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a r t i c l e
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Article history:
Received 4 October 2011
Received in revised form 9 February 2012
Accepted 3 March 2012
Available online 11 March 2012
Keywords:
Enargite
Sulfuric acid baking
Water leaching
Arsenic
a b s t r a c t
As an alternative to roasting, low-temperature (100200 C) sulfuric acid baking of an enargite concentrate
followed by water-leaching has been evaluated. Results indicate the thermal transformation of enargite
and pyrite during sulfuric acid baking. By acid baking of an enargite concentrate at 200 C for 7 h, ~ 90% Cu
and ~ 61% As were released to the leach solution, with b 1% of arsenic being released to the gas phase. The
effects of time and temperature were studied on the baking reactions. Extended reaction times (24 h) at
lower baking temperatures (170 C) resulted in lower Cu and As extraction and higher As release to the
gas phase (~11%). The pH of the water leach solution was always ~ 0.82 after extraction due to residual
acid, making it suitable for subsequent copper recovery. The oxidation-reduction potential (ORP) of the
leach solution fell within the range 491566 mV (vs. SHE) depending on the baking conditions. The ratio
of ferric/ferrous ions in the leach solution showed considerable dependence to reaction time and temperature. Based on this study, some reactions are proposed for the sulfuric acid baking of enargite.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Enargite (Cu3AsS4), also named cuprous thioarsenate (Secco et al.,
1988), is the most frequently encountered copper arsenosulde mineral and is often found in small quantities within chalcopyrite ores
(Dutrizac and McDonald, 1972; Welham, 2001). Environmental regulations have resulted in the avoidance of high-arsenic copper concentrates due to smelter penalties related to the high arsenic content.
However, with the continued depletion of traditional copper reserves
suitable for processing with current technology, successful treatment
of the arsenic-bearing copper concentrates (enargite concentrates) is
being given considerable attention.
Control of arsenic during extractive metallurgy operations requires its removal, subsequent safe disposal and the avoidance of
emissions either in gaseous or aqueous phases (Terry and Snchez,
1995; Terry et al., 1994). Removing and storing arsenic as a stable disposable solid compound or as a saleable/marketable product is a challenging task (Riveros et al., 2001).
There have been numerous attempts to reduce the arsenic content
of ores by roasting in order to drive off arsenic and produce a clean
feed for copper smelters (Acuna et al., 2005; Bjrnberg et al., 1986;
Fan et al., 1997; Holmstrm, 1988a, 1988b, 1988c; Kusik and
Nadkarni, 1988; Luganov et al., 1995; Mkipirtti and Polvi, 1977,
1979; Padilla et al., 1997, 1998, 1999, 2001, 2010a, 2010b, 2010c;
Robins, 1988; Secco et al., 1988; Smith, 1986; Smith and Paredes,
1988; Smith et al., 1985; Terry and Snchez, 1995; Terry et al.,
31
32
1200
En
En
En: Enargite
Py: Pyrite
En
1000
XRD
600
En
En
En
Intensity
800
Py
Py
Py
En
En
En
Py
Py
En
200
En
En
Py
Py
En
400
0
20
30
40
50
60
70
80
90
100
2 Theta
Fig. 1. SEM image (200) and XRD pattern of El Brocal enargite concentrate used in this study.
still wet, and any remaining acid will also be considered in the calculations. However, after 5 h, the baked mixture becomes completely
dry, and only solid material contributes to the percentage leached.
The pH of the leach solution increased from 0.9 to 2.7, and ORP decreased from 559 mV to 491 mV (vs. SHE) as the baking time increased from 0.5 h to 7 h. The increase in pH indicates that more
sulfuric acid is consumed by the conversion of suldes to sulfates as
the reaction time increases. The decrease in ORP of the solution is
most likely due to the increase in the concentration of ferrous ions
as a result of the reaction of pyrite with sulfuric acid (Reactions (1)
and (2)). According to the Nernst equation, increasing the ratio of
Fe 2+/Fe 3+ activities will result in decreased potentials. This behavior
is in full agreement with the expected trend.
FeS2 pyrite H2 SO4 FeSO4 S H2 Sg
Fig. 2 shows the extraction of Cu, As, and Fe upon water leaching.
It is observed from Fig. 2 that the extraction of all metals increases by
increasing the baking time. Two extraction regimes can be identied,
i.e., 0.5 h to 4 h and 4 h to 7 h. In the rst regime, Cu and As follow the
same trend of extraction, whereas Fe extraction linearly increases.
After 4 h of baking ~ 65% Cu, ~ 61% As, and ~28% Fe were extracted
by water leaching. However, above 4 h of baking the extraction of
Cu increases further and reaches a plateau at baking times of 6 h
and above with a maximum extraction of 90%.
Arsenic extraction levels off at ~61% for baking times above 4 h.
This behavior may be due to the formation of insoluble arsenic compounds such as ferric arsenate, which were not detected in the XRD
analyses. Fe extraction follows almost the same trend as Cu, and increases until 6 h of baking and then remains constant at ~ 51%. The
pH of the leachate varied in the range pH 12 for all leaching tests,
which shows that acid deciency cannot be the reason for the plateau
of extraction observed.
In order to identify the phase transformations that account for Cu,
As and Fe dissolution in water, XRD patterns were studied. Baking
100
It is expected that the ORP of the solution should increase for baking times above 4 h, if the Fe 3+/Fe 2+ couple is the only redox reaction
taking place. Contrary to this fact, the ORP of the solution has continuously decreased at longer baking times, as previously explained. This
may be difcult to explain for such a complex system. Individual components (pyrite, enargite, and chalcopyrite) should be studied independently. For example, the ORP can change depending upon the
concentration of sulfur species, or the presence of other parallel
redox reactions such as an arsenic/arseneous (As(V)/As(III)) couple.
80
Extraction (%)
Cu
As
Fe
60
40
20
0
Table 1
Mineralogical analysis of the enargite concentrate used in the acid bake experiments.
Mineral Enargite
Sphalerite Galena Chalcopyrite Pyrite Quartz Calcite
phase
(Cu3AsS4) (ZnS)
(PbS)
(CuFeS2)
(FeS2) (SiO2) (CaCO3)
Wt.%
52.4
6.0
0.7
7.2
21.5
10.3
2.0
t (h)
Fig. 2. The effect of baking time on the extraction of Cu, As, and Fe by water leaching
(baking conditions: temperature 200 C, weight of concentrate: 3.00 g, sulfuric acid
amount 4.95 g. Leaching conditions: temperature 70 C, time 45 min, stirring speed
500 rpm).
times of 0.5 h through 5 h produced wet materials, thereby not allowing for XRD analysis. In this case, only leach residues were sampled. In
essence, all residues contained elemental sulfur, pyrite and enargite.
Only the intensity of peaks changed, and no additional mineralogical
phases were observed. On occasion, PbSO4 and SiO2 were detected in
the XRD patterns.
The most interesting results were observed for baking the concentrate for 6 h and 7 h, which generated dry materials that were easily
friable. For these two samples, XRD analysis was performed for both
baked concentrate and leach residues. According to the results, only
weak copper sulfate peaks were detected in baked samples. No
other new phases were found to have formed upon baking other
than elemental sulfur. The low intensity copper sulfate peaks suggest
the formation of extremely ne crystals. The formation of crystalline
copper sulfate upon acid baking of ultrane (~2 m) concentrate at
400 C has already been conrmed by XRD (Safarzadeh et al., 2012).
Of course, peaks for the water-soluble copper sulfate were not
found in the leach residue.
Fig. 3 shows the SEM micrograph of the concentrate sample baked
for 7 h. A porous structure is observed, with some new phases formed
at particle surfaces. These new needle shaped phases have a particle
size no larger than ~3 m. The EDAX analysis of these needles
shows that they are most probably copper sulfate crystals formed
on the surface of enargite particles.
The SEM image of the leach residues for the sample baked for 7 h
is shown in Fig. 4. Obviously, the small needle crystals have been dissolved away and a different morphology is observed. The particle surfaces are irregular, having some small marks similar in shape to the
crystallites observed in Fig. 3. The EDAX analysis from the surface of
one of these particles suggests these particles are most likely
unreacted enargite.
It is clear from the SEM images of the baked concentrate that all
the particles reacted to a certain extent, although the fraction reacted
is probably lower for the larger enargite particles. Therefore, with a
ner grinding of the concentrate, the conversion of enargite during
baking will probably improve. The low pH of the leach solution
shows the presence of excess acid and therefore acid deciency cannot be limiting the reaction. More research will be needed to determine if the reaction is activation or transport controlled.
33
It should be noted that the average arsenic loss to the gas phase for
the sample baked for 7 h was ~ 0.59%. An important aspect of the acid
baking process is that other suldes such as pyrite also react. Pyrite
present in the concentrate provides a cheap source of iron to precipitate and stabilize arsenic as scorodite (FeAsO42H2O). In this case depression of pyrite during otation might not be necessary, but rather
recovery in the concentrate preferred so that the pyrite would act as
an iron source for arsenic stabilization. Our previous experiments
with ultrane material showed that the formation of arsenopyrite is
also likely in the presence of pyrite (Safarzadeh et al., 2012).
3.2. The effect of baking temperature
The effect of baking temperature was studied in the range
160200 C at a xed time of 7 h. Increasing the baking temperature
increased the weight loss during baking to a maximum of 12%. It
was also observed that the amount of the baked material leached
remained almost constant at ~ 67% in the temperature range
160190 C and then increased to ~ 90% at 200 C. In fact, baking the
concentrate with acid in the temperature range 160190 C produced
wet materials with varying amounts of residual sulfuric acid, which
are included in subsequent calculations. The complete separation of
the acid from the baked mud is practically impossible. However, at
200 C the baked mixture becomes completely dry and a xed solid
material contributes to the percentage leached.
The pH of the leach solution increased steadily from 0.8 to 2.0, and
ORP decreased from 566 mV to 491 mV (vs. SHE) as the baking temperature increased from 160 C to 200 C. It was noted that the pH
signicantly increased from 0.9 (corresponding to 190 C) to 2.0 (corresponding to 200 C), which shows the great sensitivity of the sulfation reaction to temperature (more acid is consumed in sulfation
reactions at higher temperatures). Initially the ORP of the solution
remained almost unchanged from 160 C to 170 C and then decreased at 180 C. By increasing the temperature to 190 C the ORP
remained almost constant and then dropped at 200 C. Similar to
the previous explanation, increasing the ratio of Fe 2+/Fe 3+ activities
will result in decreased potentials.
At higher reaction temperatures (above 190 C), the ratio of Fe 3+/
2+
Fe (measured by titration) increased. Again, it is expected that the
EDAX
Fig. 3. SEM image of the 7 h baked concentrate (500) followed by EDAX analysis of the region shown on the image (baking conditions: temperature 200 C, weight of concentrate:
3.00 g, sulfuric acid amount 4.95 g).
34
EDAX
Fig. 4. SEM image of the leach residue for the concentrate baked for 7 h (300) followed by the EDAX analysis of the region shown on the image (baking conditions: temperature
200 C, weight of concentrate: 3.00 g, sulfuric acid amount 4.95; leaching conditions: temperature 70 C, time 45 min, and stirring speed 500 rpm).
100
Extraction (%)
80
Cu
As
60
Fe
40
20
0
150
160
170
180
190
200
210
T (C)
Fig. 5. The effect of baking temperature on the extraction of Cu, As, and Fe by water
leaching (baking conditions: time 7 h, weight of concentrate: 3.00 g, sulfuric acid
amount 4.95 g; leaching conditions: temperature 70 C, time 45 min, stirring speed
500 rpm).
60
40
4. Thermodynamic considerations
100
Cu
As
80
Extraction (%)
35
Fe
20
0
90
100
110
120
130
140
150
160
170
180
T (C)
Fig. 6. The effect of baking temperature on the extraction of Cu, As, and Fe by water
leaching (baking conditions: time 24 h, weight of concentrate: 3.00 g, sulfuric acid
amount 4.95 g; leaching conditions: temperature 70 C, time 45 min, stirring speed
500 rpm).
In view of the possible reactions that might occur during the acid
baking process, it is appropriate to look at the thermodynamics of the
system. The standard free energies of formation of the compounds involved in the reactions were obtained from HSC 5.1 software except
for enargite, which was calculated from the information provided by
Padilla et al. (2001).
At this stage of process development, the reactions that occur during the acid baking of enargite in atmospheric conditions have not
been determined conclusively. However, from the experimental results a number of reactions could be considered. Most probably, the
nal product of enargite baking is copper sulfate and a soluble form
of arsenic. This could be either As2O3 or As(III)/As(V) sulfates, with
the latter not being reported in the literature. Most probably, Fe
transforms to its corresponding sulfates, depending on the conditions
(Prater et al., 1970). The formation of elemental sulfur was also
evident. Considering the major gaseous product to be SO2, Reactions
(4)(9) could be considered for the baking of enargite.
4Cu3 AsS4 s 31O2 g 12CuSO4 s 2As2 O3 s
4SO2 g
Gr
; 200 C
8720 kJ=mol
4S l
Gr
; 200 C
7542 kJ=mol
S l
Gr
; 200 C
843 kJ=mol
EDAX
Fig. 7. SEM image of the baked concentrate (500) followed by the EDAX analysis of the region shown on the image (baking conditions: temperature 170 C, time 24 h, weight of
concentrate: 3.00 g, sulfuric acid amount 4.95 g).
36
(a)
EDAX
(b)
EDAX
Fig. 8. SEM images of the leach residue (a) 500 and (b) 200 followed by the EDAX analysis of the regions shown on the images (baking conditions: temperature 170 C, time 24 h,
weight of concentrate: 3.00 g, sulfuric acid amount 4.95 g; leaching conditions: temperature 70 C, time 45 min, and stirring speed 500 rpm).
Table 2
The behavior of enargite mineral/concentrate during the acid bake-leach process.
Feed
Bake
Bake time Arsenic
Cu
Arsenic
temperature (C) (h)
volatilization (%) extraction (%) extraction (%)
CuSO4 peaks in
baked concentrate
P80 ~ 100
200
~ 0.6
~ 90
~ 61
Not strong
170
24
~ 11
~ 53
~ 46
Not strong
400
~ 73
~ 100
~7
Strong
400
~ 40
~ 75
~ 10
Strong
P80 ~ 100
Avg. 2
b 75
5 g/g of contained
copper
5 g/g of contained
copper
0.5 mL/g of
concentrate
0.5 mL/g of
concentrate
; 200 C
Gr
; 200 C
240 kJ=mol 8
9
4S l
Gr
; 200 C
1360 kJ=mol
7
11S l
37
7442 kJ=mol
10
4
HSC
Gonzalez et al.
0
-2
-4
-6
-8
-10
-12
0
100
200
300
400
500
600
700
800
900 1000
T (C)
Fig. 9. Pressure of As4O6 (g) as a function of temperature.
Fig. 10. EhpH diagram for the As-S-H2O system (temperature 70 C, concentration of
aqueous species 0.01 m).
38
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