CONVOCATORIA
TRABAJOS TÉCNICOS Y DE INVESTIGACIÓN
ENCUENTRO DE OPERADORES
PERUMIN – 30 Convención Minera
Arequipa, 12 al 16 setiembre de 2011
Remoción de arsénico y antimonio
desde muestras de enargita usando
sulfuro de sodio
Arsenic removal from enargite
samples using sodium sulphide
F. Parada Torres – E. Asselin
Department of Materials Engineering
The University of British Columbia
Resumen
Muestras de enargita que contienen
aproximadamente 40 % Cu, 12 % As y 0.5
% de Sb fueron expuestas a un solución
conteniendo hidróxido de sodio y sulfuro de
sodio bajo diferentes condiciones. La
remoción de As y Sb es rápida alcanzando
casi un 100 % en menos de 2 horas en
algunos casos y con casi nula
solubilización de cobre. El residuo sólido
libre de arsénico y antimonio contiene todo
el cobre inicial y es apto para ser tratado
vía fundición. Las nuevas fases formadas
presentan un tamaño de partícula muy fino,
probablemente con poca cristalinidad lo
que hace difícil su identificación. Algunas
fases detectadas incluyen bornita, digenita
y NaCu5S3. La Remoción de arsénico
desde la solución fuerte puede llevarse a
cabo mediante cristalización por
enfriamiento.
Abstract
Enargite samples containing approximately
40 % Cu, 12 % As and 0.5 % Sb were
treated using a solution containing sodium
hydroxide and sodium sulphide under
different conditions. Removal of As and Sb
is fast reaching almost 100 % in less than 2
hours in some cases with practically no
copper being solubilised. The solid residue
produced is suitable for smelting. The new
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phases formed present very fine particle
size, perhaps with poor crystallinity, which
makes them difficult to identify. Some
phases found include bornite, digenite and
NaCu5S3. Partial removal of arsenic can be
achieved through crystallisation via cooling.
Background
The presence of arsenic in copper
concentrates is undesirable due to the
inability of smelters to efficiently remove it,
especially at concentrations higher than 2
% (Castro 2008). Arsenic can end up in the
final copper product thus hindering its
quality. A maximum value of 0.5 % of
arsenic in copper concentrates seems to be
accepted by most smelters without
penalties (Filippou 2007).
The alkaline sodium sulphide leaching of
enargite provides a means of selectively
removing arsenic and antimony, thus
producing a clean copper concentrate
suitable for smelting. Several authors have
studied this process (Nadkarni 1975-1988,
Anderson 1994-2005-2008, Curreli 2009,
Tongamp 2009) reporting efficient removal
of arsenic and antimony.
It has also been reported that sodium
hydroxide is used to ensure the stability of
sulphide ions in solution, which should react
with enargite to dissolve arsenic as sodium
thioarsenate (Anderson 2008, Curreli
2009). The reaction that is usually proposed
for the leaching of enargite in sulphide
solutions is as follows (Nadkarni 1988):
2Cu 3 AsS 4 3Na 2 S 3Cu 2 S 2 Na 3 AsS 4 (i)
However, a much higher value for the
second dissociation constant of H2S has
been reported, which means that sulphide
ions would hydrolize and produce
hydrosulphide, which then would react with
enargite (Giggenbach 1971, Licht 1988):
 Na 2 S H 2O NaOH NaHS (ii) 2 Results

Therefore the leaching reaction can now be Note: NaOH concentrations consider the
re-written as: hydrolization of sodium sulphide

2Cu 3 AsS 4 3NaHS 3NaOH 2.1 Effect of Temperature

(iii) Leaching of enargite was tested at 50, 65,
3Cu 2 S 2 Na 3 AsS 4 3H 2 O
80 and 95ºC. Arsenic and antimony
removal was noticeably enhanced as
This reaction has been reported by temperature increased as seen in Figures 1
Tongamp et al (Tongamp 2009) when and 2 suggesting a chemically controlled
leaching enargite with sodium process.
hydrosulphide.

The purpose of this paper is to review the

leaching of enargite using sodium sulphide,
compare results with previous findings and
provide new details regarding its chemistry
that could affect the process and take these
details into account in order to optimise it.

1 Procedure

Leaching tests were performed batchwise Figure 1: Effect of temperature on As

in a 200 ml glass jacketed cell. The leach removal at 500 RPM, P80 30 μm, 3.5 M
solution was prepared by dissolving sodium NaOH and 1.0 Na2S after 2 hours.
hydroxide first and later adding sodium
sulphide. The solution was heated up to the
desired temperature using a circulating
water bath. Once the desired temperature
was reached, 10 grams of enargite sample
were added. Samples were drawn
periodically and sent for ICP analysis. Solid
residues were analysed using ICP, XRD
and scanning electron microscopy.

A phase composition for the feed is given

on Table 1:
Figure 2: Effect of temperature on Sb
Mineral Ideal formula Weight % removal at 500 RPM, P80 30 μm, 3.5 M
NaOH and 1.0 Na2S after 2 hours.
Enargite Cu3AsS4 60.4
Quartz SiO2 5.90
Tennantite (Cu,Ag,Fe,Zn)12As4S13 4.90
2.2 Effect of agitation and particle size
Covellite CuS 3.00
Maintaining particles in suspension is key in
Pyrite FeS2 25.7 hydrometallurgical reactors. In this case
agitation does not have a noticeable effect
on the dissolution of arsenic and antimony,
thus suggesting the process is not
controlled by mass transfer in the stagnant
film and supporting the idea that it is
chemically controlled.

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Figure 3: Effect of agitation on As removal
at 95ºC, P80 30 μm, 3.5 M NaOH and 1.0
Na2S after 2 hours.
Figure 4: Effect of agitation on Sb removal
at 95ºC, P80 30 μm, 3.5 M NaOH and 1.0
Na2S after 2 hours.
Particle size, on the other hand, has a more
noticeable effect. As particle size is
decreased extraction increases.
Figures 3 to 6 show the results.
Figure 5: Effect of particle size on As
removal at 95ºC, 500 RPM, 3.5 M NaOH
and 1.0 Na2S after 2 hours.
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Figure 6: Effect of particle size on Sb
removal at 95ºC, 500 RPM, 3.5 M NaOH
and 1.0 Na2S after 2 hours.
2.3Effect of sodium hydroxide and
sodium sulphide
According to reaction (i) sulphide would
react with enargite to solubilise arsenic and
produce chalcocite. In this case hydroxide
is assumed only to raise the pH to avoid
hydrolization of sulphide (Anderson 2008,
Curreli 2009). However there seems to be
some disagreement regarding the
chemistry of sulphide in solution and it has
been reported that sulphide ions would
exist in solution only at pH values of 17 or
perhaps higher (Giggenbach 1971, Licht
1988), which supports the idea that reaction
(iii) represents the leaching procedure more
accurately. Considering these facts it
seems important to study how the leaching
process takes place when modifying
hydroxide to sulphide ratios.
Results shown in Figures 7 and 8 suggest
that both reagents (hydroxide and sulphide
or hydrosulphide) are acting in the leaching
procedure. In fact, it can be seen that when
hydroxide is increased up to 3.5 M and
sulphide is lowered to 0.5 M, As and Sb
removal is almost identical when hydroxide
is decreased to 2.0 M and sulphide is
increased to 1.0 M. This fact can help to
find an optimal ratio between hydroxide and
sulphide, especially considering that
sulphide is a much more expensive
reagent.
 Table 2: Effect of NaOH and Na2S
concentration on Cu, Fe, Zn and Ag after
leaching at 95ºC, 500 RPM and P80 of 30
μm.
Cu Fe Zn Ag
Sample
(%) (%) (%) (%)
Head 38.00 12.00 0.316 0.0193
3.5 M NaOH
48.48 12.70 0.362 0.0243
1.0 M Na2S
2.0 M NaOH
48.49 15.66 0.346 0.0239
1.0 M Na2S
1.1 M NaOH
42.39 12.45 0.330 0.0241
Figure 7: Effect of NaOH and Na2S 1.0 M Na2S
concentration on As removal at 95ºC, 500 3.0 M NaOH
49.17 15.87 0.384 0.0246
RPM, and P80 30 μm. 0.5 M Na2S
1.5 M NaOH
45.65 14.64 0.342 0.0229
0.5 M Na2S

2.5 Arsenic precipitation

During the leaching procedure arsenic and
antimony are solubilised as thio
compounds. These compounds appear to
have solubilities very sensitive to changes
in temperature, making them suitable for
crystallization via cooling (Nadkarni 1988).
Figure 8: Effect of NaOH and Na2S Tables 3 and 4 show the main arsenic
concentration on Sb removal at 95ºC, 500 species detected and the main
RPM, and P80 30 μm. crystallisation parameters, respectively.

2.4 Behaviour of copper Table 3: Main crystallised arsenic species

Some advantages of this process include Sodium sulphide Arsenate Hydrate Na3AsO2S2•11H2O
its relatively fast kinetics and the possibility Sodium Sulphide Arsenate Hydrate Na3AsO2S2•7H2O
of using atmospheric conditions. However Sodium Sulphide Arsenate Hydrate Na3AsS4•8H2O
one key feature is its selectivity; copper and
other metals such as zinc and silver are
practically 100 % left in the solid residue, Table 4: Crystallisation parameters
Precipitation parameters As Sb
which becomes an upgraded copper
concentrate. Table 2 shows a comparison Highest concentration seen (M) 1.30 0.032
between the feed and the solid residue after Concentration after precipitation (M) 0.70 0.030
leaching. Content in solid precipitate (%) 11.8 0.320
Average removal from solution (%) 42.0 4.500

Removal of arsenic can reach

approximately 40 % via crystallization of
sodium thioarsenates. This method does
not remove all the arsenic and antimony
from solution, but it is a simple procedure
and the solution can be recirculated back to
the leaching stage.

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3 Conclusions
Arsenic and antimony from an enargite
sample can be leached using sodium
hydroxide and sodium sulphide to produce
a clean copper concentrate that can be
suitable for smelting.
Copper, iron, zinc and silver remain almost
completely in the solid residue, however the
new copper phases formed are difficult to
determine with XRD.Partial removal of
arsenic and antimony from solution can be
achieved by crystallization. This depends
on the concentration of As and Sb in the
PLS.
The process presents an alternative to treat
high As/Sb copper concentrates without the
need of high temperature or high pressure
and does not produce volatile As or Sb
compounds.
Acknowledgements
The authors wish to acknowledge the
financial support of Newmont Mining
Corporation and the Natural Sciences and
Engineering Research Council of
Canada (NSERC).
Filippou, D. et al, (2007), “Recovery of
metal values from copper-arsenic
minerals and other related
resources”, Mineral Processing &
Extractive Metallurgy Reviews, Vol.
28, 247-298
Giggenbach, W, (1971), “Optical spectra of
highly alkaline sulfide solutions and
the second dissociation constant of
hydrogen sulfide”, Inorganic
Chemistry, Vol. 10, No. 7, 1333-1338
Licht, S, (1988), “Aqueous solubilities,
solubility product and standard
oxidation-reduction potentials of the
metal sulfides”, J. Electrochemical
Society: Electrochemical science and
technology, Vol. 135, No. 12, 2971-
2975.
Nadkarni, R.M and C.L. Kusik, (1988),
“Hydrometallurgical removal of
arsenic from copper concentrates”,
Arsenic Metallurgy Fundam. Appl.
Proc. Symp, 263-286
Nadkarni, R.M. et al, (1975), Method for
removing arsenic and antimony from
copper ore concentrates, US Patent #
3,911,078
Tongamp, W. et al, (2009), “Arsenic
removal from copper ores and
concentrates through alkaline
leaching in NaHS media”,
Hydrometallurgy, Vol. 98, 213-218

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