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Hydrometallurgy 95 (2009) 3943

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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

Kinetics of sphalerite dissolution by sodium chlorate in hydrochloric acid


Gkhan Uar
Department of Mining Engineering, Seluk University, 42075 Konya, Turkey

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

Tel.: +90 332 223 20 30; fax: +90 332 241 06 35.
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

an oxidizing agent for leaching zinc concentrates in hydrochloric or


sulphuric acid solutions (Vazarlis, 1987; Aydogan, 2006).
Chloride systems in hydrometallurgy have been used for the treatment
and recovery of precious metals for a number of years. The leaching of
sulphide minerals in chloride media is a subject of considerable interest
and has been studied by many researchers (Dutrizac and MacDonald,
1978; Venkataswamy and Khangaonhar, 1981; Rath et al., 1988; NeouSingouna and Fourlaris, 1990; Godocikova et al., 2002; Aydogan et al.,
2005a). These studies indicated that the ferric chloride solutions could
rapidly, but unselectively leach base metals from sulphide minerals. Again,
elemental sulphur coatings hinder leaching (Buttinelli et al., 1993). The
general leaching of base metal sulphide concentrate in ferric chloride
solution may be described by Eq. (1).
MeS 2Fe3 Me2 2Fe2 S0

Various reagents can be used in the dissolution of sphalerite


including chlorine. Olanipekun and Oderinde (1999) investigated
hydrochloric acid leaching of sphalerite in the presence of an oxidizing
agent which indicated that the dissolution rate was directly affected by
increasing the temperature and concentration of reagents. Jena et al.
(1999) investigated the kinetics of chlorination of a slurry of sphalerite
concentrate by chlorine gas; whilst Ekinci et al. (1998) studied the
leaching kinetics of sphalerite with pyrite in chlorine saturated water.
They reported that the dissolution of sphalerite by chlorine takes place
as follows:
ZnSs Cl2aq ZnCl2aq Ss

In this paper, the dissolution of sphalerite was carried out with


sodium chlorate in hydrochloric acid solution. The purpose was to
study the kinetics of sphalerite oxidation by chlorate (ClO3) ion which
is a good oxidizing agent in acid medium (E = 1.45 V). This potential

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G. Uar / Hydrometallurgy 95 (2009) 3943

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 (%)

Acid insolubles (%)

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

value is adequate to oxidize almost all metal sulphides and the


reduction of chlorate ion in acidic solution is given by Petrucci and
Harwood (1989) as:
ClO3 6H 6e 3H2 O Cl

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.

When chlorate is combined with strong acid chloride medium, it


can produce chlorine as follows:

3. Result and discussion

ClO3 6H Cl 3H2 O Cl2g

3.1. Reaction of sphalerite

In this experimental study on dissolution of zinc from sphalerite,


the effects of stirring speed, hydrochloric acid and sodium chlorate
concentration, temperature and particle size were investigated and
the kinetic control mechanism determined.
2. Materials and methods
Sphalerite concentrate was enriched thorough otation of a
CuFeS2PbSZnS complex ore in the Menka otation plant (SivasTurkey) and was used in this study. The sample was wet sieved, dried
and then dry sieved to three size fractions (0.0450.075, 0.0750.106
and 0.1060.212 mm). Experiments were performed with the 0.045
0.075 mm fraction except otherwise stated. Distilled water and

The oxidation and dissolution mechanism of sphalerite in chlorine


systems still remains uncertain and a wide variety of possible
mechanisms have been proposed in the literature. Dissolution of
sphalerite in acidic FeCl3 solutions have been investigated by many
researchers, and it has been found that zinc sulphide reacts with Fe3+ in
two stages. In the rst stage, sulphide is converted to S and in the
second stage S to SO4 2 (Fuerstenau et al., 1987; Dutrizac, 1990). Copur
(2002) studied sphalerite dissolution with HNO3 and same result was
found. Habashi (1999) proposed that elemental sulphur is converted the
sulphate in aqueous chlorine at ambient temperature as follows:
S0 3Cl2 4H2 OH2 SO4 6HCl

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

Some of the sulphur was converted sulphate in presence of


dissolved chlorine or chlorate ion in the solution. Sodium chlorate
(NaClO3) is well known as an efcient oxidizing agent, and supplies

Fig. 1. The microscope photo of the leaching residues after rst 60 min of leaching time.

Fig. 2. Effect of temperature on the sphalerite dissolution.

G. Uar / Hydrometallurgy 95 (2009) 3943

41

The effect of temperature on sphalerite dissolution was studied in the


range 313 to 343 K under constant conditions. Not surprisingly, the
leaching rate increased with temperature but as shown in Fig. 2,
temperatures over 333 K have a moderate effect on the rate and overall
zinc recoveries were almost the same.
To resolve the effect of NaClO3 concentration on the rate of sphalerite dissolution, a study found that sphalerite dissolution increases
gradually with increasing sodium chlorate concentration (Fig. 3). After
150 min leaching, 22% and 99% Zn extraction were achieved with
0.25 M and 1 M NaClO3 respectively. These results show that NaClO3
has a direct effect on sphalerite dissolution.
The experiments were then carried out with various HCl concentrations in the range 0.25 to 1.25 M. As seen from Fig. 4, zinc extraction
recoveries increased from 11% to 99% with increasing HCl concentration with little change above 1.0 M HCl. It was also observed that the
dissolution curves in b0.75 M HCl were nearly linear, while above
0.75 M HCl they were parabolic for the same period indicating direct
acid dissolution. Majima et al. (1981) observed similar results investigating the leaching of sphalerite in hydrochloric acid solutions. These
authors have reported, increasing acid concentration has increased
dissolution rate of zinc which was slow at decreasing acid concentration.
Fig. 3. Effect of NaClO3 concentration on the sphalerite dissolution.

3.3. Dissolution kinetics

adequate oxygen for sulphur to sulphate production. The overall


reaction can be written as follows:
2ZnS 2NaClO3 4HCl2ZnCl2 S Na2 SO4 2H2 O Cl2g
0

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.

Understanding the mechanism of a leaching system is the main


consideration. Leaching of mineral particle may be described by a
number of reaction models already proposed in the literature. Reactions
involved in this process are heterogeneous in nature involving mass
transport reactant and product ions. In an acid leaching process, most
suldes follow a kinetic model known as the shrinking core model. This
model has a reaction zone that originates from the outside layer of
unreacted core (Levenspiel, 1972; Shon and Wadsworth, 1979). The
dissolution of sphalerite can be explained by a shrinking core model
which can be expressed as follows;

3.2. Effect of parameters

Afluid bBsolid Fluid products Solid products

The effect of stirring speed on the dissolution of sphalerite was


investigated in the range of 100 600 rpm at 333 K in solution containing
1.0 M NaClO3 and 1.0 M HCl. However, the rate and extent of dissolution of
zinc over 150 min was not changed above 400 rpm. Olanipekun and
Oderinde (1999) observed similar results in their sphalerite leaching study.
Therefore, a stirring speed of 400 rpm was used for all other experiments.

The fraction of any zinc at any time t, in a regime controlled by the


surface chemical reaction can be predicted from Eq. (9).
h
i kM C
c B A
1  1  a1=3
t kr t
9
qB ar0
where is the fraction reacted, kc is the kinetic constant, MB is the
molecular weight of the solid, CA is the concentration of the dissolved

Fig. 4. Effect of HCl concentration on the sphalerite dissolution.

Fig. 5. Plot of 1 (1 X)1/3 versus t for different temperatures (symbols as in Fig. 2).

42

G. Uar / Hydrometallurgy 95 (2009) 3943

Fig. 7. Determination of reaction order for sphalerite dissolution with respect to NaClO3
and HCl concentrations.

Fig. 6. Arrhenius plot of the data presented in Fig. 5.

lixiviant A in the bulk of the solution, a is the stoichiometric


coefcient of the reagent in the leaching reaction, r0 is the initial
radius of the solid particle, t is the reaction time, B is the density of
the solid and, kr is the rate constants which is calculated from Eq. (9).
Fig. 5 shows the straight line plot of 1 (1 X)1/3 versus time which
allows the rate to be determined from the slope.
It is generally accepted that a chemically controlled process is
strongly dependent on temperature. The rate constant, k, is exponentially dependent on temperature, Eq. (10).
k Ae Ea=RT

10

where A is the frequency factor, Ea is the activation energy of the


reaction, R is the Boltzmann constant and T is the absolute
temperature. According to Shon and Wadsworth (1979), the diffusion
control regime has a typical Ea of ~20 kJ/mol, whereas the Ea of a
reaction controlled process has a value N40 kJ/mol.
Eq. (9) was applied to the data obtained at each temperature to
determine the rate constants used in the Arrhenius plot (Fig. 6). The
activation energy was calculated as 41.1 kJ/mol, indicating a surface
chemical reaction control mechanism. This value is similar to the
activation energies for sphalerite leaching reported by various authors
(Table 2).
In order to decide the order of reaction with respect to reagent
concentration, the results on the effect of NaClO3 and HCl concentra-

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

Activation energy (kJ/mol)

Reference

Ferric chloride

41.8

Ferric chloride in hydrochloric


acid
Ammonia solution in sulphuric
acid
Hydrochloric acid

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.

G. Uar / Hydrometallurgy 95 (2009) 3943

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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