Journal of

J. Min. Metall. Sect. B-Metall. 48 (2) B (2012) 185 - 195 Mining and
Metallurgy

KINETICS AND MECHANISM OF SPHALERITE LEACHING BY

SODIUM NITRATE IN SULPHURIC ACID SOLUTION

M. Sokić*,#, B.Marković*, V. Matković*, D. Živković**, N. Štrbac**, J. Stojanović*

*Institute for Technology of Nuclear and Other Mineral Raw Materials, Belgrade, Serbia
**University of Belgrade, Technical Faculty at Bor, Bor, Serbia

(Received 30 November 2011; accepted 15 January 2012)

Abstract

Interest for application of hydrometallurgical processes in a processing of complex sulphide ores

and concentrates has increased in recent years. Their application provides better metal recoveries
and reduced emission of gaseous and toxic ageneses in the environment. The kinetics and mechanism
of sphalerite leaching from complex sulphide concentrate with sulphuric acid and sodium nitrate
solution at standard conditions was presented in this paper. The influences of temperature and time
on the leaching degree of zinc were investigated and kinetic analysis of the process was
accomplished. With temperature increasing from 60 to 90oC, the zinc leaching increased from
25.23% to 71.66% after 2 hours, i.e. from 59.40% to 99.83% after 4 hours. The selected kinetic model
indicated that the diffusion through the product layer was the rate-controlling step during the
sphalerite leaching. The activation energy was determined to be 55 kJ/mol in the temperature range
60-90oC. XRD, light microscopy and SEM/EDX analyses of the complex concentrate and leach
residue confirmed formation of elemental sulphur and diffusion-controlled leaching mechanism.

Keywords: sphalerite leaching, sodium nitrate, sulphuric acid, kinetics, mechanism

1. Introduction with other sulphide minerals, such

chalcopyrite, galena and pyrite, in
Sphalerite is the most important zinc disseminated form with complex
sulphide minerals. It is commonly associated mineralogical composition and fine-grained

# Corresponding author: m.sokic@itnms.ac.rs

DOI:10.2298/JMMB111130022S
186 M. Sokić / JMM 48 (2) B (2012) 185 - 195

structures. Both pyrometallurgical and the iron content has small affect on the
hydrometallurgical processes are applied for leaching kinetics of the silicate concentrate
processing zinc sulphide ores and by sulphuric acid.
concentrates. The conventional methods Ferric and cupric ions, bacteria, oxygen,
usually follow roasting-leaching and and other oxidants have been used as
elecrtrowinning steps.regulation on leaching agents of sphalerite in sulphate and
discharge of sulphur dioxide becomes more chloride media under atmospheric or
and more strict, hydrometallurgical pressure leaching conditions.
processes of direct leaching of sulphide ores Ferric ion, in either sulphate or chloride
and concentrates becomes more attractive. media, can be used to leach sphalerite,
The preferences of direct leaching are the according to the reaction [2, 11, 12]:
treatment low grade materials, the increase ZnS + 2Fe3+ = Zn2+ + 2Fe2+ S0 (1)
of metal recoveries and conversion of
sulphide sulphur to elemental form, which Oxidizing agents such O2 or H2O2 may be
remains in the leach residue, thus thoroughly used for oxidation of ferrous ions formed
eliminating discharge of sulphur dioxide into through reaction 1 [12,13].
the atmosphere. On the other hand, elemental Cheng et al. [14] leached zinc sulphide
sulfur formed as the main leaching product concentrate in a solution of ferric sulphate,
precipitates at the particle surfaces and tends sulphuric acid and sodium chloride. The
to inhibit the reaction rate [1-5]. dissolution process was limited by
The presence of iron in sphalerite mineral electrochemical reaction until 60-70%
has a significant influence on dissolution conversions, after which the formed sulfur
rate. Kammel et al. [6] and Crundwell [7] layer was limited the rate of reaction.
reported that the dissolution rate of sphalerite Atmospheric leaching of a sphalerite
was directly proportional to the concentrate in sulphate and chloride media
concentration of substitutional iron impurity was studied by Santos et al. [12]. The results
in the solid. Palencia Perez and Dutrizac [8], showed that using a solid /liquid ratio of 5%
noticed that the sphalerite leaching rate (w/v) it was possible to leach 95% of zinc
increases and the activation energy decreases after 2 h, at 80oC. The oxidation of Fe(II) by
with increasing iron content in sphalerite H2O2 during the leaching was studied and
structure. At the sphalerite leaching with improvement of 20% zinc extraction was
0.04 wt. % of iron by ferric chloride, the observed.
activation energy was about 70 kJ / mol, Oxygen pressure leaching, at high
while the sphalerite leaching with 12.5 wt.% temperatures, in sulphuric acid have been
of iron, activation energy was about 40 kJ / reported in several publications [15-18], and
mol. The presence of 5% galena in sphalerite it is represented by the following chemical
concentrate decreases the leaching rate of reactions:
zinc up to 13%, while the presence of 10% ZnS + H2SO4 + 1/2O2 = ZnSO4 + S + H2O (2)
pyrite increases zinc dissolution [9]. On the
Habashi [16] studied the mechanism of
other hand, Souza et al. [10], suggested that
sphalerite oxidation process and found that
 M. Sokić / JMM 48 (2) B (2012) 185 - 195 187

the dissolution rate is independent of oxygen oxygen that arises from nitric acid
pressure in the low sulphuric acid decomposition is the oxidant.
concentrations, but only on the concentration Oxidative dissolution of a sulphide
of sulphuric acid. For the higher concentrate using nitrate as an oxidant in
concentrations of sulphuric acid the sulphuric acid solution takes place with
dissolution rate depends only on the oxygen formation of elemental sulphur, and it can be
pressure. represented by one of the following chemical
During the pressure leaching, the leach reactions [23-27]:
temperatures were limited to below the 3MeS + 2NO3- + 8H+ =
melting point of sulphur, because molten = 3Me2+ + 3S0 + 2NO + 4H2O (3)
sulphur would encapsulate unleached or
sulphide and limit dissolution. The certain MeS + 2NO3- + 4H+ =
surface-active reagents inhibited the molten = Me2+ + S0 + 2NO2 + 2H2O (4)
sulphur from sulphide particles and allowed
A small part of the sulphide sulfur, under
leaching at temperatures above the melting
certain conditions, is oxidized to sulfate [28].
point of sulfur [19]. The Additive was lignin
Peng et al. [27], were studied the
sulphonate; zinc extractions increased to 96-
enhanced leaching of sphalerite concentrate
98%. Li et al. [18] investigated oxygen
in H2SO4-HNO3 solutions and the extraction
pressure leaching process of sphalerite
of sulphur with tetrachloroetylene. The zinc
concentrate in sulphuric acid in the addition
extraction without C2Cl4 was 70.1 % after
of sodium lignosulfonate lignin. The
one hour, and 99.2 % after six hours of
leaching of 99% zinc was achieved from the
leaching. In the presence of C2Cl4, zinc
concentrate under oxygen partial pressure of
extraction reached 88.2 % after one hour, and
800 kPa at leaching temperature of 150oC for
99.6 % after three hours of leaching. As a
2h, and the amount of sulphide sulphur
result, leaching rates significantly improved
oxidized to sulphate during leaching of 81%.
in the presence of C2Cl4. The rate of reaction
Babu et al. [20] investigated oxidative
was predominantly controlled by diffusion in
leaching of sphalerite with ammonium
the leaching process without C2Cl4.
persulphate in sulphuric acid media. They
The dissolution mechanism of sphalerite
achieved of 95% zinc extraction at a
is based on three main kinetic models. These
temperature of 60oC for 5 h in the presence
kinetic models are diffusion controlled,
of 20% (w/v) ammonium persulphate.
surface reaction controlled, and a mixed
Nitrate ion, due to their high oxidation
kinetic model containing diffusion and
potential, can be used as an oxidant for
surface reaction components, which
leaching sulphide minerals by sulfuric acid
simultaneously take place.
[21-22]. Habashi [21], indicated that metal
In this paper, chemical, XRD, light
sulphide oxidation by nitric acid can be
microscopy, and SEM/EDX analysis were
achieved in two ways. In the first case, NO
used to determine the characteristics of the
ion is the oxidant, and during the reaction it
samples of complex concentrate and leach
is reduced to NO or NO2. In the second case,
residue. Also, the kinetics of sphalerite
188 M. Sokić / JMM 48 (2) B (2012) 185 - 195

leaching from complex concentrate by concentrate and leach residue were

sodium nitrate in sulphuric acid was studied. determined by XRD using diffractometer
(PHILIPS PW-1710), reflected light
2. Experimental microscopic (Carl Zeiss-Jena, LENAPOL-
2.1. Materials U) and SEM-EDX (JEOL equipped with
software package PAX). The leaching
The complex concentrate enriched reaction was studied with the help of XRD,
through the flotation of a CuFeS2-PbS-ZnS light microscopy and SEM-EDX.
complex ore in the “Rudnik” flotation plant
(Rudnik – Serbia) was used in this study. It 3. Results and discussion
was wet sieved to obtain the particle size 3.1. Characterization of complex
distribution. Sodium nitrate and sulphuric concentrate
acid of analytical grade and distilled water
was used to make up all required solutions. The particle size distribution and
Analytical grade chemicals were used for chemical analysis of the concentrate and
analysis. each size fraction is shown in Table 1. The
major amount (52.4%) of the concentrate
2.2. Leaching procedure was of very small particles (– 45 μm), while
the fraction + 75 μm was in minor amount
Leaching experiments were carried (9.4%). The zinc, copper, lead and iron
out in a closed glass reactor equipped with a content in different fractions were similar.
Teflon stirrer, condenser, thermometer, glass
funnel for adding the solid sample and a Table 1. Chemical composition of different
sampling device. This set-up provides stable fractions of complex concentrate
hermetic conditions and allows heating at Particle size Fraction Element (%)
constant temperature. The 1.2 dm3 of (μm) (wt.%) Zn Cu Pb Fe
leaching solution (NaNO3 + H2SO4) was Mixed
added to the glass reactor and heated-up to - 8.79 8.92 12.66 19.8
particle
the selected temperature. When the
75 9.4 7.85 7.42 13.26 19.41
temperature was reached, the 20 g of solid
– 75 + 50 16.4 8.93 9.18 10.75 19.96
concentrate was added. The stirring started
– 50 + 37 21.8 9.27 9.53 11.03 20.03
and the reaction commenced. After selected
– 37 52.4 8.83 8.99 12.56 19.78
time intervals, the solution samples were
taken for chemical analysis, which was The X-ray diffraction analysis of the
carried out by AAS (Perkin Elmer). The concentrate sample (Figure 1) shows the
samples were chemically analyzed for the presence of sphalerite, chalcopyrite, galena,
zinc content and degree of zinc extraction pyrrhotite, and quartz.
was calculated. The leach residues were The mineralogical qualitative and
filtered, washed with distilled water, and quantitative analysis of complex concentrate
dried. The phase content of complex was realized using a reflected light
 M. Sokić / JMM 48 (2) B (2012) 185 - 195 189

Figure 1. X-ray diffractogram of the complex concentrate

microscopy and was given in Table 2. The appears in a form of liberated grains in some
correction of quantitative mineralogical 59 %. The rest mineral grains of sphalerite
analysis was obtained through the chemical are mostly in a form of concretions, simple
analysis of Cu, Zn and Pb. The sulphide and complex intergrowths.
volume content in whole sample is 69.5 %, The SEM image of complex concentrate
in which 60.9 % are sulphide-liberated is shown in Fig. 2. The EDX analysis of
grains. complex concentrate for marked area in
The main and most abundant zinc SEM micrograph presented in Fig. 2 shows a
sulphide mineral is sphalerite (13.01 %). It presence of sphalerite grains with high
content of iron (Zn – 55.49%, Fe – 11.43%
Table 2. Mineralogical composition of and S – 33.08%).
complex concentrate
Mineral Wt. (%)
Chalcopyrite 25.62
Sphalerite 13.01
Galena 14.62
Pirrhotite 15.7
Marcasite 0.25
Arsenopyrite 0.15
Sulfosalts Pb-Bi 0.07
Covellite 0.02
Native bismuth 0.04
Tetrahedrite 0.03
Limonite 0.03
Gangue minerals 30.47 Figure 2. SEM micrograph of complex
Total: 100 concentrate
190 M. Sokić / JMM 48 (2) B (2012) 185 - 195

3.2. Effect of temperature and time The reason for this was elemental sulphur,
formed during the process, precipitated at the
The influence of the temperature and time particle surfaces.
on the dissolution rate of sphalerite in the
temperature range of 60 to 90oC, and during 3.3. Kinetic analysis
the time intervals of 60 to 240 min, under
optimal following conditions: stirring speed The process of zinc sulphide leaching
300 rpm, particle size – 37 μm, 1.5 M by H2SO4 + NaNO3 solution is a complex
H2SO4, 0.6 M NaNO3, and phase ratio 20 g heterogeneous process. In order to determine
concentrate/1.2dm3, was presented in Figure the kinetic parameters and the rate-
3. Leaching degrees were calculated based controlling step of the sphalerite leaching
on the results of chemical analysis of the process, Sharps’s method of reduced half
solutions and the leach residues. time of reaction was used to select the kinetic
The temperature and time has a models [25, 29-32]
significant influence on the leaching rate. As F(x) = A × (t/t0.5) (5)
expected, zinc dissolution increases with where x is the degree of reaction, t0.5 is the
increasing the temperature and time. By time to reach x = 50 %, and constant A
increasing the temperature from 60 to 90oC, depends on a function F(x).
the dissolution rate increases from 25.23% to It is possible to determine values of the
71.66% after 2 hours, i.e. from 59.40% to reaction half time and time for different
99.83% after 4 hours of leaching. A degrees of leaching for each temperature, for
significant slowing down on the leaching the isotherms in Fig. 3. Therefore, the values
rate in the final stage of leaching was noted. of (t/t ) for different kinetic models can be
0.5
compared with the values of the
experimental results to get the best kinetic
function for linearization of the results [25,
31]. For the extraction of zinc, the
experimental curve is closest to the function:
x2 = k·t (6)
where k is the rate constant, t is the
reaction time.
This kinetic model is used for a
description of diffusion-controlled
processes. The rate of reaction may be
limited by diffusion of the reactants through
Figure 3. Effect of temperature and time on the sulphur layer, precipitated on the particle
zinc extraction (stirring speed = 300 rpm, surfaces.
particle size – 37 μm, [H2SO4] = 1.5 M, In order to determine the activation
[NaNO3] = 0.6 M, phase ratio 20 g/1.2dm3 energy, Eq. (6) was applied to the data
 M. Sokić / JMM 48 (2) B (2012) 185 - 195 191

obtained from each temperature for zinc sphalerite with ammonium persulphate in
leaching in Fig. 3. The variation in x2 = k·t sulphuric acid media. The activation energy
with time at different temperatures is shown was 41±2 kJ/mol in the temperature range
in Fig. 4. 4 The activation energy of 55 35-60oC, and the diffusion through the
kJ/mol was calculated using the Arrhenius product layer was the rate-controlling step.
equation k = A·e–Ea/RT from the slopes of the Lochmann and Pedlik [4] leached
straight lines in Fig. 4, as shown in Fig. 5. sphalerite concentrate with acidic ferric
sulphate solution and found that the
elemental sulphur layer controlled the
dissolution rate.
Bobeck and Su [33] obtained the
activation energy of 46.9 kJ/mol for
sphalerite leaching in ferric chloride solution.
During the initial stages of leaching the rate
of reaction was chemically controlled and
later, transport of ions across the product
sulphur layer determined the reaction rate.
Similar values of activation energy of 45.3
kJ/mol were determined Aydogan et al. [11],
but they were found that the sphalerite
dissolution in acidic ferric chloride solution
Figure 4. Plot of x2 vs time for zinc extraction controlled by the shrinking core model for
reaction-controlled process. Aydogan [34],
also investigated the kinetics of sphalerite
leaching with hydrogen peroxide in sulphuric
acid, and found that the leaching rate
controlled by surface reaction. The value of
activation energy was 43 kJ/mol.

3.4. Characterization of the leach

residue

The leach residue, obtained at 80oC under

the following conditions: stirring speed 300
rpm, 1.5 M H2SO4, 0.6 M NaNO3, 20 g
3
Figure5. Arrhenius plot for zinc extraction concentrate/1.2 dm and 240 min, was
chosen for chemical, X-ray, qualitative and
Various investigators were found the quantitative mineralogical analyses and
similar values of activation energy for the SEM/EDX analyses. A chemical analysis of
sphalerite leaching. Babu et al. [20] leached the leach residue is shown in Table 3.
192 M. Sokić / JMM 48 (2) B (2012) 185 - 195

Table 3. Chemical composition of the leach residue

Mass of the leach residue Element (%)
(g) Zn Cu Fe Pb Elemental S
11,78 1,96 3,57 10,75 19,75 17.02

Figure 6. X-ray diffractogram of the leach residue: T = 80oC, t = 240 min, stirring speed = 300
rpm, [H2SO4] = 1.5 M, [NaNO3] = 0.6 M, phase ratio 20 g/1.2dm3

The X-ray diffraction analysis of the leach sulphide volume content is 31.7 %, in which
residue is presented in Figure 6. Along with 37.9 % are sulphide-liberated grains. The
the unreacted minerals, the presence of sphalerite appears in a form of liberated
elemental sulphur and anglesite were grains in some 21.8 %. The rest mineral
detected. grains of sphalerite are mostly in a form of
The qualitative and quantitative concretions, simple and complex
mineralogical analysis of the leach residue intergrowths.
was realized using a reflected light
microscopy and was given in Table 4. The Table 4. Mineralogical composition of the
main components in the residue are leach residue.
elemental sulphur and anglesite, while the Mineral Wt. (%)
content of sphalerite, chalcopyrite and Chalcopyrite 10,32
galena are decrease. The elemental sulphur is Sphalerite 3,11
the oxidized product of sulphide sulphur, Galena 6,40
precipitated on the surface of concentrate Pirrhotite 11,86
particles. In mineral grains, anglesite is Anglesite 20,86
present together with galena, in which the Elemental sulphur 17.02
central parts filled with galena, while Gangue minerals 30,43
anglesite precipitated on the surface. The Total 100,00
 M. Sokić / JMM 48 (2) B (2012) 185 - 195 193

final stage of leaching. From these results

and literature data it seems as if the
dissolution process can be represented by
one of the following chemical reactions:
ZnS + 2/3NaNO3 + 4/3H2SO4 = ZnSO4 +
1/3Na2SO4 + S0 + 2/3NO + 4/3H2O (7)
ZnS + 2NaNO3 + 2H2SO4 = ZnSO4 +
Na2SO4 + S0 + 2NO2 + 2H2O (8)
ZnS + Fe2(SO4)3 = ZnSO4 + 2FeSO4 + S0 (9)
FeSO4 + 1/3NaNO3 + 2/3H2SO4 =
1/2Fe2(SO4)3 + 1/6Na2(SO4)3 +
1/3NO + 2/3H2O (10)
Figure 7. SEM micrograph of the leach
residue: T = 80oC, t = 240 min, stirring speed = The NO to NO2 ratio in gaseous products
300 rpm, [H2SO4] = 1.5 M, [NaNO3] = 0.6 M, and the elemental sulphur to sulphate ratio
phase ratio 20 g/1.2dm3 after leaching depend on the concentration of
the nitrate ion [28]. NO gas that is produced
The SEM image of the leach residue is is oxidized by the air into the NO2, which
shown in Fig. 7. The EDX analysis of dissolves in the solution and reacts with
complex concentrate for marked areas on water to form HNO3. Elemental sulphur is
SEM micrograph presented in Fig. 2 show a the main product of reaction, and a minor
presence of compact elemental sulphur (S – amount of sulphide sulphur is oxidized to
100%) (area 1) and anglesite (Pb – 50.62%, sulphate during leaching. Iron is oxidized to
S – 16.03%, O – 33.34%) (area 2) on the form ferric sulphate in the high content of
surface of sphalerite and other mineral nitrates, which then acts as a leaching agent.
particles, which inhibit their dissolution. The A low concentration of nitrates does not
morphology of the leach residue implies that result in noticeable acceleration of high
the sphalerite leaching proceeds by the temperature ferrous oxidation in a sulphuric
diffusion of lixiviant through the sulphur acid solution [35].
reaction product.
4. Conclusion
3.5. Dissolution process
The leaching kinetics and mechanism of
X-ray diffraction, qualitative and sphalerite from complex concentrate,
quantitative mineralogical analyses and enriched through the flotation of a CuFeS2-
SEM/EDX analyses of the residue indicates PbS-ZnS complex ore in the “Rudnik”
that the sulphur, which formed during the flotation plant, by sulphuric acid and sodium
reaction, precipitated at the particle surfaces, nitrate was studied and discussed. It was
and slowed down of the leaching rate in the determined that the leaching rate increased
194 M. Sokić / JMM 48 (2) B (2012) 185 - 195

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