Journal
of Metallurgical Engineering (ME) Volume 2 Issue 4, October 2013 www.me‐journal.org
Enargite Treatments and Pressure Oxidation
of Concentrates Cu/L As/PRP
Kimberly Conner1, Corby Anderson*2
Department of Metallurgical & Materials Engineering, Colorado School of Mines
1500 Illinois Street, Golden, Colorado, USA
1 [email protected]; *[email protected]
Abstract base metal sulfides (chalcopyrite, chalcocite, covellite,
Due to increasingly stringent worldwide environmental digenite, tennantite, sphalerite, galena). Enargite may
regulations for gaseous, aqueous and solid waste emissions, contain minor amounts of other elements (Sb, Ag, Fe).
conventional smelting technology causes difficulties when The presence of Sb (up to 6 wt %) is quite common,
treating materials containing arsenic. Many globally significant and important from an environmental point of view;
copper properties have copper sulfide mineralogy that has a enargite is frequently associated with Sb‐bearing
high arsenic content present as enargite. Often, the enargite minerals (Lattanzi et al. 2008).
is present as very large resources with significant amounts of
contained precious metals. As global copper, silver and gold Enargite is a complex copper‐arsenic sulfide mineral,
demand increases while significant world resources decrease, that typically contains significant gold and silver
treatment of sulfide orebodies with enargite is becoming values, and poses many process challenges. Large
increasingly important. A review of enargite treatment enargite deposits are found in Chile as well as other
technologies are discussed as well as a basic overview of an countries and the increasing demand for copper and
evaluation of the selective dissolution and fixation of arsenic gold have encouraged research into developing more
while leaving behind a clean copper and precious metals‐
effective methods of extracting metals of value from
bearing concentrate suitable as a smelter feed.
enargite concentrates (Peacey, Gupta, and Ford 2010).
Keywords
The compound Cu3(As,Sb)S4 occurs naturally in two
Enargite; Pressure Oxidation; Arsenic crystallographic forms: orthorhombic and tetragonal.
The orthorhombic form is enargite (Cu3AsS4) and the
Introduction tetragonal forms are luzonite (Cu3AsS4) and famatinite
When treated pyrometallurgically, arsenic minerals (Cu3SbS4) (Springer 1969). It has been suggested that
tend to decompose easily by forming oxides or enargite is a high temperature modification of luzonite
sulfides that are volatile and report as a gas phase. (Maske and Skinner 1971).
Some stay in the metal phase and cause an impure Enargite Surface Properties
final copper product.
In a study of the surface properties of enargite as a
High arsenic‐containing concentrates can be smelted
function of pH, it was observed that the sign and
directly, but most copper smelters limit their total
magnitude of enargite’s zeta potential is governed by
arsenic inputs for both environmental and economic
the adsorption of the hydrolysis products of the As‐
reasons. The average arsenic level in custom copper Cu‐S‐H2O system formed at the mineral/solution
concentrates has also been increasing, further limiting interface. The zeta potential of enargite was found to
the potential market for high‐arsenic enargite concentrates
be quite sensitive to changes in pH, probably due to
(Peacey, Gupta, and Ford 2010).
several simultaneous ionization and disassociation
reactions (Castro and Baltierra 2005). Electrochemical
Properties of Enargite
oxidation and reduction of enargite were performed in
Enargite, Cu3AsS4, is a blackish gray mineral with a 0.1 M HCl solution. The presence of Cu2+, sulfate and
metallic luster, Mohs hardness of 3, a density of 4.5 chloride were detected at potentials above 0.2V, while
g/cm3 and acts as a semiconductor. Copper is in the at potentials below 0.6V the oxidation of arsenic was
monovalent state, and arsenic in the pentavalent state. detected. Dissolved sulfur increased under reducing
In most natural occurrances, enargite is associated conditions forming H2S and at oxidizing conditions
with pyrite, and other copper and/or arsenic and/or forming sulfoxy species. The sulfur was believed to be
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responsible for the observation of an active‐passive Fornasiero, and Ralston 1999b). These two studies
transition at 0.3V (SCE) (Ásbjörnsson et al. 2004). provided a qualitative perspective on the species
present at the mineral surface.
Selective flotation of synthetic enargite (18.94% As)
from natural chalcopyrite under varied pulp potentials Work was performed to investigate the effect of
was conducted to investigate the feasibility of enargite milling in different atmospheres on the leaching of
removal from a chalcopyrite concentrate. The sample enargite with HCl. Extended ball milling of enargite
for flotation consisted of 50% synthetic enargite and concentrate for 50 hours in an argon atmosphere
50% natural chalcopyrite. The test results indicate that resulted in little change in solubility. An air
chalcopyrite began to oxidize quickly at a much lower atmosphere showed a slow increase in dissolution
potential than enargite. Selective flotation revealed with increased milling. The milling of enargite in an
that enargite can be successfully removed from oxygen atmosphere at elevated temperature led to
chalcopyrite through controlling the pulp potential increased linear solubility of enargite due to the
above +0.2V and below +0.55V (SCE). The flotation formation of CuSO4 and As2O3, both of which are
results show that at a pulp potential of 0.5V (SCE), soluble in the 0.5M HCl leachant. The oxygen partial
93.4% enargite was floated into the concentrate with a pressure, following first‐order kinetics, appeared to
grade of 92.8% enargite, and 92.6% chalcopyrite was have the largest effect. (Welham 2001).
recovered in the tailings at 93.2% chalcopyrite (Guo
and Yen 2005). The electrochemical behavior of natural Enargite Treatments
enargite in an alkaline solution was studied under
Pyrometallurgical Processing
conditions pertinent to those used in flotation of
sulfide minerals. Photoelectrochemical experiments Pyrometallurgical processing of enargite concentrates
confirmed that the samples studied were p‐type has been shown to remove arsenic, but the problem is
semiconductors. The potential range where the handling of the arsenic‐containing species and long
photocurrent was noticeable (below ‐0.4 ±0.2V vs. SCE) term stability (Kusik and Nadkarni 1988).
is more negative than the potential range of flotation Decomposition of enargite in a nitrogen atmosphere at
(near 0.0V vs. SCE). It is believed that a surface layer 575‐700˚C proceeded in two sequential steps forming
forms over the potential range studied, and the law for tenantite as an intermediate compound (Padilla, Fan,
the growth of this layer corresponds to two processes: and Wilkomirsky 2001). Sulfidation of chalcopyrite‐
the formation and dissolution of the layer (Pauporté enargite concentrate at 350‐400˚C resulted in rapid
and Schuhmann 1996). conversion of the chalcopyrite to covellite and pyrite.
This was followed by pressure leaching in sulfuric
The oxidation of synthetic and natural samples of acid with oxygen (Padilla, Vega, and Ruiz 2007).
enargite and tennantite were compared through
dissolution and zeta potential studies. The changes in One commercial process for treating large quantities of
zeta potential with pH and oxidizing conditions are enargite concentrates is the Outotec Partial Roasting
consistent with the presence of a copper hydroxide Process. It includes partial roasting at 600‐750˚C to
layer covering a metal‐deficient sulfur‐rich surface. produce a low‐arsenic calcine and arsenic trioxide for
The amount of copper hydroxide coverage increases sale or storage. The low‐arsenic calcine was sold to
with oxidation conditions. Arsenic dissolution was copper smelters. The sale of significant amounts of
arsenic trioxide is no longer possible but scrubbing
much lower than copper and does not appear to
from copper smelter gases and fixation in an
contribute to the mineral oxidation. The work showed
environmentally acceptable manner is well‐proven
that the natural samples of tennantite and enargite
(Lattanzi et al. 2008; Peacey, Gupta, and Ford 2010).
oxidize more than the synthetic samples in alkaline
conditions, and tennantite oxidizes more than enargite The Namibia Custom Smelter (NCS), owned by
(Fullston, Fornasiero, and Ralston 1999a). The surface Dundee Precious Metals, Inc. (DPM), is located in
oxidation of synthetic and natural samples of enargite Tsumeb, Namibia which is approximately 430 km
and tennantite were monitored by X‐ray photoelectron north of the capital, Windhoek. The smelter is one of
spectroscopy (XPS). The XPS results showed that the only a few in the world able to treat arsenic and lead
oxidation layer on the mineral surface is thin and the bearing copper concentrate. Chelopech, also owned
products are comprised of copper and arsenic by DPM, sends their concentrate to be processed by
oxide/hydroxide, sulfite, and a sulfur‐rich layer of this smelter. For the year of 2011, NCS processed
metal‐deficient sulfide and/or polysulfide (Fullston, 88,514 mt of Chelopech concentrate and 91, 889 mt of
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concentrate from third parties for a total of 180,403 mt. into crystalline CuO and arsenic dissolves forming
Since acquiring NCS in 2010, DPM embarked on an AsO43‐. The reaction rate was very fast and chemically
expansion and modernization program designed to controlled (Curreli et al. 2005; Vinals et al. 2003).
bring the smelter into the 21st century from a health,
Dissolution of enargite in acidified ferric sulfate
safety and environmental perspective. The first phase
solutions at 60‐95˚C yielded elemental sulphur, sulfate
of the project was designed to address arsenic
sulfur and sulfate with dissolved copper and arsenic.
handling. They expanded the Ausmelt furnace, a
The dissolution kinetics were linear and copper
superior furnace from an environmental point of view,
extraction increased with increasing ferric sulfate and
enabling them to perform all primary smelting
sulfuric acid concentration (Dutrizac and MacDonald
through the Ausmelt, allowing the older reverbatory
1972). Leaching of enargite in acidic sulfate and
furnace to be used as a holding furnace. A new
chloride media resulted in complete dissolution at
baghouse was also being installed and all the existing
temperatures above 170˚C (Riveros, Dutrizac, and
systems designed to manage the arsenic were
Spencer 2001). At <100°C, enargite dissolves slowly in
upgraded. Upon completion of the two phases of the
either Fe(SO4)1.5 or FeCl3 media, and the dissolution
project, the specialty smelter at Tsumeb will be
rate obeys the shrinking core model. The rate
repositioned to be one of the most unique smelters in
increases with increasing temperature and the
the world, with the ability to treat DPM and third
apparent activation energies are 50‐64 kJ/mol. The rate
party complex concentrates in a responsible and
increases slightly with increasing FeCl3 concentrations
sustainable manner that meets Namibian as well as
in 0.3M HCl media. The leaching of enargite at
global health, safety and environmental standards
elevated temperatures and pressures was also
(“Annual Review 2011” 2012).
investigated. Potentially useful leaching rates are
Hydrometallurgical Processing achieved above 170°C, at which temperature sulfate,
rather than sulfur, is produced. Lower temperatures
Several new hydrometallurgical processes have been (130‐160°C) lead to fast initial leaching rates, but the
developed to treat copper sulfide concentrates and dissolution of the enargite is incomplete because of the
may be suitable for enargite including atmospheric coating of the enargite particles by elemental sulfur
leaching, bio‐oxidation and pressure oxidation. The (Riveros and Dutrizac 2008).
advantage of hydrometallurgy over roasting is that the
arsenic can be precipitated directly within the leach Enargite dissolution in ammoniacal solutions was
reactor as ferric arsenate (Peacey, Gupta, and Ford slow and 60% of copper was extracted after 14 hours
2010). (Gajam and Raghavan 1983).
The study of the separation of enargite and tennantite In the case of gold‐bearing enargite concentrates,
from non‐arsenic copper sulfide minerals by selective leaching with basic Na2S has been shown to selectively
oxidation or dissolution showed that it is difficult to solubilize the arsenic, and some gold, but does not
use flotation to separate chalcocite, covellite or affect the copper. The copper is transformed in the
chalcopyrite from enargite or tennantite under normal leach residue to a species Cu1.5S and the gold is partly
oxidation conditions. Improved separation occurred solubilized in the form of various anionic Au‐S
at pH 5.0 after selective oxidation with H2O2, or at pH complexes. The gold and arsenic could then be
11.0 after oxidation with H2O2 followed by EDTA recovered from solution. The author did not quantify
addition to selectively remove surface oxidation the gold leached (Curreli et al. 2009). Other work had
products (Fornasiero et al. 2001). indicated that leaching with sodium sulfide in 0.25M
NaOH at 80‐105°C will dissolve sulfides of arsenic,
Bulk oxidation of enargite in air is a slow process.
antimony and mercury (Nadkarni and Kusik 1988; C.
Thermodynamics suggests that enargite should not be
G. Anderson 2005; C. Anderson and Twidwell 2008).
stable in acidic solutions. At acidic to neutral pH,
The selective leaching of antimony and arsenic from
oxidation/dissolution is slow but is accelerated by the
mechanically activated tetrahedrite, jamesonite and
presence of ferric iron and/or bacteria (Lattanzi et al.
enargite in alkaline solution of sodium sulfide is
2008).
temperature‐sensitive. (Baláz and Achimovicová 2006).
Arsenic dissolved from concentrate by leaching The treatment of copper ores and concentrates with
enargite with sodium hypochlorite under alkaline industrial nitrogen species catalyzed pressure leaching
oxidizing conditions where the enargite is converted and non‐cyanide precious metals recovery was
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effective in leaching copper and oxidizing the sulfide electrochemical study of enargite bioleaching by
to sulfate in a minimum amount of time while keeping mesophilic and thermophilic microorganisms showed
the arsenic out of solution through in‐situ precipitation (C. that enargite dissolution increased at higher temperatures,
G. Anderson 2003). or thermophilic conditions (Munoz et al. 2006). Leach
tests on composited sulfide ores containng enargite
Bornite, covellite and pyrite were reacted hydrothermally
and covellite achieved higher copper extraction at
with copper sulfate solutions at pH 1.1‐1.4 to produce
thermophilic conditions than mesophilic conditions
digenite which was then transformed to djurleite,
chalcocite, and chalcocite‐Q and trace djurleite (Lee et al. 2011). Arsenic‐tolerant acidithiobacillus
respectively. The bornite reaction is diffusion controlled ferrooxidans achieved oxidation dissolution of
while the covellite and pyrite are chemically controlled. enargite by forming elemental sulfur, arsenate and
A Chilean copper concentrate was hydrothermally oxidized sulfur species (Sasaki et al. 2009). The study
treated at 225‐240˚C with copper sulfate solutions to of CO2 supply on the biooxidation of an enargite‐
remove impurities. The mineral phases behaved in a pyrite gold concentrate showed a marked effect on the
similar manner as described above. Arsenic was kinetics of growth and bioleaching. Four percent
described as being moderately eliminated (20‐40%) carbon dioxide resulted in the best suspended cell
(Fuentes, Vinals, and Herreros 2009a; Fuentes, Vinals, population as well as maximum extraction of Fe, Cu
and Herreros 2009b). Hydrothermally reacting and As (Acevedo, Gentina, and García 1998).
sphalerite with acidified copper sulfate solution by
Other Processing Technologies
metathesis reaction at 160‐225°C resulted in digenite
at lower temperature and chalcocite at higher A pyro‐hydrometallurgical approach is the acid‐bake
temperature. Copper sulfide formed in a compact leach which achieved approximately 90% copper
layer around a core of sphalerite retaining the same extraction when baking at 200˚C with less than 1% of
size and shape of the original particle. The work arsenic reporting to the gas phase. Results show that
shows that sphalerite could be removed from a upon baking with 5 grams concentrated sulfuric acid
digenite or chalcopyrite copper concentrate (Vinals, per gram of contained copper, the enargite,
Fuentes, Hernandez and Herreros 2004). chalcopyrite, sphalerite and galena will be converted
Complete dissolution of enargite at 220˚C, 100 psi in to their corresponding sulfates (Safarzadeh, Moats,
120 minutes was achieved and found a sulfuric acid and Miller 2012a; Safarzadeh, Moats, and Miller
content over 0.2 molar had a negligible effect on 2012b).
dissolution (Padilla, Rivas, and Ruiz 2008). Leaching
Arsenic Fixation
of enargite in sulfuric acid, sodium chloride, and
oxygen media found arsenic dissolution was very Because arsenic is most hazardous when mobile, it
slow. About 6% of the arsenic dissolved in 7 hours at must be fixed to get it in a stable form for long‐term
100˚C (Padilla, Giron, and Ruiz 2005). Enargite storage. Two stable forms include ferrihydrite and
dissolved faster when pressure leaching in the scorodite.
presence of pyrite at 160‐200˚C than the dissolution of
pure enargite which is thought to be the result of ferric In treating hydrometallurgical solutions and waste
ions (Ruiz, Vera, and Padilla 2011). streams for the removal of arsenic, the use of
coprecipitation with Fe(III) has been specified by the
Bio‐Oxidation US EPA as the Best Demonstrated Available
Technology (BDAT). This technology has been widely
Enargite was leached faster by bacteria in sulfuric acid
adopted over the last century, and developments have
with ferric sulfate than by chemical leaching at the
been well reviewed (L. G. Twidwell, Robins, and
same or higher ion concentration (Escobar, Huenupi,
Hohn 2005). This technology has also been selected as
and Wiertz 1997). Arsenic‐bearing copper ores and
one of the Best Available Technologies (BAT) for
concentrates could be leached by Sulfolobus BC in the
removing arsenic from drinking waters (L. Twidwell
presence of ferric iron due to precipitation of ferric
and McCloskey 2011).
arsenate (Escobar et al. 2000). In evaluating bio‐
oxidation of a gold concentrate prior to cyanidation of Two ferric precipitation arsenic removal technologies
high pyrite and enargite content, the bacterial attack are presently practiced by industry: ambient
was directed toward pyrite with minimal effect on the temperature ferrihydrite/arsenic co‐precipitation and
enargite (Canales, Acevedo, and Gentina 2002). The elevated temperature precipitation of ferric arsenate.
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Journal of Metallurgical Engineering (ME) Volume 2 Issue 4, October 2013 www.me‐journal.org
The ambient temperature technology is relatively effectively generate sulfuric acid at mine sites for use
simple and the presence of commonly associated in stockpile leaching operations. Freeport‐McMoRan
metals such as copper, lead and zinc and gypsum have Copper & Gold or FCX was looking to treat
a stabilizing effect on the long term stability of the chalcopyrite concentrates with this technology and
product. The disadvantages of the adsorption developed both high and medium temperature
technology are the formation of voluminous waste processes (Marsden, Wilmot, and Hazen 2007a);
material that is difficult to filter, the requirement that (Marsden, Wilmot, and Hazen 2007b).
the arsenic be present in the fully oxidized state as Anaconda Copper Company performed work on ores
arsenate, and the question as to long term stability of from the Butte area to evaluate the possibility of
the product in the presence of reducing substances. converting chalcopyrite to digenite at about 200°C to
The disadvantages of the ferric arsenate precipitation upgrade and clean the concentrate to the point where
are that the treatment process is more capital intensive, it could be shipped as a feed to a copper smelter. They
the compound may dissolve incongruently if the pH showed that this reaction is possible and a significant
is >4, and it may not be stable under reducing or amount of the iron and arsenic (along with other
anaerobic bacterial conditions (L. G. Twidwell, Robins, impurities) were removed from the solid product
and Hohn 2005). while retaining the majority of the copper, gold and
The production of scorodite, especially from arsenic‐ silver in the concentrate. The upgrading process also
rich and iron‐deficient sulfate solutions offers a results in a lower mass of concentrate to ship, thereby
number of operational advantages such as high decreasing shipping costs. Primarily, the process
arsenic content, stoichiometric iron demand, and consists of chemical enrichment that releases iron and
excellent dewatering characteristics. sulfur from the chalcopyrite, followed by solid‐liquid
separation with treatment of the liquid effluent. This
There are two process options of industrial relevance; is followed by flotation with recycle of the middling
the hydrothermal option that involves autoclave product back to the enrichment process and rejection
processing at elevated temperature (≥150˚C) and of the tailing. The resultant product is digenite formed
pressure and the atmospheric process based on as a reaction product layer around the shrinking core
supersaturation‐controlled precipitation of scorodite at of each chalcopyrite grain. About 80% of the zinc
90‐95˚C. impurities reported to the liquor, while arsenic,
In addition to hydrothermal production of scorodite bismuth and antimony were evenly distributed
between the discharge liquor and the enriched product.
the work done by Demopoulos has determined that
Gold, silver and selenium followed the copper
it is feasible to produce scorodite by step‐wise
(Bartlett 1992); (Bartlett et al. 1986).
lime neutralization at 90°C. The atmospheric scorodite
possesses the same structural and solubility
Research Approach
characteristics with the hydrothermally produced
scorodite. Thermodynamic calculations determined The work at Colorado School of Mines was performed on
that scorodite is stable in the presence of ferrihydrite a copper‐enargite concentrate sample. The investigation
under oxic conditions up to pH 6.75 at 22°C or higher was devoted to the specific objectives below:
pH at lower temperature and gypsum‐saturated 1. A detailed thermodynamic evaluation of the
solutions (Demopoulos 2005). effects of pressure, temperature and redox
potential on the fate of the minerals present in
Pressure Oxidation the enargite. The evaluation includes the reactions
Many companies have been investigating hydrometallurgical taking place during the oxidation process, the
treatment methods for the leaching of copper corresponding values of enthalpy of reaction
concentrates as an alternative to conventional smelting and equilibrium constants, and prediction of
technology by pressure oxidation. Freeport‐McMoRan phase stability with varying conditions.
Copper&Gold has developed a sulfate‐based pressure 2. The use of a laboratory batch autoclave to
leaching technology for the treatment of copper perform the experiments.
sulfide concentrates. The main drivers for the activity 3. Developing an understanding of the kinetics of
were the relatively high and variable cost of external the proposed reactions, the products that are
smelting and refining capacity, the limited availability formed and the fate of the deleterious impurity
of smelting and refining capacity and the need to cost‐ elements.
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4. Mineralogical characterization of the feed based on experimental factors.
materials and leached solid products to 6. Fixation of arsenic from solution as ferrihydrite
optimize and confirm the desired copper phase or scorodite.
transformation.
Eh‐pH diagrams were generated using Stabcal for
5. Design‐of‐Experimentation‐based testing and enargite illustrating other solid copper phases are
modeling to quantify effects and interactions shown below:
Eh(volts)
pH
FIG. 1 Eh‐pH DIAGRAM AT 25˚C
Eh(volts)
pH
FIG. 2 Eh‐pH DIAGRAM AT 200˚C
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The experimental work is subject to confidentiality scale Continuous Bio‐oxidation of a Gold Concentrate of
constraints agreed to with Freeport‐McMoRan Copper High Pyrite and Enargite Content.” Process Biochemistry
and Gold.
37 (10): 1051–1055.
ACKNOWLEDGMENT Castro, S. H., and L. Baltierra. 2005. “Study of the Surface
Properties of Enargite as a Function of pH.” International
The authors wish to express sincere gratitude to
Freeport‐McMoRan Copper & Gold for supporting Journal of Mineral Processing 77 (2): 104–115.
this research project, especially Rick Gilbert at the FCX Curreli, L., C. Garbarino, M. Ghiani, and G. Orrų. 2009.
Technology Center. “Arsenic Leaching from a Gold Bearing Enargite
Flotation Concentrate.” Hydrometallurgy 96 (3): 258–263.
REFERENCES
Curreli, L., M. Ghiani, M. Surracco, and G. Orrų. 2005.
Acevedo, F., J. C. Gentina, and N. García. 1998. “CO2 Supply “Beneficiation of a Gold Bearing Enargite Ore by
in the Biooxidation of an Enargite‐pyrite Gold Flotation and As Leaching with Na‐hypochlorite.”
Concentrate.” Biotechnology Letters 20 (3): 257–259. Minerals Engineering 18 (8): 849–854.
Anderson, C. G. 2003. “Treatment of Copper Ores and Demopoulos, G.P. 2005. “On the Preparation and Stability of
Concentrates with Industrial Nitrogen Species Catalyzed Scorodite.” In Arsenic Metallurgy, 25–50. San Francisco,
Pressure Leaching and Non‐cyanide Precious Metals CA: TMS.
Recovery.” JOM Journal of the Minerals, Metals and Dutrizac, J. E., and R. J. C. MacDonald. 1972. “The Kinetics of
Materials Society 55 (4): 32–36. Dissolution of Enargite in Acidified Ferric Sulphate
Anderson, C.G. 2005. “The Treatment of Arsenic Bearing Solutions.” Canadian Metallurgical Quarterly 11 (3): 469–
Ores, Concentrates and Materials with Alkaline Sulfide 476.
Hydrometallurgy.” In Arsenic Metallurgy, 255–263. San Escobar, B., E. Huenupi, I. Godoy, and J. V Wiertz. 2000.
Francisco, CA: TMS. “Arsenic Precipitation in the Bioleaching of Enargite by
Anderson, CG, and LG Twidwell. 2008. “Hydrometallurgical Sulfolobus BC at 70° C.” Biotechnology Letters 22 (3):
Processing of Gold‐Bearing Copper Enargite Concentrates.” 205–209.
Canadian Metallurgical Quarterly 47 (3): 337–346. Escobar, B., E. Huenupi, and J. V Wiertz. 1997. “Chemical
“Annual Review 2011.” 2012. Dundee Precious Metals, Inc. and Biological Leaching of Enargite.” Biotechnology
Ásbjörnsson, J., G. H. Kelsall, R. A. D. Pattrick, D. J. Vaughan, Letters 19 (8): 719–722.
P. L. Wincott, and G. A Hope. 2004. “Electrochemical and Fornasiero, D., D. Fullston, C. Li, and J. Ralston. 2001.
Surface Analytical Studies of Enargite in Acid Solution.” “Separation of Enargite and Tennantite from Non‐arsenic
Journal of the Electrochemical Society 151: E250–E256. Copper Sulfide Minerals by Selective Oxidation or
Baláz, P., and M. Achimovicová. 2006. “Selective Leaching of Dissolution.” International Journal of Mineral Processing
Antimony and Arsenic from Mechanically Activated 61 (2): 109–119.
Tetrahedrite, Jamesonite and Enargite.” International Fuentes, G., J. Vinals, and O. Herreros. 2009a.
Journal of Mineral Processing 81 (1): 44–50. “Hydrothermal Purification and Enrichment of Chilean
Bartlett, R. W. 1992. “Upgrading Copper Concentrate by Copper Concentrates:: Part 1: The Behavior of Bornite,
Hydrothermally Converting Chalcopyrite to Digenite.” Covellite and Pyrite.” Hydrometallurgy 95 (1‐2): 104–112.
Metallurgical and Materials Transactions B 23 (3): 241– ———. 2009b. “Hydrothermal Purification and Enrichment
248. of Chilean Copper Concentrates. Part 2: The Behavior of
Bartlett, R. W., D. B. Willson, B. J. Savage, and R. J. Wesely. the Bulk Concentrates.” Hydrometallurgy 95 (1‐2): 113–
1986. “A Process For Enriching Chalcopyrite 120.
Concentrates.” Hydrometallurgical Reactor Design and Fullston, D., D. Fornasiero, and J. Ralston. 1999a. “Oxidation
Kinetics: 227–246. of Synthetic and Natural Samples of Enargite and
Canales, C., F. Acevedo, and J. C Gentina. 2002. “Laboratory‐ Tennantite: 1. Dissolution and Zeta Potential Study.”
121
www.me‐journal.org Journal of Metallurgical Engineering (ME) Volume 2 Issue 4, October 2013
Langmuir 15 (13): 4524–4529. Padilla, R., Y. Fan, and I. Wilkomirsky. 2001.
———. 1999b. “Oxidation of Synthetic and Natural Samples “Decomposition of Enargite in Nitrogen Atmosphere.”
of Enargite and Tennantite: 2. X‐ray Photoelectron Canadian Metallurgical Quarterly 40 (3) (January 1): 335–
Spectroscopic Study.” Langmuir 15 (13): 4530–4536. 342.
Gajam, S., and S. Raghavan. 1983. “A Kinetic Study of Padilla, R., D. Giron, and M. C. Ruiz. 2005. “Leaching of
Enargite Dissolution in Ammoniacal Solutions.” Enargite in H2SO4‐NaCl‐O2 Media.” Hydrometallurgy
International Journal of Mineral Processing 10 (2): 113– 80 (4): 272–279.
129. Padilla, R., C. A. Rivas, and M. C. Ruiz. 2008. “Kinetics of
Guo, H., and W.‐T. Yen. 2005. “Selective Flotation of Pressure Dissolution of Enargite in Sulfate‐Oxygen
Enargite from Chalcopyrite by Electrochemical Control.” Media.” Metallurgical and Materials Transactions B 39
Minerals Engineering 18 (6): 605–612. (3): 399–407.
Kusik, C.L., and R.M. Nadkarni. 1988. “Pyrometallurgical Padilla, R., D. Vega, and M. C Ruiz. 2007. “Pressure
Removal of Arsenic from Copper Concentrates.” In Leaching of Sulfidized Chalcopyrite in Sulfuric Acid‐
Arsenic Metallurgy Fundamentals and Applications, oxygen Media.” Hydrometallurgy 86 (1‐2): 80–88.
263–286. Phoenix, AZ: TMS. Pauporté, T., and D. Schuhmann. 1996. “An Electrochemical
Lattanzi, P., S. Da Pelo, E. Musu, D. Atzei, B. Elsener, M. Study of Natural Enargite Under Conditions Relating to
Fantauzzi, and A. Rossi. 2008. “Enargite Oxidation: A Those Used in Flotation of Sulphide Minerals.” Colloids
Review.” Earth‐Science Reviews 86 (1‐4): 62–88. and Surfaces A: Physicochemical and Engineering
Lee, J., S. Acar, D. L Doerr, and J. A Brierley. 2011. Aspects 111 (1‐2): 1–19.
“Comparative Bioleaching and Mineralogy of Composited Peacey, John G., Mark Z. Gupta, and Kevan J.R. Ford. 2010.
Sulfide Ores Containing Enargite, Covellite and Chalcocite “Review of Process Options to Treat Enargite Concentrates.”
by Mesophilic and Thermophilic Microorganisms.” In Proceedings of Copper 2010, 3:1035–1050. Hamburg,
Hydrometallurgy 105 (3): 213–221. Germany: GDMB.
Marsden, J. O., J. C. Wilmot, and N. Hazen. 2007a. “Medium‐ Riveros, P. A., and J. E. Dutrizac. 2008. “The Leaching of
temperature Pressure Leaching of Copper concentrates‐ Tennantite, Tetrahedrite and Enargite in Acidic Sulphate
Part I‐Chemistry and Initial Process Development.” and Chloride Media.” Canadian Metallurgical Quarterly
Minerals and Metallurgical Processing 24 (4): 193–204. 47 (3): 235–244.
———. 2007b. “Medium‐temperature Pressure Leaching of Riveros, P. A., J. E. Dutrizac, and P. Spencer. 2001. “Arsenic
Copper concentrates‐Part II‐Development of Direct Disposal Practices in the Metallurgical Industry.”
Electrowinning and an Acid‐autogenous Process.” Canadian Metallurgical Quarterly 40 (4): 395–420.
Minerals and Metallurgical Processing 24 (4): 205–217. Ruiz, M.C., M.V. Vera, and R. Padilla. 2011. “Mechanism of
Maske, Siegfried, and Brian J. Skinner. 1971. “Studies of the Enargite Pressure Leaching in the Presence of Pyrite.”
Sulfosalts of Copper; I, Phases and Phase Relations in the Hydrometallurgy 105 (3‐4) (January): 290–295.
System Cu‐As‐S.” Economic Geology 66 (6): 901–918. doi:16/j.hydromet.2010.11.002.
Munoz, J. A., M. L. Blazquez, F. Gonzalez, A. Ballester, F. Safarzadeh, M. Sadegh, Michael S. Moats, and Jan D. Miller.
Acevedo, J. C. Gentina, and P. Gonzalez. 2006. 2012a. “Acid Bake‐leach Process for the Treatment of
“Electrochemical Study of Enargite Bioleaching by Enargite Concentrates.” Hydrometallurgy. http://www.
Mesophilic and Thermophilic Microorganisms.” sciencedirect.com/science/article/pii/S0304386X12000606.
Hydrometallurgy 84 (3‐4): 175–186. ———. 2012b. “Recent Trends in the Processing of Enargite
Nadkarni, R.M., and C.L. Kusik. 1988. “Hydrometallurgical Concentrates.” Mineral Processing and Extractive
Removal of Arsenic from Copper Concentrates.” In Metallurgy Review (just‐accepted). http://www.tandfonline.
Arsenic Metallurgy Fundamentals and Applications, com/doi/abs/10.1080/08827508.2012.723651.
263–286. Phoenix, AZ: TMS. Sasaki, K., K. Takatsugi, T. Hirajima, N. Kozai, T. Ohnuki,
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Journal of Metallurgical Engineering (ME) Volume 2 Issue 4, October 2013 www.me‐journal.org
and O. H Tuovinen. 2009. “Bioleaching of Enargite by pursuing a Doctor of Philosophy in metallurgical and
materials engineering from Colorado School of Mines to be
Arsenic‐Tolerant Acidithiobacillus Ferrooxidans.” Advanced
completed in fall 2013.
Materials Research 71: 485–488.
She has worked as a Metallurgical Engineer for Newmont
Springer, G. 1969. “Compositional Variations in Enargite and Gold Corporation at the Malozemoff Technical Facility in
Luzonite.” Mineralium Deposita 4 (1): 72–74. Englewood, Colorado since May 2013. She has worked as a
Twidwell, L.G., R.G. Robins, and J.W. Hohn. 2005. “The Research Engineer for Freeport‐McMoRan Copper and Gold
at their Process Technology Center in Safford, Arizona from
Removal of Arsenic from Aqueous Solution by 2006‐2008. She worked as a Draftsman/Intern for Reynolds
Coprecipitation with Iron (III).” In Arsenic Metallurgy, Engineering Company in Alamosa, Colorado from May to
3–24. San Francisco, CA: TMS. August 2003.
Twidwell, LG, and JW McCloskey. 2011. “Removing Arsenic Ms. Conner is a professional member of SME and TMS and
has served on the SME MPD Separations Unit Committee for
from Aqueous Solution and Long‐term Product Storage.”
5 years, Student Member Affairs Committee for 3 years, and
JOM Journal of the Minerals, Metals and Materials chaired several technical sessions at various SME Annual
Society 63 (8): 94–100. Meetings.
Vinals, J., A. Roca, M. C. Hernandez, and O. Benavente. 2003. Corby G. Anderson holds a Bachelor of Science in Chemical
“Topochemical Transformation of Enargite into Copper Engineering, a Master of Science in Metallurgical
Oxide by Hypochlorite Leaching.” Hydrometallurgy 68 Engineering and a PhD in Mining Engineering – Metallurgy.
He has over 34 years of global experience in minerals, metals
(1‐3): 183–193.
and chemicals. He has held positions of responsibility in
Welham, N. J. 2001. “Mechanochemical Processing of industrial operations, management, research, consulting,
Enargite (Cu3AsS4).” Hydrometallurgy 62 (3): 165–173. design, teaching and professional sevice. He is a registered
engineer and a member in good standing of multiple
Kimberly D. Conner earned a Bachelor of Science degree in professional societies. Currently, he is the Harrison Western
metallurgical and materials engineering from the Colorado Professor of Metallurgical and Materials Engineering at the
School of Mines in Golden, Colorado in 2006 and is currently Colorado School of Mines in Golden Colorado.
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