Hydrometallurgy 75 (2004) 177 187

www.elsevier.com/locate/hydromet

Transformation of sphalerite particles into copper sulfide particles

by hydrothermal treatment with Cu(II) ions
J. Vinalsa,*, G. Fuentesb, M.C. Hernandezb, O. Herrerosc
a

Department of Chemical Engineering and Metallurgy, University of Barcelona, Mart i Franques 1, E-08028 Barcelona, Spain
b
Department of Metallurgical Engineering, Universidad Catolica del Norte, Angamos 0610, Antofagasta, Chile
c
Faculty of Engineering, Universidad de Antofagasta, Angamos 601, Antofagasta, Chile
Received 31 May 2004; accepted 31 July 2004

Abstract
The nature of the hydrothermal reaction between sphalerite and copper solutions was investigated in the range 160225 8C.
Digenite (Cu1.8S) was the main reaction product at 160212 8C, and chalcocite (Cu2S) at 225 8C. The reaction was
characterized by the formation of a compact layer of copper sulfide around the sphalerite nuclei. Final particles retained the size
and shape of the original ZnS. Reaction rate followed a parabolic kinetic law. No significant effect of aqueous copper
concentration was observed in the range 110 g/L. An activation energy of 147 kJ/mol was obtained, indicating kinetic control
by solid-state counter diffusion of Cu+ and Zn2+ ions through the copper sulfide layer. A possible electrochemical mechanism is
discussed. The removal of zinc from digenite or chalcocite bearing copper concentrates is effective at ~225 8C, in which a high
sphalerite conversion can be achieved in times allowing autoclave processing (~1 h).
D 2004 Elsevier B.V. All rights reserved.
Keywords: Copper concentrates; Zinc removal; Sphalerite

1. Introduction
Improving bcleanQ technology in copper pyrometallurgy is expected to solve a number of environmental problems, particularly those associated with
the processing of wastes containing hazardous heavy
metals. Copper concentrates are usually produced by
selective flotation from complex sulfide minerals.
* Corresponding author. Tel./fax: +34 934021291.
E-mail addresses: vinyals@material.qui.ub.es (J. Vinals)8
gfuentes@ucn.cl (G. Fuentes)8 oherreros@uantof.cl (O. Herreros).
0304-386X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2004.07.005

Sphalerite is one of the more common impurities in

these concentrates. Mielczarski et al. (1999) have
studied and reviewed the causes of non-selective
flotation: surface activation by ions of the solution;
activation by migration of ions in solid solution to the
surface; and galvanic effects from contact with other
sulfides. Although measures can be taken to improve
selective flotation, it is currently difficult to keep zinc
levels below 2% with many complex copper ores.
The behavior of zinc during copper smelting has
been studied by Yazawa (1974) and more recently by
Degterov et al. (2000). Under the normal oxidant

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J. Vinals et al. / Hydrometallurgy 75 (2004) 177187

conditions, sphalerite is oxidized to ZnO, which

distributes mainly between the slags and dusts of the
smelting and converting processes. The prior removal
of sphalerite is beneficial not only as it reduces the
quantity of zinc in slags and dusts, but also because
sphalerite is one of the most common carriers of
extremely toxic metals (Cd, Tl, etc.). Its removal can
therefore reduce the production of hazardous wastes
in copper refineries.
Naboichenko et al. (1979) and Naboichenko and
Khudyakov (1981) studied the hydrothermal interaction of Cu2+ solutions with chalcopyrite, pyrite,
galena and sphalerite in the range 130200 8C. The
reported reactions for sphalerite were,
ZnS CuSO4aq YCuS ZnSO4aq

5ZnS 8CuSO4aq 4H2 OY4Cu2 S

5ZnSO4aq 4H2 SO4aq

with reaction (2) becoming dominant at higher

temperatures. Kinetic data showed first-order dependency of the [Cu2+] for CuSO4/ZnSb1, and reaction
order b1 for CuSO4/ZnSN1 ratios. The reported
activation energy was 58 kJ/mol at initial rates and
96 kJ/mol at high solid conversion. On the other hand,
Serova et al. (1992) have studied the hydrothermal
reaction of Cu2+ with a complex Cu/Zn concentrate in
the range 160190 8C. The best reported conditions
were at 190 8C, in which a concentrate containing
20.3% Zn and 8.5% Cu can be converted into a final
concentrate with 6.6% Zn and 42.4% Cu.
The hydrothermal reactions of chalcopyrite have
been studied more extensively than those of sphalerite
and several patents were already published during the
1950s (McGauley and Roberts, 1951; Roberts et al.,
1953; McGauley et al., 1956). Barlett (1992) and
Peterson and Wadsworth (1994) showed that the
2+
chalcopyrite reaction with Cu(aq)
occurs as follows:
3CuFeS2 6CuSO4aq 4H2 OY5Cu1:8 S
3FeSO4aq 4H2 SO4aq

The kinetics were reported as mixed diffusion/

chemical reaction control (Peterson and Wadsworth,
1994) with an activation energy of 90100 kJ/mol in
the range 125200 8C. An electrochemical mechanism has been proposed in which Cu+ and Cu2+ ions
diffuse in the lattices of the copper sulfide layers.

The enrichment of chalcopyrite concentrates has

also been studied with the controlled injection of O2
and without Cu2+ addition, in the range 170200 8C
(Barlett, 1992; Jang and Wadsworth, 1993; Jang and
Wadsworth, 1994):
1:8CuFeS2 4:8O2 0:8H2 OYCu1:8 S
1:8FeSO4aq 0:8H2 SO4aq

In this case, kinetics appeared to be electrochemically

controlled as the sulfide layers are highly porous.
The objective of the present study is to examine the
nature of the reaction of sphalerite with copper ions,
as well as the major kinetics dependencies of the
process. A significant departure from previous
research is the extension of the temperature range to
225 8C. Reaction rates increase dramatically under
these conditions, which permits to obtain extensive
conversion of sphalerite particlesas large as 50
Amwithin a time frame permitted by autoclave
processing. Preliminary research on Chilean copper
concentrates indicated the possibility of the removal
of about 80% Zn by treatment at 225 8C, 1 h, 8 g/L
Cu2+ (Vinals et al., 2004a). Under these conditions,
the simultaneous removal of about 80% Cd, Tl and Bi
is also obtained (Vinals et al., 2004b).

2. Experimental
2.1. Materials
The sphalerite used in this research was taken from
a single 4-cm crystal from La Union (Murcia, Spain).
Characterization by X-ray diffraction (XRD), and
Scanning Electron Microscopy coupled by Energy
Dispersive Spectrometry (SEM/EDS) confirmed a
single phase product. The composition determined
by Electron Microprobe Analysis (EMPA) was
61.14% Zn, 4.46% Fe and 33.74% S. The samples
for autoclave experiments were prepared from the
ground crystal by wet sieving. Particle sizes of b25,
2540, 80106 and 140180 Am were used.
2.2. Autoclave experiments
Experiments were performed in a Teflon-coated
stainless steel PARR-4563 stirring reactor with a

J. Vinals et al. / Hydrometallurgy 75 (2004) 177187

programmable heating controller. The stirring speed

was 800 min1 in all experiments. The system was
raised to the working temperature at a rate of ~5 8C/
min , then maintained at this temperature for a fixed
time (nominal time), until it was cooled to the
ambient temperature, again at a rate of ~5 8C/min.
After this treatment, the pH and the solution volume
were measured. Copper, zinc and iron in the final
solution were determined by A.A. Residual solids
were characterized by XRD, reflected-light microscopy and SEM/EDS and selected samples were
analyzed by EMPA. In order to detect the possible
formation of elemental sulfur, samples of residual
solids were treated by CS2. No significant amounts
of elemental sulfur were detected in the range
studied.
The nature of the reaction of sphalerite with copper
ions was investigated in the range 160225 8C. 0.1 g
of 2540 Am sphalerite particles was treated with 100
cm3 of slightly acidified ( H2SO4, pH 1.3) copper
sulfate solutions of known concentrations. Under
these conditions, there is sufficient Cu2+ excess to
assume practically constant copper concentration, pH
and solution volume. However, other experiments
were performed with b25 Am sphalerite and a much
lower excess of Cu2+ (0.8 g sphalerite in 80 cm3 of
solution), in order to correlate the Cu2+ consumed
with the Zn2+ and Fe2+ in solution as well as with the
SO42 increment.
The kinetics of the process was also studied in the
range. Experiments were performed in the same way
as previously described for large excess Cu2+/sphalerite, studying the effects of particle size, copper
concentration and temperature. The fraction of sphalerite reacted was computed as the ratio Zn2+ in
solution/initial Zn in the solid. Selected samples of
intermediate and final solid products were studied in
SEM to measure the thickness of the layer of copper
sulfides.

3. Results and discussion

3.1. Nature of the reaction
3.1.1. Solid phase composition and textures
Fig. 1 shows the complete transformation of
sphalerite into copper sulfidein this case Cu2Sat

179

Fig. 1. Transformation of ZnS to Cu2S (225 8C, Cu2+ 5 g/L, pH

1.1). (A) Initial sphalerite. (B) 60 min. (C) 120 min (SEMBSE).

225 8C. The reaction occurs across a compact copper

sulfide layer and the final copper sulfide particles
retain practically the same size and shape of the
original sphalerite.
The results obtained by XRD on solid phase
composition are shown in Fig. 2 and Table 1. Digenite
(theoretically Cu1.8S) was the dominant, almost
exclusive solid product in the range 180212 8C.
Amongst the numerous phases of composition
approaching bCu2SQ, the preferential formation of
digenite is probably due to its thermodynamic stability
under the conditions of pH, EH and temperature
studied. Whilst digenite (at ~200 8C) and sphalerite

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J. Vinals et al. / Hydrometallurgy 75 (2004) 177187

Fig. 2. XRD spectra of reacted solids at different temperatures (conditions as in Table 1). (1) Sphalerite. (2) Digenite. (3) Covellite. (4)
Chalcocite-Q. (5) Chalcocite-M.

are both isometric, digenites structure (space group

Fm3m) and cell parameter (5.589 A) (Will et al.,
2002) are quite different from those of sphalerite
(space group F-43m, 5.409 A) (Skinner, 1961). Fig. 3
shows the digenite layers observed in this temperature
interval. No intermediate covellite (CuS) layer was
detected between ZnS nuclei and digenite.
However, on increasing the reaction temperature to
225 8C, the stability of digenite decreases under the
conditions studied. It is initially formed during the
heating process but evolves to chalcocite by 225 8C;

first tetragonal chalcocite (Chalcocite-Q) (Fig. 4) then

monoclinic chalcocite (Chalcocite-M) (Fig. 1C). The
true phase during longer reaction times is probably
hexagonal chalcocite (Chalcocite-H), but this phase
reverts to chalcocite-M below 103 8C (Gaines et al.,
1997).
The formation of small amounts of covellite during
the hydrothermal reaction of sphalerite was also
detected in the interval 160200 8C (Table 1).
Covellite was found as relatively large laminar
crystals over an initially formed digenite layer in

J. Vinals et al. / Hydrometallurgy 75 (2004) 177187

Table 1
Fraction reacted and phase composition of final solids (2540 Am
sphalerite)
Temp. [Cu2+]
(8C)
(g/L)

Time pHf
(min)

Sphalerite Reaction products

reacted (%) (XRD) (I i /I j : ratio
of main peak intensity)

160

60

1.2

180

60

1.2

14

190*

10*

200

60

1.1

29

200

60

1.2

29

200

60

1.1

25

200

10

60

1.2

34

212
225

5
5

60
15

1.1
1.1

53
32

225

60

1.1

60

120* 1.2* 81*

181

Table 2 shows the results of a stoichiometric

experiment at 190 8C to correlate the mole of
sphalerite reacted with the mole of Cu2+ consumed,
as well as the mole SO42 generated. Sphalerite reacts
stoichiometrically giving a molar ratio (Zn/Fe) in the

Digenite,
covellite I dig/I cov ~ 1
Digenite,
covellite I dig/I cov ~ 4
Digenite,
possible anilite
(Cu7S4) in trace*
Digenite,
covellite I dig/I cov ~ 10
Digenite,
covellite I dig/I cov ~ 13
Digenite,
covellite I dig/I cov ~ 30
Digenite,
covellite I dig/I cov ~ 30
Digenite
Digenite,
chalcocite-Q
Chalcocite-M

* Experiment performed with sphalerite particles of b25 Am

and pH0=1.5.

some anomalous reacted grains (Fig. 5). These

abnormal grains appear when the initial digenite layer
is physically separated from the sphalerite core due to
a rupture, probably of mechanical origin (Fig. 5). It
seems covellite develops when digenite is not in
galvanic contact with sphalerite. However, the relative
amount of covellite decreases with increasing temperature in the interval 160200 8C. Higher copper
concentration also reduces the formation of covellite.
For [Cu2+] 10 g/L, covellite is practically absent even
at 190 8C.
3.1.2. Stoichiometry
In accordance with the solid phase composition,
the expected general stoichiometry for the sphalerite
reaction would be:
2  xCu2
aq 5  x=4ZnS
1  xH2 O ! Cu2 xS 5  x=4Zn2
aq

1  x=4SO2
4aq 21  xH

where theoretically, x=0 for chalcocite and x=0.2 for

digenite.

Fig. 3. Digenite layers at different temperatures. (Cu 5 g/L, 60 min)

(A) 160 8C, (B) 180 8C, (C) 200 8C, (D) 212 8C (SEMBSE).

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J. Vinals et al. / Hydrometallurgy 75 (2004) 177187

Table 2
Results of a stoichiometric experiment (0.850 g sphalerite, b25 Am,
190 8C, 2 h)
Solutions

Volume
(cm3)

Cu2+
(g/L)

S
(g/L)

Zn2+
(g/L)

Fe2+
(g/L)

pH

Initial
Final

80
76

9.96
1.82

6.56
7.43

0.00
5.56

0.00
0.41

1.5
1.2

Stoichiometric ratios (molar)

Fig. 4. Optical micrograph of a layer showing lamellae transformation of digenite (medium gray) to chalcocite (white) at 225 8C.
(Cu2+ 5 g/L, pH 1.1, 15 min).

aqueous solution practically identical to that found in

the sphalerite sample. The stoichiometric coefficients
for (DCu/Zn+Fe) and (DSO4/Zn+Fe) in the aqueous solution, were 1.52 and 0.18, respectively.
Taking x=0.2, these values are consistent with the
general reaction (5), as digenite was the phase
obtained at 190 8C.
Considering the reaction stoichiometry and the
molar volume of the pure phases (23.2, 25.7 and 27.4
cm3/mol for ZnS, Cu1.8S and Cu2S, respectively), the
theoretical PillingBedworth ratios are 0.93 for
digenite and 0.95 for chalcocite. These values suggest
that the layers could have a low but significant
microporosity, despite the fact that SEM observations
on layers formed at z200 8C did not detect pores.

(Zn/Fe)solution/
(Zn/Fe)solid

DCusolution/
P

DS
/
P solution

0.99

1.48

0.18

Zn+Fe solution

Zn+Fe solution

However, EMPA of these layers gives a sum of

components very close to 100% (Table 3), which
indicates, in any case, very low microporosity.
3.2. Kinetics
3.2.1. Effect of reaction time
SEM measurements of copper sulfide layers
obtained at different times showed nonlinear rates.
Fig. 6 shows the results obtained at 200 8C in which a
parabolic rate law was obtained, strongly suggesting
kinetic control by solid layer diffusion.
Consequently, kinetic data were treated by the
following shrinking core model:
F a 1  2=3a  1  a2=3 kex t

kex kPL =r02

where a is the fraction reacted, t the time, k ex the

experimental rate constant, r 0 the initial particle radius

Table 3
EMPA data on sphalerite core and layers of reaction products

S
Zn
Fe
Cu
Total

Fig. 5. Covellite laths on digenite layer in partially or completely

void grains (180 8C, 60 min, Cu2+ 5 g/L, pH 1.1) (SEMBSE).

Sphalerite core*

Digenite
(200 8C)**

Chalcocite-M
(225 8C)**

32.92% (0.37)std
59.65% (2.43)std
4.35% (2.21)std
2.39% (0.68)std
99.31%

20.42% (0.73)std
0.64% (0.29)std
0.15% (0.06)std
78.27% (1.87)std
99.48%
molar Cu/S=1.9

20.12% (0.43)std
0.36% (0.38)std
0.06% (0.05)std
79.16% (0.69)std
99.70%
molar Cu/S=2.0

Apparatus: Cameca SX-50; Program: PAP.

Conditions: 20 kV; 20 nA; counting time 10 s.
Standards: Pyrite (S Ka); Sphalerite (Zn Ka); Pyrite (Fe Ka);
Chalcopyrite (Cu Ka).
* Average 20 points.
** Average 10 points.

J. Vinals et al. / Hydrometallurgy 75 (2004) 177187

183

Fig. 6. Effect of the reaction time on the growth of copper sulfide

layer.

Fig. 8. Plot of 12/3a(1a)2/3 vs. time for different particle

radius.

and k PL the rate constant for product-layer diffusion

control (Sohn and Wadsworth, 1979).

radius as it was expected from the theoretical model

(Eqs. (6) and (7)).

3.2.2. Effect of particle size

Fig. 7 shows the conversion/time data at 200 8C,
[Cu2+] 5 g/L and pH 1.31.1, for three shortened
particle sizes: r 0=16F4, 47F2 and 80F10 Am. Fig. 8
is the application of the conversion model. Rate
conversion decreases very significantly with increase
in particle size. Fig. 9 shows a plot of the experimental
rate constants from the inverse of the square particle

3.2.3. Effect of copper concentration

The copper concentration effect was studied at 200
8C, pH 1.31.1, r 0 16F4 Am and for copper
concentrations: 1, 2, 5 and 10 g/L. Reaction rate
was not very sensitive to the aqueous copper
concentration as is shown in Fig. 10. In order to
corroborate the data obtained from solution analysis,
SEM measurements of the copper sulfide layers were
also performed for different copper concentrations.
Layer thickness observed at 200 8C after 1 h were
almost identical (1.31.4 Am) in the interval Cu2+ 1
10 g/L, confirming that if copper concentration is in
excess of the stoichiometric consumption requirements, the reaction rate is practically independent of
[Cu2+].
This effect is similar to that found by Peterson and
Wadsworth (1994) for the hydrothermal reaction of
chalcopyrite. At least in the present study, this effect is
also clearly inconsistent with the control by pore
diffusion of aqueous copper ions to the sphalerite
interface. More likely, diffusion control involves
copper ions in solid state. Consequently, the gradient
of these ions from the watercopper sulfide interface

Fig. 7. Effect of particle radius on the conversion rate.

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J. Vinals et al. / Hydrometallurgy 75 (2004) 177187

Fig. 9. Experimental rate constants against the inverse of the square particle radius.

to the copper sulfidesphalerite interface would be

limited by the gradient of lattice vacancies and not by
any gradient of the aqueous copper ions. Considering
that in chalcocite and digenite (also in covellite) the
Cu ions of the lattice are Cu+ (Nakai et al., 1978,
Termes et al., 1987), it seems reasonable to expect that
copper diffuses as Cu+ in these layers.

(Fig. 6): 160 8C 0.5F0.1 Am; 180 8C 0.8F0.1 Am;

200 8C 1.4F0.1 Am; 212 8C 2.5F0.1 Am; 225 8C
4.2F0.1 Am. The obtained k PL from SEM measurements were similar to those obtained from solution
analysis with a maximum difference of less than 25%
(Fig. 12).

3.2.4. Temperature effect

Temperature effect was studied at [Cu2+] 5 g/L , pH
1.31.1, r 0=16F 4 Am and 160, 180, 200, 212 and
225 8C. Fig. 11 is the plot of the reaction model. The
Arrhenius plot of the product-layer rate constants
(k PL) from data in Fig. 11 is shown in Fig. 12. The
estimated constants from SEM layer measurements
were also included in Fig. 12, computed from layer
thickness obtained after 1 h at various temperatures
(Figs. 1 and 3), and assuming a parabolic rate law

Fig. 10. Effect of the copper concentration.

Fig. 11. Plot of 12/3a(1a)2/3 vs. time for different

temperatures.

J. Vinals et al. / Hydrometallurgy 75 (2004) 177187

185

Fig. 12. Arrhenius plot of the rate constants.

The obtained activation energy in the interval 180

225 8C was 147 kJ/mol (35 kcal/mol), a typical value
for diffusion in solid state, which confirms this kinetic
reaction control for the hydrothermal conversion of
the sphalerite. The rate at 160 8C was not considered
in the determination of the activation energy, as at this
temperature conversion is very slight and, in relative
terms, the formation of covellite was of the same
magnitude as that of digenite (Table 1).
Peterson and Wadsworth (1994) reported an
activation energy for the hydrothermal reaction of
chalcopyrite, significantly lower (99.7 kJ/mol) than
that obtained in the present study for sphalerite, in
spite of the fact that the ionic diffusion must occur
through the same lattice (digenite). This may be due to
the reported intermediate layer of covellite, the
presence of a different counter diffusing ion, Fe2+,
and mixed chemical-diffusion kinetics.
On the other hand, the product layer rate constants
for sphalerite are much lower than for chalcopyrite at
V200 8C. For instance, the reported k PL for chalcopyrite
was about 3 Am2/h at 150 8C (Peterson and Wadsworth,
1994). Values of this magnitude for sphalerite were not
reached until about 200 8C (Fig. 12). Consequently,
whereas chalcopyrite treatment can be technically
feasible at b200 8C, the analogous treatment for
sphalerite requires N200 8C. However, the high
activation energy for sphalerite permits to obtain high

reaction rates at 225 8C (~17 Am2/h), which ensure high

sphalerite conversion in times allowing autoclave
processing (~1 h).
3.3. Overall mechanism
Hydrothermal conversion of the sphalerite to
chalcocite or digenite involves cathodic (the reduction
of Cu2+ to Cu+) and anodic processes (the oxidation of
1/5 or 1/6 of the S2 from sphalerite to SO42, for
chalcocite and digenite, respectively). Fig. 13 shows a
schema of the possible mechanism. In this formulation, it is assumed counter diffusion of Cu+ and Zn2+
through the lattice of the copper sulfide. Only two
interfaces are consideredsphalerite/copper sulfide
and copper sulfide/waterbecause no experimental
evidence of an intermediate covellite zone was found.
For comparative purpose, all the reactions are written
for 1-mol ZnS.
3.3.1. Sphalerite/copper sulfide interface
Cu+ ions displace the Zn2+ ions of sphalerite with the
consequent growth of the copper(I) sulfide phase. At
225 8C, chalcocite would be the more stable arrangement, whereas digenite would be more stable at b225
8C. However, the formation of digenite would require
an oxidation process to compensate the cation deficit. In
this formulation, the release of electrons is assumed, but

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J. Vinals et al. / Hydrometallurgy 75 (2004) 177187

Digenite:

1:5Cu2
aq 1:5eY1:5Cus

13

2
1=6Cu1:8 Ss 4=6H2 OY0:3Cu
s 1=6SO4aq

8=6H
aq 1:3e
2
Zn2
s YZnaq

14
12

3.3.3. Overall
Chalcocite:
2
ZnSs 1:6Cu2
aq 0:8H2 OY0:8Cu2 Ss Znaq

0:2SO2
4aq 1:6Haq

15

Digenite:
Fig. 13. Schema of the possible mechanism.

ZnSs 1:5Cu2
aq 4=6H2 OY5=6Cu1:8 Ss

it is also possible that this process could be effected

through positive electron holes coupled with cation
vacancies. The Zn2+ ions diffuse through the copper
sulfide lattice to the copper sulfide/water interface.
Chalcocite:
ZnSs

2Cu
s YCu2 Ss

2

Zn2
aq 1=6SO4aq 8=6Haq

4. Conclusions
(1)

Zn2
s

Digenite:
2
ZnSs 1:8Cu
s YCu1:8 Ss Zns 0:2e

3.3.2. Copper sulfide/water interface

Cu2+ ions from the solution are adsorbed and
reduced to Cu+ ions in surface cathodic sites. For
electronic balance, S2 ions of the Cu(I) sulfide are
oxidized to sulfate in surface anodic sites. The Cu+
ions diffuse through the copper sulfide lattice to the
sphalerite/copper sulfide interface. For ionic charge
balance, Zn2+ ions desorb to the aqueous solution.
Chalcocite:

1:6Cu2
aq 1:6eY1:6Cus

1:6H
aq 1:6e
2
Zn2
s YZnaq

1  xH2 O ! Cu2x S 5  x=4Zn2

aq

1  x=4SO2
4aq 21  xH

(2)

(3)
11
12

The reaction of sphalerite with Cu2+ sulfate

solutions at pH 1.11.3 produces mainly digenite (Cu1.8S) at 180212 8C and chalcocite (Cu2S)
at 225 8C. The general stoichiometry of the
hydrothermal reaction can be written as:
2  xCu2
aq 5  x=4ZnS

10

2
0:2Cu2 Ss 0:8H2 OY0:4Cu
s 0:2SO4aq

16

The reaction occurs through a compact layer of

copper sulfide surrounding the sphalerite nuclei.
Final copper sulfide particles retain the size and
shape of the original sphalerite. Reaction rate
follows a parabolic kinetic law, indicative of a
solid layer diffusion control.
The negligible effect of the aqueous copper
concentration and the very high activation
energy (147 kJ/mol) are consistent with a
reaction control by solid state counter diffusion
of Cu+ and Zn2+ through the copper sulfide
layer.

J. Vinals et al. / Hydrometallurgy 75 (2004) 177187

(4)

The removal of sphalerite from digenite or

chalcocite bearing copper concentrates is effective at ~225 8C, in which a high conversion can
be achieved in times allowing autoclave processing (~1 h).

Acknowledgements
The authors wish to thank the Universidad Catolica
del Norte (Chile) for the financial support of this
research in the framework of a Doctorate Program in
collaboration with the Universidad de Barcelona
(Spain). The support of the bServeis CientficoTe`cnics de la Universidad de BarcelonaQ and Mrs.
E. Vilalta in the characterization studies is also
gratefully acknowledged.

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