Minerals Engineering 130 (2019) 156–164

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Pyrometallurgical processing of a low copper content concentrate based on a T

thermodynamic assessment
⁎
Rodrigo Souza , Carlos Queiroz, José Brant, Eduardo Brocchi
Chemical and Materials Engineering Department, Pontifical Catholic University of Rio de Janeiro, Rua Marquês de São Vicente, 225, CEP: 22453-900 Rio de Janeiro, RJ,
Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: Concentrates containing sulphide minerals are an important raw material source in the extractive metallurgy of
Copper sulphate nonferrous metals. This study aims to evaluate the pyrometallurgical processing of a sulphide concentrate with a
Iron oxide relatively low copper content through an alternative methodology (roasting-leaching route), in order to selec-
Sulphide roasting tively obtain CuSO4 and Fe2O3 for the chemical industry. The thermodynamic behaviour of the concentrate was
Low grade copper concentrate
evaluated in order to identify the conditions to fulfil the aforementioned selectivity. The presence of SO2(g) in
the reaction system could be responsible for increasing CuSO4 stability without compromising FeSO4 dissocia-
tion. Subsequently, experiments were carried out to evaluate the temperature and chemical composition of the
atmosphere. Both obtained products and raw materials were characterized using common techniques (e.g. X-Ray
Diffraction and SEM/EDS). Finally, some roasting products were submitted to water solubilisation tests in order
to verify, in practice, the selective conversion of copper and iron sulphides into CuSO4 and Fe2O3. The proposed
methodology allowed for complete separation of Cu from Fe, roasting experiments conducted at 873 K (600 °C)
and 923 K (650 °C). This was observed in praxis through the formation of a blue liquor, typically copper sul-
phate, and a brown solid residue which was deprived of Cu, as verified by the applied characterization methods.

1. Introduction by-product of the electrowinning industry (Habashi, 1997). So, low

Copper (Cu) is a chalcophile element whose occurrence in the
earth’s crust is usually in the form of sulphides (Habashi, 1997).
Therefore the vast majority of known Cu occurrences are associated to
sulphides minerals (Davenport et al., 2002). In the most traditional
route, copper concentrates are chemically processed in two furnaces
that operate under an oxidizing atmosphere (Habashi, 2002; Davenport
et al., 2004; Vignes, 2011b). This pyrometallurgical route can be very
demanding in terms of Cu content, particularly in Flash Furnace op-
erations. Thus, for metal obtaining processes, it is almost imperative
that the final concentrates exhibit a minimum Cu content of around
30% in weight (Davenport et al., 2002, 2004; Habashi, 1997).
In parallel to this metallurgical requirement, with increasing de-
mands for more competitive chemicals for agriculture, the industry has
focused on alternatives which may be economically attractive
(Chapman, 2000). In this sense, roasting operations could be used to
produce copper sulphate which is an important chemical used in agri-
culture for the preparation of Bordeaux mixture, as well for correction
of copper deficiency in soils. This chemical is mainly produced from
metallic copper, blister and scrap, through the Harike method or as a
grade copper concentrates unsuitable for traditional copper me-
tallurgical industries could be used in this context as a raw-material to
produce this chemical. Considering that low-grade concentrates are
usually a marginal product of the mining industry, their commerciali-
zation could be implemented at competitive prices, motivating the
aforementioned applications. However, it is necessary to pursue op-
erational conditions for copper-iron sulphides, such as chalcopyrite
(CuFeS2) and bornite (Cu5FeS4), which allows the selective separation
between Cu and Fe.
It is well known that, depending on the temperature and imposed
oxygen partial pressure, is possible to favour the stability of minor
sulphides, sulphates, oxides or even metallic copper (Moore, 1994;
Yildirim, 2002; Zhao et al., 2015; Vignes, 2011a). This characteristic
has been the basis of several studies on Cu recovery (Yianatos and
Antonucci, 2001; Ferron and de Cuyper, 1992). For copper-iron sul-
phides, it is possible to provide a controlled atmosphere that enables
the simultaneous formation of copper sulphate and iron oxide (Prasad
and Pandey, 1999). These reaction products could be separated through
water solubilisation followed by filtering the non-soluble materials
(iron oxides) from the liquor (copper sulphate solution). The salt could

⁎
Corresponding author.
E-mail address: rsouza@puc-rio.br (R. Souza).

https://doi.org/10.1016/j.mineng.2018.10.015
Received 29 November 2017; Received in revised form 17 October 2018; Accepted 19 October 2018
Available online 30 October 2018
0892-6875/ © 2018 Elsevier Ltd. All rights reserved.
R. Souza et al.
be crystallized later in its hydrated form and used in agriculture ac-
tivities as mentioned above.
Although well-detailed in the literature, this route can be further
explored focusing on the expansion of the roasting operational condi-
tions. This could be carried out by means of SO2(g) atmosphere en-
richment through gaseous products recycling in the furnace itself. This
alternative approach may be considered a contribution to low-grade
concentrate extractive metallurgy, as this is still a current research topic
in mineral industry (Norgate and Jahanshahi, 2010). Literature review
indicates a paucity of alternatives within the sulphide roasting spec-
trum, since pyrometallurgical options relies mainly on reducing agents
(Kim et al., 2008; Balasanov et al., 2010) while other developments
opted for hydro (Gok and Anderson, 2013; Liu et al., 2012) or bio-
hydrometallurgical routes (Africa et al., 2013; Conić et al., 2014).
Therefore, the general purposes of the present study are associated
with the development of a preliminary assessment of this type of re-
action system in order to selectively produce CuSO4 and Fe2O3 from a
low grade copper concentrate. Thus, a thermodynamic evaluation of
this reaction system was carried out to identify the operational condi-
tions in which the proposed transformation is feasible, for both tradi-
tional and sulphur dioxide enrichment routes. This study also in-
corporates an experimental procedure to evaluate temperature effects,
as well as the chemical composition of the atmosphere, over the CuSO4
and Fe2O3 formation.
2. Materials and methods
2.1. Materials characterization
This study was carried out using a sulphide concentrate from a
marginal occurrence in a Brazil, obtained after mineral processing
procedures. Both raw-material and reaction products were character-
ized using the conventional techniques of X-ray Diffraction (XRD),
Scanning Electron Microscopy (SEM) and Energy-Dispersive X-ray
Spectroscopy (EDS). For the XRD analysis, a Panalytical equipment
(model XPERT PRO) was used under the Bragg-Brentano geometry and
with a copper source, while the SEM analysis was carried out using a
DSM960Zeiss equipment. This microscope was also equipped with an
Oxford Instruments kit for EDS analysis. For better evaluation of
copper, iron and sulphur content in the raw-material, an inductively
coupled plasma mass spectrometry (ICP-MS) analysis was carried-out
on a Perkin Elmer spectrometer (Optima 4300 DV).
2.2. Thermodynamics assessment
In order to assess the thermodynamics features of these reaction
systems, it was performed equilibrium composition calculations as well
as the construction of predominance diagrams. These were carried out
using the HSC Chemistry software (Roine, 2006).
2.3. Experimental procedure
2.3.1. Copper-iron sulphides roasting
The pyrometallurgical processing experiments were conducted in a
tubular furnace, where 1.0 g of concentrate was disposed in a ceramic
crucible. After heating to the desired temperature, the sample was then
subjected to a controlled gas flow of approximately 0.3 L min−1. The
temperature in which the reactions take place and the atmosphere
composition of the system were evaluated. The former ranged from
873 K (600 °C) to 1023 K (750 °C), while the latter could be assessed
offering to the reaction system compressed air, pure oxygen and oxygen
enriched with sulphur dioxide produced by the system itself. Fig. 1
presents a schematic view of the experimental apparatus.
2.3.2. Selective solubilisation of reaction products
Solubilisation tests were performed using slightly heated deionized
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Minerals Engineering 130 (2019) 156–164
water and, after that, the produced solid-liquid suspension was filtered
to separate the non-soluble materials.
3. Thermodynamics assessment (Souza, 2012)
As described in the literature, it is possible to create a reaction en-
vironment in which the formation of oxides, sulphates, sulphides and
even metals is thermodynamically feasible, by varying only roasting
operational conditions, like temperature and atmosphere chemical
composition. This is a specific characteristic of metallic sulphide reac-
tion systems in the presence of an oxidizing atmosphere and can be
expressed by the following reactions (Moore, 1994; Parker, 1983).
MS2(s) + O2(g) ↔ MS(s) + SO2(g) (1)
MS2(s) + 2.5O2(g) ↔ MO(s) + 2SO2(g) (2)
MS2(s) + 3O2(g) ↔ MSO4(s) + SO2(g) (3)
MS2(s) + 2O2(g) ↔ M(s) + 2SO2(g) (4)
In order to simplify the calculations and better understand thermo-
chemical tendencies towards copper and iron sulphides behaviour in
these reaction atmospheres, a thermodynamics appraisal was first
performed considering Cu-S-O and Fe-S-O as isolated systems, since
these metals display distinct chemical behaviour as a function of the
studied variables.
3.1. Predominance diagrams
Under the perspective of assessing temperature and atmosphere
composition over Cu-S-O and Fe-S-O reaction systems, predominance
diagrams were constructed at two conditions: fixed temperature and
fixed oxygen partial pressure.
Fig. 2 display the predominance diagram associated to the Cu-S-O
reaction system at a fixed temperature of 873 K (600 °C).
The diagram indicates the required operational settings to maintain
copper as its respective sulphate, as this compound is only stable at high
partial pressures of oxygen and sulphur dioxide. Moreover, it is note-
worthy that, starting from a condition where CuS is the predominant
species, O2(g) partial pressure must be increased, allowing for higher
atmosphere oxidizing power. Furthermore, in order to achieve the
stability region for CuSO4, the reaction system must enter the pre-
dominance areas of Cu2S, as well Cu2O and, possibly, the CuO·CuSO4
region, depending on the partial SO2(g) pressure inside the reactor. This
particular scenario indicates a possible thermochemical mechanism in
which the Cu fraction of a copper-iron sulphide is transformed into
copper sulphate at a fixed temperature.
Fig. 3 exhibits the predominance diagram as a function of tem-
perature and SO2(g) partial pressure, fixing the O2(g) partial pressure at
21 × 103 Pa. For any SO2(g) condition, copper sulphate is the most
stable species at low temperatures, while copper oxide is predominant
at high temperatures. It is interesting to highlight that sulphur dioxide
increments make CuSO4 stable at a higher temperature.
Following the same approach, Fig. 4 illustrates the predominance
diagram of Fe-S-O at a fixed temperature of 873 K (600 °C).
The resulting diagram displays substantial similarities to the one
associated with the Cu-S-O system. FeSO4 is, as expected, the main iron
bearing compound at high partial pressures of oxygen and sulphur di-
oxide. However, it is noteworthy that its predominance region is
smaller than the one associated with copper sulphate. This particular
distinction between the two diagrams shows a direct impact over the
operational conditions necessary to obtain FeSO4 from FeS, as more
oxygen is required to form this sulphate. This Fe-S-O system char-
acteristic significantly alters the possible selectivities of the composite
reaction system once copper is included as a fourth chemical element.
In summary, depending on the implemented operational conditions, it
possible to obtain both sulphates together or a mixture containing
R. Souza et al.
Fig. 1. Experimental apparatus schematic design.
Fig. 2. Cu-S-O reaction system at a fixed temperature of 873 K (600 °C).
Fig. 3. Cu-S-O reaction system at a fixed O2(g) partial pressure of 21 × 103 Pa.
CuSO4 and Fe2O3, as the copper sulphate region encompasses the dia-
gram area associated with iron sulphate.
Fig. 5 shows the predominance diagram as a function of tempera-
ture and SO2(g) partial pressure, fixing the O2(g) partial pressure at
21 × 103 Pa. Comparing the resulting diagram with the one obtained
previously (Fig. 3), FeSO4 dissociates at lower temperatures in com-
parison to CuSO4. It is important to mention that, at these temperatures,
the operational conditions are auspicious for copper maintenance as
sulphate while iron oxidizes.
Although it is possible to draw some conclusions regarding the ne-
cessary circumstances for CuSO4 and Fe2O3 transformation, this ther-
modynamics approach does not consider the possibility of simultaneous
formation, as only one species bearing copper or iron is described as
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Minerals Engineering 130 (2019) 156–164
Fig. 4. Fe-S-O reaction system at a fixed temperature of 873 K (600 °C).
Fig. 5. Fe-S-O reaction system at a fixed O2(g) partial pressure of 21 × 103 Pa.
feasible at a certain condition.
Therefore, in order to evaluate this scenario, calculations employing
Gibbs free energy minimization methods should be carried out. This
could also be presented in terms of diagrams showing the equilibrium
composition as a function of temperature.
3.2. Equilibrium compositions
3.2.1. Sulphates thermal stability
As discussed previously, there is an indicative that it is possible to
obtain CuSO4 and Fe2O3 selectively, since copper sulphate tends to be
more stable at a higher temperature. Sulphates thermal decomposition
starts at specific temperatures and continue until complete exhaustion
R. Souza et al. Minerals Engineering 130 (2019) 156–164

Fig. 6. Equilibrium composition for CuSO4 thermal decomposition.

Fig. 8. Equilibrium composition for CuS and FeS oxidizing roasting.

Fig. 7. Equilibrium composition for FeSO4 thermal decomposition.

of the salt while forming preferentially oxides and SO2(g)/SO3(g).

Therefore, these are appreciated for copper and iron sulphates, re-
spectively, in Figs. 6 and 7.
It can be observed that FeSO4 starts to decompose at around 700 K
(427 °C) while the same process for CuSO4 initiates at about 900 K
(627 °C). The former is completely depleted at 1100 K (927 °C) while
the latter is no longer present in the diagram after 1300 K (1027 °C).
Thus, it is thermodynamically possible to begin dissociating iron sul- Fig. 9. Equilibrium composition for CuS and FeS sulphatizing roasting.
phate to its respective oxides, starting as Fe2O3, maintaining the copper
sulphate unchanged, while the opposite is unfeasible. oxidizing roasting is no longer present. In this scenario, combining
oxygen and sulphur dioxide, CuSO4 is the sole copper bearer compound
until 950 K (677 °C). In spite of narrowing the temperature range in
3.2.2. Copper-iron sulphides roasting
which the desired selectivity is possible, the results are stimulating
In this section, the roasting of copper-iron sulphide minerals is ap-
regarding the operation of this particular system, since it provides
preciated for CuS and FeS. From this perspective, the equilibrium
safety improvements in relation to temperature variations within the
composition associated with an oxidizing roasting was calculated for a
process furnaces, as copper sulphate now dissociates at a higher tem-
pure oxygen atmosphere. The results are shown in Fig. 8.
perature.
It can be noticed that, as expected, copper and iron sulphates are
Therefore, it is clear that it is thermodynamically feasible to oxidize
formed at low temperatures. However, for these conditions, iron oxide
copper and iron sulphides forming selectively copper sulphate and iron
is also formed in the whole temperature range. Moreover, CuSO4 de-
oxide within a particular temperature range, as demonstrated through
composition behaviour is distinct at this environment, with a slight
the minimum Gibbs free energy calculation of this reaction system.
decrease in its composition above 600 K (327 °C) followed by small
increments of CuO and CuO·CuSO4 quantities. Nevertheless, the selec-
tive formation of CuSO4 and Fe2O3 is possible but with some loss in 4. Results and discussion
copper recovery due to oxides formation.
On another approach, Fig. 9 presents the equilibrium composition 4.1. Concentrate sample characterization
results related to a sulphatizing roasting of CuS and FeS.
With sulphur dioxide enrichment, the reaction atmosphere provided Regarding size distribution, the received material exhibited 54% of
conditions for sulphates stabilization at higher temperatures. The pre- its particles smaller than 100 mesh (0.150 mm), while 21% of the
sence of SO2(g) leads to a more significant effect through iron, stabi- material was retained in a 24 mesh sieve (0.850 mm). Therefore, the
lizing this element as Fe2(SO4)3 until about 800 K (527 °C) without the sample was ground until all particles were smaller than 150 mesh
premature formation of Fe2O3. For copper, the observed behaviour in (0.105 mm), in order to obtain a homogeneous material. This was

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Fig. 10. XRD pattern of the sulphide concentrate.

evaluated as an interesting procedure to also mitigate the effects asso- Table 2

ciated to particle size distribution in the subsequent gas-solid reactions. ICP-MS analysis of the copper concentrate.
Fig. 10 presents the concentrate sample XRD pattern and Rietveld Samples Weight/%
analysis. Chalcopyrite (CuFeS2), in its two phases, is the main con-
stituent of the concentrate with a contribution of around 83%. Quartz Cu Fe S
(SiO2) was also identified in this material. The difference of the ob-
1 21.5082 21.2396 22.9905
tained signal and the one calculated for the Rietveld analysis indicates 2 21.3381 20.9818 23.0602
that other minerals may be present in the concentrate, in lower
amounts.
The SEM-EDS analysis presented in Table 1 indicates that these as the proposed pyrometallurgical process to produce CuSO4 and Fe2O3.
minor occurrences could be associated to other gangue minerals, since,
besides quartz, Mg, Al, K, Ca, Mn and Zn were also detected. The re-
spective weight percentage of chalcopyrite elements (e.g. Cu, Fe and S) 4.2. Copper-iron sulphides roasting
were of around 20%, consistent with the value identified in the ICP-MS
analysis (Table 2). Thus, for this concentrate and characterization The chemical processing experiments were evaluated as function of
equipment, the SEM-EDS method can be applied to analyse the weight the total weight variation as each one of the possible reaction system
percentage of these elements in a semi-quantitative approach, with a selectivities is preferentially associated with a certain value as it can be
certain degree of confidence. observed in Table 3.
The characterization results indicate that this concentrate presents a The full conversion into sulphates is associated with a mass gain of
copper weight percentage that seems incompatible with the usual metal around 70%, while the formation of the respective higher oxides is
extraction processes, classifying this material as low grade copper associated to a mass loss of about 26%. The remaining selectivities are
concentrate and, thus, encouraging its use in alternative processes, such related to the concomitant formation of sulphate and oxide, and display
a positive weight percentage variation between 26 and 30%. However,
the thermodynamics evaluation indicated that CuSO4 and Fe2O3 se-
Table 1
SEM-EDS analysis of the concentrate.
lectivity display a higher probability of occurrence, especially in an
SO2(g) enriched atmosphere. Therefore, a mass gain around 30% is an
Element Weight/% adequate indicative of the desired selectivity.
O 25.09 Preliminary experiments indicated that the chemical processing of
Mg 0.84 the concentrate should be carried out in temperatures below 1073 K
Al 2.46
Si 4.16 Table 3
S 19.57
Reaction system mass balance.
K 0.76
Ca 1.11 Reaction system selectivity Weight variation/%
Mn 0.93
Fe 21.21 CuSO4 + FeSO4 +69.75
Cu 20.57 CuO + Fe2O3 −26.29
Zn 3.30 CuO + FeSO4 +26.12
Total 100.00 CuSO4 + Fe2O3 +30.48

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Table 4
SEM-EDS analysis of the material roasted in
air.
Element Weight/%

O 39.30
Mg 1.09
Al 3.10
Si 4.25
P 0.99
S 11.46
K 0.31
Ca 0.82
Mn 4.21
Fe 14.41
Cu 14.87
Zn 5.19
Total 100.00

dissociation with increasing temperature. However, a more oxidizing

Fig. 11. Roasting results as a function of temperature for each evaluated re-
action atmosphere chemical composition.
(800 °C), since the system displayed mass loss behaviour in this con-
dition. This was identified in an experiment conducted with compressed
air, with material weight loss of around 27%. Therefore, the upper limit
for the reaction temperature in this study is 1023 K (750 °C); while the
lower limit is 873 K (600 °C) in order to allow iron sulphate dissocia-
tion.
Fig. 11 presents the experimental results as function of total weight
variation, reaction temperature as well as atmosphere inside the tubular
furnace.
All curves display a total weight variation associated to a mass loss
at 1023 K (750 °C). However, it is interesting to note that the trend for
mass loss seems to begin at 973 K (700 °C), both for the compressed air
atmosphere and sulphur dioxide enriched atmosphere. This behaviour
is not observed in the curve associated to a pure oxygen atmosphere, as
this highly oxidizing atmosphere appears to favour sulphate
atmosphere provides a weight variation at 600 K (873 °C), closer to the
one associated with CuSO4 and Fe2O3 formation compared to the one
obtained in a compressed air atmosphere. This particular behaviour
could be associated to insufficient oxygen offering to the system in the
latter reaction atmosphere, minimizing the chemical attack over chal-
copyrite. Regarding the O2(g) atmosphere enriched with SO2(g), a mass
gain of around 25% at 873 K (600 °C) and 923 K (650 °C) is a good
indication of copper sulphate formation alongside with iron oxide. As
expected, the sulphur dioxide presence within the reaction atmosphere
seems to dislocate the copper sulphate dissociation equilibrium, stabi-
lizing it at higher temperatures. In order to appraise the selective for-
mation of the desired products, samples from the most interesting re-
sults were collected and submitted to characterization methods.
4.3. Reaction products characterization
Fig. 12 presents the XRD pattern of the material roasted in com-
pressed air at 873 K (600 °C) while Table 4 displays the SEM-EDS results
for the same sample.

Fig. 12. XRD pattern of the material roasted in air.

161
R. Souza et al.
Fig. 13. XRD pattern of the material roasted in the enriched atmosphere.
Fig. 14. Blue liquor obtained after filtering.
The XRD pattern indicates that varying species were formed.
However, the semi-quantitative analysis by the Rietveld method in-
dicated a significant percentage of chalcocyanite (CuSO4) and hematite
(Fe2O3), at 44.69 and 40.00% respectively. This suggests a higher
conversion of chalcopyrite contained in the concentrate into com-
pounds with the desired selectivity, even considering a semi-quantita-
tive evaluation. Nevertheless, the presence of certain sulphides, such as
chalcocite (Cu2S) and marcasite (FeS2), indicate that the oxygen offered
to the system may well be below the necessary amounts for selective
CuSO4 and Fe2O3 formation. Regarding the SEM-EDS analysis, oxygen
weight percentage increments are associated to copper, iron and, most
expressively, sulphur depletion. This is an interesting indicative that the
reaction is being processed according to the desired formation. In
general terms, it can be said that some oxygen could have been in-
corporated either as sulphate or oxide with some sulphur removal,
probably as SO2(g), which can be used to then stabilize the copper
sulphate.
As suggested by the total weight variation, the enriched atmosphere
exhibited the best results regarding the desired selectivity. The resulting
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Minerals Engineering 130 (2019) 156–164
XRD pattern for a sample collected after an experiment carried out at
923 K (650 °C) is displayed in Fig. 13.
It seems that, under these operational conditions, chalcocyanite
formation is indeed enhanced, as it was the only copper bearing com-
pound identified in this analysis, at about 56% of the sample. The ab-
sence of minor iron sulphides indicates that full conversion into an
oxide was also favoured as hematite, at approximately 35%, was the
only Fe containing constituent.
In order to evaluate the formation of a soluble fraction associated
with CuSO4, a test was carried out in slightly heated deionized water to
determine the solubility of the resulting material, after roasting with
O2(g) and SO2(g). After filtering, a blue liquor was obtained (Fig. 14),
possibly associated to copper sulphate, as well a brownish powder
which was also characterized by XRD and SEM-EDS. No copper material
was detected in the solid material, indicating a high recovery of this
metal as CuSO4 in the blue liquor. The non-soluble fraction character-
ization is presented in Fig. 15, where it is possible to observe that the
non-soluble fraction is mainly composed by hematite, with a con-
tribution around 86%, and with the minor presence of quartz at about
14%. No copper bearing phase was identified in the solid, confirming
that all Cu content is probably being transferred to the blue liquor.
These results indicate that, in a first evaluation, it is possible to
selectively produce and also separate CuSO4 and Fe2O3 using a simple
method (e.g. roasting with the re-use of the formed SO2(g) and solu-
bilisation in water). This method could be a promising use of low grade
copper concentrates, leading to applications in the non-metallurgical
sector. It is worth mentioning that the roasting-leaching route has be-
come an established method to process certain materials, such as
copper-cobalt sulphidic ores from the Central African Copperbelt
(Güntner and Hammerschmidt, 2012). However, the results reported
herein confirmed the thermodynamics of the process and also proposed
the incorporation of the generated gaseous products as atmosphere
enrichment. A positive effect on CuSO4 and Fe2O3 formation, as well as
recycled a fraction of sulphur dioxide, was observed, thereby providing
a certain level of mass integration, without compromising the process
conversion.
R. Souza et al.
Fig. 15. XRD pattern of the non-soluble fraction of the roasted material.
5. Final remarks
The copper bearing sulphide concentrate used herein is very sensi-
tive to roasting operational conditions. Its transformation from copper
and iron sulphides into CuSO4 and Fe2O3 can be achievable after the
implementation of a specific condition, in which the reaction quotient
favours the desired selectivity through recycling of the SO2(g) gener-
ated by the chemical reaction itself.
The thermodynamic evaluations carried out herein indicate the
feasibility of the simultaneous formation of copper sulphate and iron
oxide. The calculations are in agreement with the expectations of de-
creasing sulphate stability with increasing temperatures. CuSO4 begins
decomposing at around 900 K (627 °C), while the same process for
FeSO4 begins at about 700 K (427 °C). Assessments on the presence of
SO2(g) in the reaction system indicated that this trend remains the same
with copper sulphate dissociating at a higher temperature than in the
previous case. Therefore, the implementation of a reactive atmosphere
containing a certain SO2(g) partial pressure, allows for CuSO4 stability
without compromising FeSO4 dissociation.
Roasting results were improved in terms of total weight variation. In
fact, the proposed methodology allowed for complete separation of Cu
from Fe. To achieve this, the roasting must be conducted above 873 K
(600 °C), in order to promote ferrous sulphate dissociation. As expected,
the presence of sulphur dioxide within the reaction atmosphere seems
to hinder the copper sulphate dissociation, stabilizing the reaction at a
higher temperature.
The resulting material characterizations clearly point out the pos-
sibility of selectively obtaining CuSO4 and Fe2O3 by applying the pro-
posed methodology using a low copper content concentrate. The solu-
bilisation tests conducted using the roasted materials indicate complete
copper containing species solubility, as the filtered material was mainly
consisted of hematite (Fe2O3) and quartz (SiO2), as revealed by XRD.
Acknowledgments
This study was financed in part by the Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) –
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Minerals Engineering 130 (2019) 156–164
Finance Code 001. The authors are also grateful for the financial sup-
port and scholarships from the Conselho Nacional de Desenvolvimento
Científico e Tecnológico – Brasil (CNPq) – and the Fundação de Amparo
à Pesquisa do Estado do Rio de Janeiro – Brasil (FAPERJ).
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