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Hydrometallurgy 119120 (2012) 3039

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

Acid bake-leach process for the treatment of enargite concentrates


M. Sadegh Safarzadeh, Michael S. Moats, Jan D. Miller
Department of Metallurgical Engineering, College of Mines and Earth Sciences, University of Utah, 135 South 1460 East, Room 412 William C. Browning Building, Salt Lake City, UT 84112-0114, USA

a r t i c l e

i n f o

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.,

Corresponding author. Tel.: + 1 801 5815160; fax: + 1 801 5814937.


E-mail address: jan.miller@utah.edu (J.D. Miller).
0304-386X/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2012.03.002

1994; Wilkomirsky et al., 1998). Upon roasting (reductive or neutral)


or smelting enargite concentrates, arsenic-bearing gases are released
(mostly As2S3), which need to be captured, separated, oxidized, and
stabilized. This imposes further gas/dust collection and separation facilities that make such processing quite expensive. Furthermore,
pressure on smelters to reduce the quantities of SO2 and toxic metals
in fugitive gases is increasing. These features make it difcult to consider a pyrometallurgical process for the treatment of enargite rich
concentrates.
Presently, the maximum allowable arsenic content in copper concentrates for smelting is set at 0.5%. This gure is expected to be lowered in the future with an arsenic level of 0.3% being under
consideration (Baxter et al., 2010).
The leaching of refractory complex concentrates such as enargite
represent a major metallurgical challenge and several hydrometallurgical options have been shown to be unsuccessful for the leaching of
enargite concentrates. Most recently, the processing of enargite concentrates has been reviewed by Safarzadeh et al. (2011). This review
revealed that the treatment of enargite concentrates by low temperature heating in the presence of sulfuric acid has not been reported.
The invention of the acid bake-leach process dates back to 1933
(Morgan, 1933), where Morgan found that when copper suldes
were heated with concentrated sulfuric acid, all of the copper and
most of the iron present in the concentrate transformed to watersoluble sulfates. Thirty seven years later, a group of researchers
from Kennecott Utah Copper Corporation took up this process and
studied it in more detail (Prater et al., 1970). Natural specimens of
chalcopyrite, covellite, chalcocite, digenite, bornite and pyrite were
sulfated with hot concentrated sulfuric acid (180260 C). It was
found that chalcopyrite is the most reactive of the suldes with

M.S. Safarzadeh et al. / Hydrometallurgy 119120 (2012) 3039

~ 99% copper sulfation after 1 h at 190 C. The other suldes in order


of decreasing reactivity were covellite, pyrite, bornite, chalcocite,
and digenite.
While Prater et al. (1970) believed that H2S is a reaction product
during the acid bake process; Fuchs (1973) gave no indication of
H2S production in the bake reactions. It should be noted that chalcopyrite, generally known as the most refractory copper sulde in hydrometallurgical processes, was the most reactive in the acid bake
system. The authors mentioned the following advantages for the
acid bake-leach process:
The ability to treat both low and high grade copper concentrates.
The formation of elemental sulfur in the reaction.
Most of the sulfuric acid used for the process can be regenerated
from the sulfur dioxide and elemental sulfur reaction products.
Waste streams from an acid bake plant represent few disposal
problems.
While in their review of chalcopyrite treatment options Prasad
and Pandey (1998) believed that the process suffers from the release
of large amounts of iron to solution and the precipitation of iron before copper recovery has to be performed, Professor Habashi in one
of his keynote addresses remarked that the process was abandoned
because of SO2 emissions (Habashi, 2005).
The process was named the AnacondaTreadwell process
(Habashi, 2005; Subramanian and Jennings, 1972), since the Anaconda
company piloted the process in 1971 and treated ve tons/day of copper concentrate. The process was claimed to be economically competitive to smelting at that time.
There are a few reports of using the acid bake-leach process for the
treatment of other materials such as spent catalysts. The application
of sulfuric acid baking for the treatment of molybdenite concentrates
(Spedden et al., 1971), converter slags (Bulut, 2006; Hamamci and
Ziyadanogullari, 1991), and spent Ni-Mo/Al2O3 hydro-processing catalysts (Kim et al., 2009a, 2009b) has been reported. The acid bake
process, which generally is performed at a lower temperature than
its roasting counterpart, results in the direct transformation of some
metal suldes to water-soluble sulfates.
While the behavior of arsenic during the acid baking process for
copper concentrates has not been reported, Chizhikov (1966) has
studied the behavior of arsenic during the acid baking of electrolytic
zinc residues in some detail. It was shown that the presence of hydrogen sulde assists in the removal of arsenic. In this respect the reactions between the metal suldes and sulfuric acid, as a result of
which hydrogen sulde is formed, have additional signicance. For
example, after 4 h of acid baking at 200300 C ~10% of the arsenic
was volatilized from a lead dust containing 0.4% arsenic. Subsequently ~70% of the arsenic was dissolved in water leaching. Increasing the
baking temperature from 250 C to 350 C increased the arsenic volatilization by a factor of 23.
Since the acid bake-leach process was successful in the treatment
of chalcopyrite and other sulde minerals, it was decided to investigate this process for the treatment of enargite concentrates. The purpose of this study is to investigate the effect of sulfuric acid baking of
an enargite concentrate on the subsequent leaching of copper and arsenic, and the fractionation of these elements during baking and
leaching. It was experimentally shown for an enargite concentrate
that the acid baking process rendered copper, arsenic and part of
the iron soluble in water.
2. Materials and methods
An enargite concentrate from El Brocal, Peru, was used in all experiments. The concentrate had a P80 (80% passing) of ~100 m.
Fig. 1 shows a SEM micrograph of the concentrate. A variety of particle sizes and particle shapes are observed in the concentrate. The

31

mineralogical composition of the concentrate as determined by


QEMSCAN and EMPA analyses is given in Table 1.
The concentrate sample was also characterized by X-ray diffraction (XRD) analysis (see Fig. 1). The results showed diffraction lines
for enargite (Cu3AsS4) and pyrite (FeS2) conrming these are the
major minerals in the concentrate. The other components did not appear in the pattern, most likely because of their low content in the
concentrate. According to mixed acid digestion and ICP analysis, the
concentrate contained ~ 28.0 wt.% Cu and ~9.5 wt.% As.
A mufe furnace (Barnstead Thermolyne 1300 model) was used
for the purpose of baking. Analytical grade sulfuric acid (Mallinckrodt
Chemicals, 9598%) was used in the baking experiments. DI water
was used for the purpose of leaching. The leaching temperature was
controlled within 1 C with a temperature probe connected to the
hot plate. A stirring speed of 500 rpm was provided during water
leaching using a magnetic stirrer.
The acid baking experiments were performed in a porcelain crucible. Before the baking experiments, the concentrate was rinsed with
acetone to remove otation chemicals, and dried at room temperature. In each experiment, 3.00 g of concentrate was weighed and
put in the crucible. Then a certain amount of acid (5 g/g of contained
copper) was added to the concentrate and thoroughly mixed. The
crucible was weighed, and transferred to the mufe furnace, which
was preheated to the desired temperature (100, 150, 160, 170, 180,
190 and 200 C). There was no atmosphere control and the baking
was done open to the ambient atmosphere in a standard laboratory
fume hood. After a certain time (0.5, 1, 2, 3, 4, 5, 6, 7 and 24 h), the
crucible was taken out of the furnace, cooled down in the ambient atmosphere to room temperature and weighed. The amount of arsenic
released to the gas phase was calculated based upon the mass balance
between the concentrate and the baked concentrate.
The baked material, which was dry and easily friable in some
cases, and still wet in other cases, was removed from the crucible. If
dry, the baked concentrate was ground using a mortar and pestle. A
sample was taken for XRD. A 3.00 g portion of the ground material
was used for the leaching experiments. However, if the baked concentrate was still wet, the whole material was leached. The leaching
experiments were performed in a 500 mL Erlenmeyer ask. The
baked concentrate was leached for 45 min at 70 C. The volume of
DI water and the amount of baked and ground material were always
200 mL and 3.00 g, respectively. Each experiment was performed
twice, and the average of the two runs was considered for nal
calculations.
At the end of each leaching experiment, the suspension was ltered and solid residues were rinsed with DI water and dried in a furnace at 70 C over night. The residues were then weighed and
sampled for XRD. The ltrate was subjected to pH and Eh measurements. A sample of ltrate was also taken and diluted for copper, arsenic, and iron analysis by ICP-OES. Each solution was analyzed 3
times and the average value was taken as the concentration in subsequent calculations. The concentration of ferrous ions in the ltrate
was determined using the standard potassium dichromate titration
procedure.
3. Results and discussion
3.1. The effect of baking time
The effect of baking time was studied at 200 C. Increasing the
baking time increased the weight loss during baking to a maximum
of 12% within 6 h, which remained constant through 7 h of baking.
It was also observed that the amount of the baked material leached
increased by ~ 1.7% until 5 h. By increasing the time to 6 h, the amount
of the leached material decreased from 66.9% to 64.2% and then increased again to 66.8%. This behavior can be explained by the fact
that by baking the concentrate with acid until 5 h, the mixture is

32

M.S. Safarzadeh et al. / Hydrometallurgy 119120 (2012) 3039

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

FeS2 2H2 SO4 FeSO4 2S SO2 2H2 O

However, at longer reaction times (above 4 h), the scenario


changes and the ratio of Fe 2+/Fe 3+ decreased. This may have occurred as a result of Reaction (3).

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 (%)

FeSO4 ferrous sulfate 2H2 SO4 Fe2 SO4 3 SO2 2H2 O

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).

M.S. Safarzadeh et al. / Hydrometallurgy 119120 (2012) 3039

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

M.S. Safarzadeh et al. / Hydrometallurgy 119120 (2012) 3039

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).

ORP of the solution should increase for baking temperatures of above


190 C, if the Fe 3+/Fe 2+ couple is the only redox reaction taking
place. However, the ORP of the solution continuously decreased at
higher temperatures. One more complexity to explain in this case is
the higher Fe 3+/Fe 2+ ratio observed at 160 C. As stated earlier, it is
difcult to explain this behavior only based on the Fe 3+/Fe 2+ redox
couple.
Fig. 5 shows the extraction of Cu, As, and Fe upon water leaching.
It can be observed that the extraction of all metals increased by increasing the baking temperature. Cu extraction steadily increases
with a linear trend from ~ 25% at 160 C to ~90% at 200 C. Arsenic extraction follows the same trend as Cu with slightly lower extractions
and nally levels off at ~ 64% at 190 C. This may be due to the contribution to copper extraction from chalcopyrite, or the formation of insoluble arsenic compounds. Fe extraction steadily increases from ~ 8%
at 160 C to ~51% at 200 C.
In order to further investigate the phase transformations during
the baking reaction at different temperatures, XRD patterns of the

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).

leach residues were studied. Baking temperatures lower than 200 C


produced wet materials, which did not allow for XRD sampling.
Therefore, only leach residues were sampled. The results showed
that all residues contained elemental sulfur, pyrite and enargite, and
only the relative amounts of each mineral phase changed. No different mineralogical phases were found.
3.3. The effect of baking temperature at prolonged baking times
It was decided to examine the effect of prolonged acid baking at
low temperatures on the extraction of Cu, As, and Fe. Therefore,
three experiments were run at 100 C, 150 C, and 170 C over 24 h.
Increasing the baking temperature increased the weight loss to a
maximum of ~ 10% for 24 h of baking. Also the amount of the baked
material leached increased from ~67% at 150 C to ~ 70% at 170 C,
showing only ~ 3% increase. It should be noted that baked samples
at 100 C and 150 C were in the form of mud with residual acid at
the end of 24 h of baking. However, the sample baked at 170 C for
24 h went to dryness.
The pH increased from 0.7 to a maximum of 1.1 and the ORP decreased from 568 mV to 541 mV (vs. SHE) as the baking temperature
increased from 100 C to 170 C. This trend is similar to the previous
cases and hence the same explanations hold true.
At 170 C ferric ions started to form, and the ratio of Fe 3+/Fe 2+ increased. This shows the importance of time in the formation of ferric
ions, as it was noted that for 7 h of baking at 170 C, practically no ferric ions formed.
Fig. 6 shows the extraction of Cu, As, and Fe upon water leaching.
According to Fig. 6 the extraction of all metals has increased by increasing the baking temperature. Cu and As extractions have increased with the same trend reaching maxima of ~ 53% and ~46%
respectively at 170 C. Also Fe extraction reached a maximum of
~31% at 170 C.
Therefore it can be observed that extended baking times at lower
temperatures does not appear to be successful in terms of metal extraction. Also, ~11% arsenic is released to off-gases, which is another
complication with extended baking times.
The XRD patterns of the leach residues for the rst two samples,
and the baked concentrate and leach residue for the sample baked

M.S. Safarzadeh et al. / Hydrometallurgy 119120 (2012) 3039

60

porous aggregates are observed in Figs. 8a and b. The EDAX analysis


of these aggregates showed that they are composed of elemental sulfur. It can also be seen that the dense particles with smooth surfaces
observed in Fig. 8b are unreacted pyrite particles.
The behavior of copper and arsenic during the baking process
under different conditions is compared in Table 2.

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).

at 170 C were performed. Similar to the previous cases, all residues


contained elemental sulfur, pyrite and enargite, and only the relative
amount of phases changed. No different mineralogical phases were
observed. For the concentrate baked at 170 C, there were weak
peaks that could not be identied or assigned to a particular mineral
phase.
Fig. 7 shows a SEM micrograph of the concentrate sample baked at
170 C for 24 h. It is clear that the morphology of the baked concentrate is quite different from the concentrate baked at 200 C for 7 h.
Instead of the enargite particles covered with copper sulfate crystallites, a network of aggregates has been formed that makes particle
differentiation very difcult. Higher magnications indicated the formation of a layered structure within the aggregates. The EDAX analysis of these layers showed that they are most probably copper and/or
iron sulfate crystals formed on the surface of enargite particles.
The SEM images of the leach residues for the sample baked for
24 h at 170 C are shown in Fig. 8. As can be seen from Fig. 8a, the layered crystallites have disappeared and a different morphology is observed. Enargite and pyrite particles are exposed, with some marks
and cracks on the surface of enargite particles. Small white and

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

4Cu3 AsS4 s 27O2 g 12CuSO4 s 2As2 O3 s

4S l

Gr

; 200 C

7542 kJ=mol

8Cu3 AsS4 s H2 SO4 l CuSO4 s As2 O3 s H2 Sg

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

M.S. Safarzadeh et al. / Hydrometallurgy 119120 (2012) 3039

(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

Particle size Acid


(m)
amount

Bake
Bake time Arsenic
Cu
Arsenic
temperature (C) (h)
volatilization (%) extraction (%) extraction (%)

CuSO4 peaks in
baked concentrate

Enargite concentrate (present


work)
Enargite concentrate (present
work)
Enargite concentrate (Safarzadeh
et al., 2012)
Enargite
mineral
sample
(Safarzadeh et al., 2012)

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

M.S. Safarzadeh et al. / Hydrometallurgy 119120 (2012) 3039

2Cu3 AsS4 s 31H2 SO4 l 6CuSO4 s As2 O3 s 31H2 O


33SO2 g Gr

; 200 C

G 31289:16140:24T 32:98TlogT cal=mol

2Cu3 AsS4 s 9H2 SO4 l 6CuSO4 s As2 O3 s 9H2 O

Gr

; 200 C

240 kJ=mol 8
9

4Cu3 AsS4 s H2 SO4 l 26O2 g


12CuSO4 s 2As2 O3 s H2 O SO2 g

4S l

Gr

; 200 C

1360 kJ=mol
7

11S l

37

7442 kJ=mol

While Reaction Reaction (6) is not favorable, Reactions Reactions


(4), (5), and (9) are more likely to happen. Considering the above
reactions, the reason for incomplete enargite reaction may be oxygen
starvation. If the process is proved to be controlled by oxygen starvation, the reactor design becomes of primary importance. Therefore in
future experiments, the bed height of the material to be baked should
be carefully considered for experiments in a stationary bed reactor.
Sulfuric acid seems to be a sulfate donor in the process.
While copper is oxidized from +1 state to +2 state in all of the
reactions considered, less is known about the chemical state of arsenic. Considering the + 5 state for arsenic in enargite, it is always reduced to the +3 state.
5. Regarding arsenic trioxide (As2O3)
Three allotropic modications of arsenic trioxide have been
reported in the literature. The cubic form, arsenolite (melting point
272 C), is stable below 13 C. The monoclinic form, claudetite
(melting point 313 C), is stable at higher temperatures. Arsenic trioxide has a boiling point of 465 C but sublimes at 193 C (McLean
et al., 2007). An amorphous, glassy modication has also been
reported. Arsenolite is made up of As4O6 molecules. The cubic form
is slightly soluble in water. The solubility of arsenic trioxide in 100 g
of water is 1.2 g at 0 C, 2.1 g at 25 C, and 5.6 g at 75 C. The rate of
dissolution of the amorphous form is higher than that of claudetite.
Arsenic trioxide begins to sublime at 135 C (Arsenic, 1977).
It has been shown that even under low oxygen potential As2O3 gas
is stable at temperatures as low as 380390 C. The following reaction
shows the equilibrium between solid and gaseous As2O3 (Gonzlez
et al., 2003).
2As2 O3 s As4 O6 g

10

A plot of As4O6 pressure against temperature is shown in Fig. 9. It


is observed that PAs4O6 is ~ 10 3.5 atm at a temperature of 200 C.
There is a good agreement between the data obtained from HSC software and Gonzlez et al. (2003) until 325 C.
It has also been found that the oxygen potential has a strong effect
on the arsenic distribution among condensed and gas phases. For example, at high oxygen potential it is possible to form As2O5.
Arsenic trioxide is highly soluble in sulfuric acid solutions. For example its solubility in 10% sulfuric acid at 70 C is higher than 24 g/L
(Stefanakis and Kontopoulos, 1988). However, the formation of an arsenic sulfate species in aqueous solutions has not been reported. An
EhpH diagram for the As-S-H2O system at 70 C is shown in Fig. 10.
The experimental region of Eh and pH has been shown on the Eh
pH diagram. It can be observed that the major arsenic species are
arsenous acid (H3AsO3) and arsenic acid (H3AsO4) under these experimental conditions.
6. Concluding remarks
As a pyro-hydrometallurgical treatment option, the acid bakeleach process holds considerable promise for the treatment of enargite concentrates. The unique chemistry of this process allows the
treatment of refractory sulde concentrates such as chalcopyrite
and enargite. The process has been identied and applied to an
enargite-pyrite concentrate. Initial results with an enargite concentrate show that ~90% copper extraction can be achieved with only
b1% of the arsenic being released to the gas phase. According to the
results, enargite, chalcopyrite, sphalerite and galena are transformed
into their corresponding sulfates upon baking at 200 C with the addition of 5 g concentrated sulfuric acid/g of contained copper.
Of particular interest is the minimum arsenic release to the gas
phase with baking at 200 C for 7 h. Considering the lower temperatures applied in sulfuric acid baking when compared to a roasting
process, less off-gas will be produced and therefore, the size of the
equipment for gas scrubbing/purication is expected to be smaller.
The amount of produced dust is also expected to be considerably
less than in a typical roasting process.
It was shown that prolonged baking (24 h) at lower temperatures
(170 C) was not benecial as less copper extraction and more arsenic release to the gas phase were found. While no strong XRD peaks for copper
sulfate were observed in the baked samples, SEM images showed the
likely formation of copper sulfate crystallites with different morphologies

4
HSC

Gonzalez et al.

Log P As4O6 (g)

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

M.S. Safarzadeh et al. / Hydrometallurgy 119120 (2012) 3039

on the surface of enargite. Another major reaction product is elemental


sulfur, which was observed both in the XRD patterns and also in SEM
images.
The potential advantages of this process over conventional roasting are lower operating temperature, simplied copper recovery, production of elemental sulfur, and reactor design features. Further
investigation is needed to study the effects of agitation, gas phase
composition, particle size, and acid amount on the baking process.
Of critical interest is arsenic retention in the baked concentrate. Research is in progress at the University of Utah to better understand reaction stoichiometry and mechanisms involved in the acid bake-leach
process.
Important future research to improve the acid bake processing of
enargite concentrates is needed to explore the effect of particle size
and acid amount on the baking reaction. Of equal importance is also
the effect of baking atmosphere (oxidative/neutral/reductive) on
the chemistry of the process. An interesting aspect of the process is
that any galena or sphalerite is also converted to their corresponding
sulfates (detected in XRD patterns), which allows for the selective
separation of lead sulfate in the leaching stage. It is also noted, as
expected, that no chalcopyrite was observed in the leach residue, indicating its complete conversion to copper sulfate.
Acknowledgements
The authors would like to acknowledge with thanks the Newmont
Mining Corporation for providing the required funds to initiate this project and Mr. Marc LeVier, in particular, for his enthusiasm/encouragement for enargite research. We would also like to acknowledge Mr. G.
Plenge for providing the enargite concentrate. Ms. Meg Dietrich's contributions to analytical evaluations are highly recognized. The training
of STABCAL software for solution chemistry provided by Professor H-H
Huang, Montana Tech, during his stay at the University of Utah and
his continued support is greatly appreciated. Our appreciation is also
extended to Ms. Dorrie Spurlock for proofreading of the manuscript.
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