International Journal of Mineral Processing 125 (2013) 1–4

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International Journal of Mineral Processing

journalhomepage:www.elsevier.com/locate/ijminpro

Evaluation of processing options to avoid the passivation of chalcopyrite

a, a b b
Gianfranco Debernardi , Juan Carlos Gentina , Pablo Albistur , Gino Slanzi
a Escuela de Ingeniería Bioquímica, Pontificia Universidad Católica de Valparaíso, Chile. Avenida Brasil 2950, Valparaíso, Chile
b Codelco división Andina, Santa Teresa 513, Los Andes, Chile

article info abstract

Article history: The feasibility of two options to avoid the passivation of a chalcopyrite concentrate was evaluated in an oxidative process by
Received 25 June 2013 ferric ion at 30 °C. These options attempt to reduce the formation of a layer of iron precipitates, and sequentially inoculate the
Received in revised form 6 August 2013 bacterium Acidithiobacillus thiooxidans to consume the elemental sulfur layer, without modifying the oxidizing power of the
Accepted 2 September 2013 Available leaching solution.
online 17 September 2013
QEMSCAN analysis revealed a reduction in ferric compound precipitation over the mineral surface from 32% to 2% by mass
by controlling the formation of precipitates. However, the increase in the rate of copper extraction was insignificant,
Keywords:
Chalcopyrite passivation increasing this only from 3.8% to 4.0% in 30 days. The observed precipitates were mostly of type Fe-sulfates, with minor
Oxidative leaching appearance of jarosite. In neither case, QEMSCAN analysis revealed formation of elemental sulfur on the mineral.
Elemental sulfur layer Consequently, the inoculation of sulfur oxidizing bacterium A. thiooxidans in a controlled precipitation system produced no
Jarosite layer improvement in the extraction of copper.
Polysulfides The leaching behavior fitted with the model of SCM (shrinking core model), indicating the formation of a layer of undetected
compounds which exerts an effect on the diffusion of the leaching agent. Therefore, none of the op-tions taken to avoid the
passivation of chalcopyrite were successful, indicating that passivation occurs even in the absence of iron precipitation and the
presence of sulfur oxidizing bacteria.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction
Chalcopyrite passivation has been widely investigated, with no sci-entific
consensus about its causes and how to avoid it (Watling, 2006; Klauber, 2008;
Debernardi and Carlesi, 2013). To date only three possi-ble causes for this
phenomenon have been identified (i) the formation of an iron precipitate layer
that blocks the contact between chalcopyrite and the leaching solution (Stott
et al., 2000; Córdoba et al., 2008),
(ii) the formation of an elemental sulfur layer, which reduces the diffu-sion of
the leaching agent to the mineral reacting surface (Carneiro and Leão, 2007;
Munoz et al., 1979), and (iii) the formation of an intermedi-ate layer during
the dissolution reaction of chalcopyrite, such as sulfides, disulfides or
polysulfide compounds (referred to as polysulfide layer in this paper), which
have slow dissolution kinetics and hence controls the net rate of the process
(Klauber, 2008; Harmer et al., 2006; Parker et al., 2008).
The removal of the iron precipitate layer, once it has formed, has not been
successful (Stott et al., 2000). This happens because amorphous iron
precipitates undergo a crystallization process to minerals that are practically
insoluble in oxidizing conditions, such as jarosite. The in-crease in porosity of
the elemental sulfur layer has been reported as the cause of increased copper
extraction rates found when leaching with chloride-based solutions (Carneiro
and Leão, 2007; Dutrizac,
Corresponding author at: Gómez Carreño 336, Recreo Alto, Viña del Mar, Chile. Tel.: +56
9 77073926.
E-mail address: gdebernardit@gmail.com (G. Debernardi).
1990). This higher porosity diminishes the diffusional barrier created by
accumulated sulfur to the flow of leaching agents. The sulfur oxidiz-ing
bacteria Acidithiobacillus thiooxidans is capable of oxidizing elemen-tal
sulfur to sulfuric acid (Blight et al., 2009), whereby it is expected that their
presence can decrease the effects of this layer on chalcopyrite leaching rate.
In heap leaching, it is often difficult to control the conditions of the
leaching solution to avoid the formation of iron precipitates and to pro-vide
good conditions for bacterial activity. Thus, the objective of this study was to
evaluate the importance of controlling iron precipitation and the presence of
sulfur-oxidizing bacteria in solution, on the rate of copper extraction from
chalcopyrite at 30 °C with a leaching solution representative of industrial
operations.
2. Experimental procedures
2.1. Mineral concentrate
A chalcopyrite concentrate obtained from Codelco's Andina division was
used. This concentrate was dry sieved, later ET-sieved and finally fluidized
within a reactor to remove all fine particles not retained at the operating flow
rate. The recovered sample was washed with ace-tone, ethanol and distilled
water, and then dried overnight in oven at 60 °C. The particle size distribution
was 90% over 40 μm, and 5% above
100 μm. The concentrate contained 11.26% of pyrite, and the copper dis-
tribution was 98% chalcopyrite, 0.92% covellite, 0.62% bornite, 0.36%

0301-7516/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
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2 G. Debernardi et al. / International Journal of Mineral Processing 125 (2013) 1–4
enargite, 0.12% chalcocite, 0.04% tennantite/tetrahedrite, and 0.01% cop-per
oxide.
2.2. Bacterial culture
A. thiooxidans ATCC 19377 was cultured in a medium adapted from Kim
et al. (2002), referred to as SJ medium, and it contained (NH4) H2PO4 2.6
g/L, MgSO4·7H2O 0.2 g/L, KCl 0.1 g/L. The propagation was carried out in a
2 L reactor at 30 °C, with 0.5% of elemental sulfur,
1 vvm aeration, 500 rpm and pH controlled at 1.8. The sulfur was grav-ity
settled by stopping agitation and airflow, and the supernatant was centrifuged
at 15,000 ×g for cell concentration.
2.3. System description and experimental development
The chalcopyrite concentrate was fluidized by the leaching solution flow
in a fluidized bed reactor (FBR) with a decanter in its upper part, for retain by
gravity mineral particles inside the reactor. The leaching solu-tion was fed
from a stirred tank reactor (STR) to the FBR, and subse-quently recirculated
to the STR (Fig. 1). The pulp density in the FBR was 40%, with a residence
time of 0.42 min. Considering the whole sys-tem volume, the pulp density
was 3.5%.
The experimental method is based in direct comparison of copper
extraction rate from batches in the presence or absence of iron precipi-tates
and/or elemental sulfur. The batch “Control”, is performed in abi-otic media,
in the presence of 9 K medium, which is known for to generate high iron
precipitation, but without ferrous sulfate. The com-position of this medium
was (NH4)2SO4 3.0 g/L, K2HPO4 0.5 g/L, MgSO4·7H2O 0.5 g/L, KCl 0.1 g/L
and Ca(NO3)2 0.01 g/L. The second batch, called “No-Fe pp”, is analogous to
batch “Control”, but changing the 9 K medium to SJ medium. SJ medium was
confirmed to present low amounts of iron precipitation (data not shown). The
third batch, called “Biotic”, is analogous to batch “No-Fe-pp”, but the
bacterium A. thiooxidans is inoculated at zero time, to consume the elemental
sul-fur layer formed during chalcopyrite dissolution. This bacterium has no
direct oxidant effect on chalcopyrite (Bevilaqua et al., 2002).
This experimental scheme permits to evaluate the net effect of iron
precipitate layer and/or elemental sulfur on chalcopyrite extraction rate.
In all batches the conditions of the leaching solution were controlled and
adjusted in the STR to maintain the intrinsic chalcopyrite dissolu-tion
kinetics. The parameters chosen were 5 g/L of ferric ion and less than 0.1 g/L
ferrous ion (Eh N 500 mV Ag/AgCl), pH 1.8–2.0, and 30 °C. These
bioleaching parameters are representative of industrial conditions (Watling,
2006). The total iron concentration was kept con-stant by adding a ferrous
sulfate solution and H2O2 was used to oxidize ferrous ion. pH was controlled
with concentrated sulfuric acid and sodi-um carbonate solutions as necessary.
The temperature was set to 30 °C
30°
Eh pH
Fluidized bed reactor Stirred tank reactor
(FBR) (STR)
Fig. 1. Experimental setup and control parameters.
by a bath-circulator, and an oxygen saturation of about 95% was kept by
feeding air at 1 L/min to the STR. To avoid the presence of iron-oxidizing
bacteria, the mineral was heat sterilized in autoclave (Brickett et al., 1995).
The reactors and solutions used were sterilized properly.
2.4. Analytical methods
Liquid samples were taken from the STR and centrifuged for 10 min at
10,000 ×g to remove precipitates. Ferric ion and total iron were ana-lyzed by
the sulfosalicylic acid method (Karamanev et al., 2002), ferrous ion by the
modified o-phenanthroline method (Herrera et al., 1989) and total copper by
the modified bicinchoninic acid method (Debernardi et al., 2012). Eh and pH
were measured in the STR. The bacterial count was performed with non-
centrifuged samples.
Solid samples were collected using a small sterile spoon introduced at the
top of FBR to the reaction zone, removing close 2 g of mineral. The sample
was suspended in acidified water (pH 2.0) and gravity settled, discarding the
supernatant. The process was repeated 2 times. Finally the sample was dried
in oven at 60 °C.
QEMSCAN analysis was used to identify mineralogical species and
particle size distribution in solid samples. This technology confines min-eral
particles in a briquette, and then the briquette is polished. Mineral species
larger than 3 μm depth occurring in the border of the polished particles can be
detected. The equipment used was a third generation QEMSCAN, with a
SEM Zeiss EVO-50, and 4 EDS detectors.
3. Results
3.1. Effect of iron precipitates on chalcopyrite leaching
Leaching conditions were successfully controlled, achieving at all times a
ferric ion concentration between 4 and 5 g/L, Eh N 500 mV, and pH in the
range 1.8–2.0 (Fig. 2). Rapid precipitation, mainly in 9 K medium, forced the
iron additions to maintain the defined conditions, as shown in Fig. 4.
Analysis of the solid samples (Fig. 3) in “Control” batch shows an in-
creased average particle size of 50 to 80 μm, due to iron precipitation over
particles, mainly Fe-sulfates, which reach up to 30% mineral mass.
Crystalline precipitates as jarosite only reached 5% mineral mass. By
contrast, in “No Fe-pp” batch there was no increase in particle size,
precipitating 2% Fe-sulfates and less than 0.1% of jarosite. This indi-cates
that despite the iron precipitation of 7 g/L “No-Fe-pp” batch (Fig. 4) this was
not deposited on the mineral surface, accomplishing the objective of a
chalcopyrite leaching without coating the mineral by iron precipitates.
10 600
9
(g/L)
Ag/AgCl)
8 550
7 500
(mV
pH, FeT
6
5 450
Potential
2
3 400
350
1
0 300
0 5 10 15 20 25 30
time (d)
Fig. 2. Behavior of the leaching solution for batches “Control” and “No Fe-pp”. (Circles: pH,
triangles: total iron, rhombus: redox potential. Control batch: close symbols; No Fe-pp
batch: open symbols).
 G. Debernardi et al. / International Journal of Mineral Processing 125 (2013) 1–4 3

100 40 4.5
35
90 4.0

%
80 30
3.5

Copper extraction (%)

Particle 70 3.0

Mass percent,
size 25
60
(µm) 20 2.5
50
15 2.0
40
10 1.5
30
20 1.0

10 5 0.5

0
0 0.0
0 10 20 30
0 10 20 30 time (d)
time (d)

Fig. 3. Particle size and percent of iron compound precipitates on mineral particles in batches Fig. 5. Kinetics of copper extraction obtained in batch “Control” and the lot “No Fe-pp”.
“Control” and “No Fe-pp”. (Circles: particle size, triangles: Fe-sulfate content, rhombus: jarosite (●: Control, ○: No Fe-pp).
content. Control batch: close symbols; No Fe-pp batch: open symbols).

The copper extraction is presented in Fig. 5. The rapid initial leaching
corresponds to secondary sulfides, chalcocite and covellite, which con-stitute
approximately 1% copper. From this moment the leaching is chalcopyrite
based. No dissolution of enargite occurs. After 30 days there is an
insignificant difference in the extraction of copper from both batches (3.8%
vs. 4.0%), and the data fit successfully to model SCM solution (Table 1).
3.2. Effect of elemental sulfur formation in the leaching of chalcopyrite
The difference between the “Biotic” and “No Fe-pp” batches is the in-
oculation of A. thiooxidans to the startup of the “Biotic” batch. Cell adhe-sion
was quantified as cell disappearance from the leaching solution. Adherence
9
was completed within the first 4 h, reaching a concentration of 8 × 10 cells/g.
9
This value is higher than 1.5 × 10 cells/g reported by Harneit et al. (2006) as
maximum cell adhesion on a chalcopyrite concentrate (size 50–100 μm). At
regular intervals, liquid samples from STR were inoculated into flasks with
identified on the surface of chalcopyrite. This result has been found in
samples of the “Control” and “No Fe-pp” batches (data not shown).
4. Discussion
The kinetics of copper extraction were not affected by the processing
options evaluated. The poor results are of the order of those reported by
Peacey et al. (2003), who with a chalcopyrite concentrate of size
− 100# + 200# at 20 °C extracted 2% copper in 43 d.
Table 1 shows the kinetic constants obtained by fitting copper ex-tractions
to the SCM model according to Eq. (1), where X represents the percent of
copper extraction, t the reaction time, and k the kinetic constant. The proper
fitting of the results indicates the presence of a passive layer that affects the
diffusion of the oxidizing agent to the chal-copyrite surface in all batches.
2=3
1−2=3X−ð1−XÞ ¼ k t: ð1Þ

commercial elemental sulfur, presenting sulfur oxidizing activity in all cases.

The results of batch “Biotic” were similar to the “No Fe-pp” batch, re-
garding the control of the leaching solution (Fig. 2), and the formation of iron
precipitates (Fig. 3).
The copper extraction kinetics (Fig. 6) did not show any difference
compared to that observed in batch “No Fe-pp”, even the slope obtained by
fitting the data to the SCM model (Table 1) is similar. This is consis-tent with
the analysis of solid samples, in which elemental sulfur is not
12
g/L
The large decrease in the formation of Fe-sulfate precipitates among
batches “Control” and “No Fe-pp” indicates that the cause of passivation is not
related to these compounds. Nevertheless, the low amounts of jarosite, a high
crystallinity compound, found in “Control” batch (b5%), does not permit to
evaluate its passivating effect in larger quantities.
In neither batch elemental sulfur was detected by the mineralogical
analysis. It is possible that this layer was thinner than 3 μm, impeding its
detection by QEMSCAN, or that it could be volatilized by the vacuum en-
vironment where the QEMSCAN briquettes are sealed (Klauber, 2008).
In either case, there is a passivating layer which cannot be con-sumed by

10 A. thiooxidans. Recently, Blight et al. (2009) reported that A. thiooxidans is

able to consume orthorhombic elemental sulfur (commercial type sulfur), but
does not consume polymeric elemen-tal sulfur. It has not been demonstrated
Iron precipitates,

8 that the elemental sulfur formed on chalcopyrite is of orthorhombic nature.

6
Instead, Parker et al. (2008) detected by Raman spectroscopy an inactive
sulfur
4

2
Table 1
0 Fitting of copper extractions to the SCM model.

Batch −1 2
Kinetic constant (d ) R
0 10 20 30
Control 2.98E−6 0.968
time (d) No Fe-pp 3.49E−6 0.966
Biotic 3.28E−6 0.981
Fig. 4. Total iron precipitation in batches “Control” and “No Fe-pp”. (●: Control, ○: No Fe-pp).
4 G. Debernardi et al. / International Journal of Mineral Processing 125 (2013) 1–4

4.5 References
(%) 4.0

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