6. The most obvious change from the pre-leached, thermally treated

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concentrate results is the increased abundance of pyrite relative to Cu-rich phases – this is due to the
addition of pyrite to the Cpy conc. before leaching to assist copper leaching via galvanic
interaction(Dixon et al., 2008). The other important point to note is that in the pre-treated samples
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where there was significant conversion of chalcopyrite to the metal-rich derivative phases, the leach
process has caused these phases to convert into chalcopyrite, typically the high-temperature cubic
form, or to Cu-depleted phases such as cubanite. It is noted however that the ratio of pyrite to
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chalcopyrite (±cubanite) is much greater than the 3:1 used in the original pre-leach mixture. In the
samples treated under nitrogen the post-leach ratio is up to 15:1 pyrite:chalcopyrite (550°C, N2
leached sample) consistent with dissolution of some copper. The ratio however, decreases to <10:1
in the samples pre-treated under a reducing atmosphere. While this observation initially suggests
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less copper dissolution we believe it is more likely due to enhanced dissolution of the Fe-deficient
sulfide troilite (pyrrhotite) which also formed in the reduced concentrates (Filippou et al., 1997;
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Majima and Peters, 1966), This was previously noted by Nicholson et al. (1994) who determined
that in low temperature, acidic environments such as found in mine waste tailings, pyrrhotite was
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less refractory than pyrite. Minor amounts of elemental sulfur were also noted in the leached
residues.
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The EPMA map results on residues recovered from the 800°C N2 leached and the 800°C H2
reduced samples are shown in Figure 7. For the 800°C N2 leached sample (Figure 7a) the textures
within the reduced chalcopyrite grains are complex and appear to be composed of mixtures of
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cubanite with chalcopyrite set in a matrix of largely unreacted pyrite. During leaching, oxidation of
the metal-rich chalcopyrite derivatives mooihoekite and talnakhite observed in the unleached
sample revert back to a mixture of chalcopyrite and Cu-deleted cubanite. The complex textures
present in the residues precluded accurate EPMA of these phases. Sulfur was present at very low
levels – we believe the lack of elemental S observed in the EPMA maps is likely due to plucking of
the softer material during sample preparation.

The 800°C reduced and leached sample (Figure 8b) comprised a large proportion of pyrite with
residual trolilte (pyrrhotite) remaining from the original unleached sample. Compositions for each
of these phases are provided in Table 1. The copper metal and copper sulfide phases chalcocite and
geerite had been completely removed leaving only chalcopyrite and unidentified Cu-Fe sulfides as
the Cu-rich phases present. These latter two phases are intimately intergrown forming complex
textures as shown in Figure 3. The fine-grained textures were below the resolution of the EPMA
mapping technique, typically 1-2 micron, meaning it was not possible to uniquely identify their
composition – see Table 1. The XRD data however indicated they were likely a mixture of
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chalcopyrite and cubanite. Elemental sulfur was present in the residue according to the quantitative
XRD results, but was not located during the map analysis.

5. CONCLUSION

The current study has demonstrated the influence of thermal pre-treatment (inert and reducing
atmosphere) on leaching of chalcopyrite. The XRD and EPMA results showed no observable
changes in the samples heated to 200°C under both inert and reducing conditions. At 550°C in both
atmospheres, the chalcopyrite began to decompose into talnakhite and very minor bornite, Further
heating of chalcopyrite to 800°C led to significant differences in the decomposition under both

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atmospheres. The heating at 800C in inert atmosphere led to the decomposition of chalcopoyrite
and formation of the metal-rich phases’ talnakhite and mooihoekite along with minor bornite and
geerite. The heating under reduced atmosphere led to extensive decomposition leading to the

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formation of bornite, cubanite, chalcocite, troilite, geerite and metallic copper.

The subsequent leaching study of the pre-treated chalcopyrite showed higher copper extractions for

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the H2 treated samples compared to the N2 treated samples. The 800°C H2 treated sample exhibited
the highest extraction (~78% Cu extraction) compared to the un-treated chalcopyrite sample (~12%
Cu extraction). This was attributed to the formation of less refractory copper mineral phases in the
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hydrogen treated sample.

It is important to note that the results obtained where in the absence of an external oxidant (eg. in
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the form of ferric iron, hydrogen peroxide or air) to facilitate chalcopyrite leaching. A further
comprehensive study is required to ascertain optimisation of chalcopyrite leaching under various
pre-treatments. It should be noted that whilst the current results look promising, from a commercial
perspective it may not be practical to treat low grade chalcopyrite ore under hydrogen at high
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temperature. Low grade ores have a large amount of gangue minerals associated with them and
hence it would be impractical and energy intensive to thermally treat a large volume of low grade
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ore. Furthermore, hydrogen gas is expensive and would likely need to be generated on site, thus
contributing to the cost of operations. This technique however may be practical for the treatment of
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medium to high grade chalcopyrite ores and concentrates. A similar process was patented by
Sherritt Gordon Mines Limited and Cominco Limited whereby chalcopyrite concentrates were
roasted under an oxidising atmosphere (air) followed by a reducing atmosphere (H2) and sulfuric
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acid leaching of the roasted material was conducted to remove soluble iron and produce a higher
grade copper sulfide concentrate for sale or further processing (Swinkels and Maschmeyer, 1980).
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6. ACKNOWLEDGEMENTS

The authors are grateful to the RMMF Microscopy facility for use of the SEM/EDAX equipment.
Cameron Davidson (CSIRO - sample preparation), and Aaron Torpy (CSIRO – EPMA set-up and
data analysis) are thanked for their contributions to this work.
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7. REFERENCES

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Table 1: Summary of quantitative EPMA results on the starting materials and the pre-treated
samples and residues from samples heated in a reducing Ar/5%H2 atmosphere.

Sample Element (wt%) Total

As Zn Fe S Cu
Untreated samples
Cpy 0.003 0.001 30.60 35.06 34.40 100.06
Pyrite 0.004 0.008 45.94 54.14 0.04 100.13

Samples treated in a reducing Ar/5%H2 atmosphere

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550°C unleached
Cpy 0.003 0.008 31.00 34.00 35.63 100.63

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550°C leach residue
Pyrite 0.002 0.000 47.30 53.17 0.06 100.52
Cpy Cu-depleted† 0.000 0.000 33.39 35.06 30.67 99.10

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800°C unleached
Troilite 0.010 0.007 62.72 36.07 2.58 101.39
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Cu metal 0.013 0.000 1.82 0.14 100.43 102.40
Chalcocite 0.008 0.005 4.01 21.63 76.28 101.93
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800°C leach residue

Pyrite 0.000 0.008 47.19 53.21 0.06 100.46
Cpy Cu-depleted† 0.000 0.000 35.99 35.27 27.40 98.63
† although close to Cpy in composition, this analysis most likely represents a mixture of fine-grained phases.
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Table 2: XRD results from the thermally treated samples, pre-leach. Relative wt.% values are ±5%.
Sample Phase Nominal ICDD Relative
composition Database No. wt.%
a) Samples treated in an inert N2 atmosphere
200°C, N2 Chalcopyrite (tet) CuFeS2 37-0471 n.d.†

550°C, N2 Chalcopyrite (tet) CuFeS2 37-0471 74.0

Talnakhite Cu18.32Fe15.9S32 1-071-2438 23.6
Bornite (orth) Cu5FeS4 42-1405 2.5

800°C, N2 Geerite Cu1.6S 1-081-5205 1.8

Bornite (orth) Cu5FeS4 42-1405 2.4

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Mooihoekite Cu9Fe9S16 1-071-0527 40.3
Talnakhite Cu18.32Fe15.9S32 1-071-2438 55.3

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b) Samples treated in a reducing (Ar/H2 - 95%/5%) atmosphere
200°C, 5%H2 Chalcopyrite (tet) CuFeS2 37-0471 n.d.

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550°C, 5%H2 Chalcopyrite (tet) CuFeS2 37-0471 36.1
Talnakhite Cu18.32Fe15.9S32 1-071-2438 62.5
Bornite (orth) Cu5FeS4 42-1405 1.4
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800°C, 5%H2 Geerite Cu1.6S 1-081-5205 16.2
Bornite (orth) Cu5FeS4 42-1405 12.0
Troilite FeS 1-089-3039 48.3
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Chalcocite Cu1.96S 29-0578 19.5

Cubanite CuFe2S3 47-1749 2.3
Copper Cu 4-0836 1.7
†n.d. = not determined.
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Table 3: Test conditions for the leach studies on the pre- and thermally-treated Cpy conc.

Cpy conc. Py conc. Treatment Gas Leach

Test pH
(g) (g) Temp (°C) atmosphere Temp (°C)
1 1.8 0.5 1.5 None - 50

2 1.8 0.5 1.5 200 Ar/H2 - 95%/5% 50

3 1.8 0.5 1.5 550 Ar/H2 - 95%/5% 50
4 1.8 0.5 1.5 800 Ar/H2 - 95%/5% 50

5 1.8 0.5 1.5 200 N2 50

6 1.8 0.5 1.5 550 N2 50

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7 1.8 0.5 1.5 800 N2 50

8 1.8 0.5 1.5 None - 30

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9 1.8 0.5 1.5 None - 50

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10 1.8 0.5 1.5 200 Ar/H2 - 95%/5% 30
11 1.8 0.5 1.5 200 Ar/H2 - 95%/5% 50
12 1.8 0.5 1.5 800 Ar/H2 - 95%/5% 30
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Table 4: XRD results on residues from the thermally treated and leached samples. Relative wt.%
values are ±5%.
Sample Phase Nominal ICDD Relative
composition Database No. wt.%
a) Samples treated in an inert N2 atmosphere
200°C, N2 Chalcopyrite (tet) CuFeS2 37-0471 n.d.†
Pyrite FeS2 42-1340 n.d.

550°C, N2 Chalcopyrite (tet)‡ CuFeS2 37-0471 5.9

Pyrite FeS2 42-1340 86.4
Sulfur S8 1-073-5065 7.7

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800°C, N2 Chalcopyrite (cub) CuFeS2 1-075-0253 3.9
Pyrite FeS2 42-1340 85.6
Sulfur S8 1-073-5065 6.1

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Cubanite CuFe2S3 47-1749 4.5

b) Samples treated in a reducing (Ar/H2 - 95%/5%) atmosphere

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200°C, 5%H2 Chalcopyrite (tet) CuFeS2 37-0471 n.d.
Pyrite FeS2 42-1340
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550°C, 5%H2 Chalcopyrite (tet)‡ CuFeS2 37-0471 13.0

Pyrite FeS2 42-1340 81.2
Sulfur S8 1-073-5065 5.8
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800°C, 5%H2 Chalcopyrite (cub) CuFeS2 1-075-0253 3.1

Pyrite FeS2 42-1340 83.6
Troilite FeS 1-089-3039 5.0
Sulfur S8 1-073-5065 3.6
Cubanite CuFe2S3 47-1749 4.7
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‡ the degree of splitting of the tetragonal chalcopyrite reflections (e.g. the (220) and (024) at ~57° 2θ) is reduced in the
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550°C N2 and 550°C H2 residue samples compared to the 550°C N2 and 550°C H2 unleached samples. This observation
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indicates that the chalcopyrite in the residues was on its way to forming cubic chalcopyrite (ICDD 1-075-0253) but the
conversion was incomplete.
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Figure 1: Phase relations in the Cu-Fe-S system at 600°C (a) and 800°C (b) showing the stability
fields for the chalcopyrite-derivative phases (iss), the bornite (bnss) and pyrrhotite (poss) solid
solution series, and the development of a liquid phase region. Phase diagram after Cabri (1973) and
Tsujimura and Kitakaze (2004).

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Figure 2: Back-scattered electron (BSE) image (a) and corresponding EPMA map (b) for the 800°C
H2 reduced sample. Note that the EPMA results indicate the presence of significant pyrrhotite
whereas the XRD data (Table 1) indicate this phase is troilite. The map data is also not able to
identify the presence of geerite and cubanite. The mis-identification is due the rapid EPMA
mapping procedure being unable to distinguish subtle differences in chemistry between these and
related phases.

a) b)

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100 µm
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Figure 3: High resolution BSE and SE images showing a) the complex internal textures within
reduced chalcopyrite grains from the 800°C H2 reduced sample. The bright worm-like phase is
exsolved chalcocite, the medium grey matrix phase is bornite and the separate dark grey phase is
troilite (labelled as pyrrhotite in Figure 1b); b) metallic copper, c) a mixture of phases including;
metallic copper (Cu), a bornite/chalcocite particle (CuFe) and pyrrhotite (Po), and, d) a magnified
view of a bornite/chalcocite particle showing well faceted crystals on the surface of a thermally
transformed chalcopyrite particle. Scale bar in each image represents 10 µm.

a) b)

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c) CuFe d)
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Cu Po
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Figure 4: Plots showing % Cu extracted vs. Time for: (a) the N2 pre-treated Cpy conc at 200°C,
550°C and 800°C vs. pre-treated Cpy conc., and, (b) the H2 pre-treated Cpy conc. at 200°C, 550°C
and 800°C vs. pre-treated Cpy conc; at a leach temperature of 50 °C, pH of 1.8 and a Cpy conc. to
Pyr conc. ratio of 1:3

a)

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Figure 5: Plot showing % Cu extracted vs. Time at leach temperatures of 30ºC and 50°C for the N2
treated Cpy concentrate and H2 treated Cpy concentrate. Both thermally treated samples are directly
compared against results for the untreated Cpy concentrate.

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Figure 6: Rietveld output for XRD data collected for the 800°C H2 residue sample. Experimental
data are shown as a blue solid line, the calculated pattern a red solid line, and the difference pattern
the black solid line below. The vertical lines are the Bragg reflection markers for (upper to lower)
pyrite, sulfur, troilite, cubanite and chalcopyrite.

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Figure 7: Back-scattered electron (BSE) images and maps showing the distribution of phases in the
residues for samples; (a) 800°C, N2 and, (b) 800°C H2 reduced sample. Both samples were leached
at 50°C for 7 days. Scale bar represents100 µm.

a)

CP
2040

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100 µm
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Pyrite Chalcopyrite
Cubanite Sulphur

b)
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100 µm 100 µm

Pyrite Chalcopyrite
CuFeS intergrowths Pyrrhotite
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Figure 8: High resolution BSE images showing the complex dissolution textures developed after
leaching of the sample pre-treated by heating in a H2 atmosphere at 800°C. a) BSE image of a grain
mount polished surface – dark grey grains are pyrrhotite/troilite while light grains represent Cu-Fe
sulfide grains, b)-d) images showing various dissolution features developed in the Cu-Fe sulfide
grains. The sample was leached at 50°C for 7 days.

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