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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t
A R T I C L E
I N F O
Article history:
Received 31 January 2008
Received in revised form 4 April 2008
Accepted 11 April 2008
Available online 22 April 2008
Keywords:
Sphalerite
Sodium chlorate
Leaching
Kinetic model
A B S T R A C T
The extraction of zinc from a sphalerite concentrate using sodium chlorate as an oxidant in hydrochloric acid
solutions was examined. It was determined that stirring speed did not signicantly affect zinc extraction
compared with other experimental parameters. The dissolution rate increased with increasing sodium chlorate
and hydrochloric acid concentrations and temperature, but decreased with increasing particle size. The kinetic
study showed that the dissolution of zinc could be represented by a shrinking core model with surface chemical
reaction. The activation energy (Ea) for the dissolution reaction was calculated as 41.1 kJ/mol.
2008 Elsevier B.V. All rights reserved.
1. Introduction
Sphalerite is the principal zinc mineral that produces zinc from sulde
ores. It is often associated with other sulphide minerals, such as galena
(PbS), chalcopyrite (CuFeS2) and pyrite (FeS2) which are generally
separated from each other by froth otation methods. The conventional
method of recovering zinc from sphalerite involves the roastingleaching
electrowining process. The roasting step produces SO2 gas which must be
captured or converted to sulphuric acid. Hydrometallurgical processing
becomes more attractive especially for low grade and complex sulphide
ores. The advantage of hydrometallurgical process is that sulphur in the
ore is usually converted to elemental sulphur, thus avoiding the production of SO2. However, the elemental sulphur formed during oxidative
leaching with many oxidizing agents such as ferric ion usually covers the
ore particles to reduce the leaching rate of the metal being extracted (Chen
and Dutrizac, 2004; Peng et al., 2005; Dutrizac and MacDonald, 1978,
Bobeck and Sue, 1985; Dutrizac, 1990; Aydogan et al., 2005a).
Crundwell (1988) has studied the effect of iron impurity in sphalerite concentrate on the rate of dissolution. It has been shown that the
dissolution rate of sphalerite increases with increasing iron content in
the sphalerite lattice. Various leaching studies on zinc extraction have
been performed in acidic medium using nitric, hydrochloric and sulphuric acid (Pandey, 1998; Copur, 2001; Mizoguchi and Habashi, 1981;
Majima et al., 1981; Demopoulos and Baldwin, 1999) or using basic
medium such as ammonia solution (Babu et al., 2002, Aydogan et al.,
2005b). In addition, hydrogen peroxide has been successfully used as
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E-mail address: gokucar@selcuk.edu.tr.
0304-386X/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2008.04.008
40
Table 1
Chemical analysis of each fractions of sphalerite concentrate
Particle size (mm)
0.2120.106
0.1060.075
0.0750.045
Element (%)
Zn (%)
Fe (%)
Cu (%)
S (%)
57.87
59.97
60.14
0.98
0.16
0.09
0.05
29.32
30.15
30.93
11.83
9.72
8.79
reagent grade chemicals were used to prepare all the solution. The
chemical analysis of each size fraction is given in Table 1.
Experiments were carried out by agitation leaching using a covered
1 L pyrex beaker in a water bath and mechanically stirred with a Teon
impeller at 02000 rpm. Typically, sphalerite concentrate (0.5 g) was
added to acidic sodium chlorate solution (250 mL) and 1 mL samples
were withdrawn at various time intervals for analysis. For calculation
of the fraction of zinc leached, an equation developed by Demopolous
and Papangelakis (1998) was used which includes correction factors to
account for volume losses during sampling. Zinc in the solution was
determined using ame atomic absorption spectrophotometer (GBC
Scientic Equipment, SensAA Model, Australia). Each experiment was
repeated at least three times and the results averaged.
In this study, elemental sulphur was observed by naked eye at the end
of leaching process but the exact amount was not measured or quantied.
After 60 min of leaching, the microscope photo of the leach residues
show elemental sulphur completely covering the particle surface (Fig. 1
(ab)). Elemental sulphur produced in the rst step by reaction of
sphalerite with chlorate ion in hydrochloric acid can be given as follows:
ZnS NaClO3 6HClZnCl2 S0 NaCl 3H2 O 2Cl2g
Fig. 1. The microscope photo of the leaching residues after rst 60 min of leaching time.
41
After leaching, the solution was analyzed for SO4 ion by adding
0.1 M BaCl2 solution (BaSO4 (Ksp = 1.08.10 10). Barium sulphate
precipitated without delay conrming the formation of SO4 2 ion
during the reaction. In order to determine zinc chloride (ZnCl2) in
solution, ammonium chloride (2 g) was added to form ammonium
tetrachloro-zincate ((NH4)2ZnCl4) as the reaction product.
Fig. 5. Plot of 1 (1 X)1/3 versus t for different temperatures (symbols as in Fig. 2).
42
Fig. 7. Determination of reaction order for sphalerite dissolution with respect to NaClO3
and HCl concentrations.
10
tions, obtained from Figs. 3 and 4, were applied to this kinetic model.
The k r values for each HCl and NaClO3 concentrations were
determined. From the corresponding kr and HCl and NaClO3
concentrations values, plots of ln kr versus ln [HCl] and ln [NaClO3]
were obtained. As seen from Fig. 7, the order of reaction was found
proportional to power 2.0 of HCl concentration ([HCl]2.0) and power
1.5 of NaClO3 concentration ([NaClO3]1.54).
Finally, the effect of particle size on the rate of sphalerite
dissolution was examined by measuring the reaction rates for three
different size fractions (0.0450.075, 0.0750.106 and 0.106
0.212 mm) at 333 K in solutions containing 1.0 M NaClO3 and 1.0 M
HCl. The rate constants were determined from the surface chemical
reaction model and were plotted versus the reciprocal of particle
radius, yielding a linear relationship with a correlation coefcient of
0.99 (Fig. 8). This conrmed that a surface chemical reaction was the
rate controlling step during dissolution.
Table 2
Reported activation energies for leaching of sphalerite with different leaching
Leaching reagent
Reference
Ferric chloride
41.8
45.3
Dutrizac and
MacDonald (1978)
Aydogan et al.
(2005a)
Babu et al. (2002)
Ferric chloride
46.9
41
15
Potassium chlorate in
43
hydrochloric acid
Hydrogen peroxide in sulphuric 43
acid
Mizoguchi and
Habashi (1981)
Bobeck and Sue
(1985)
Olanipekun and
Oderinde (1999)
Aydogan (2006)
Fig. 8. Dependence of kr on 1/r0.
4. Conclusions
The dissolution kinetics of sphalerite concentrate increases with
increasing hydrochloric acid and sodium chlorate concentrations and
temperature, and with decreasing particle size. However, stirring
speed N400 rpm did not signicantly affect the leaching rate. The
optimum leaching conditions with 2 g/L solid/liquid ratio were
determined as: 1.0 M NaClO3; 1.0 M HCl, 333 K; stirring speed
400 rpm with a particle size of 0.0450.075 mm. Under these
conditions, 99.4% zinc was extracted in 150 min. The activation energy
was found to be 41.1 kJ/mol which indicates a surface chemical
reaction. Empirical orders of the sphalerite dissolution reaction with
respect to sodium chlorate and hydrochloric acid concentrations are
1.5 and 2.0 respectively.
Acknowledgements
This study was supported by The Research Foundation of Selcuk
University.
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