Hydrometallurgy 144145 (2014) 8690

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Hydrometallurgy
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Technical note

Leaching and kinetic modeling of calcareous bornite in ammonia

ammonium sulfate solution with sodium persulfate
Zhi Xiong Liu a,c,, Zhou Lan Yin b, Shao Feng Xiong a, Yi Guan Chen c, Qi Yuan Chen b
a
b
c

College of Physics and Mechanical & Electrical Engineering, Jishou University, Jishou 416000, PR China
School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, PR China
The Key Laboratory of Plant Resources Conservation and Utilization, College of Hunan Province, Jishou University, Jishou 416000, PR China

a r t i c l e

i n f o

Article history:
Received 22 May 2013
Received in revised form 30 November 2013
Accepted 7 January 2014
Available online 24 January 2014
Keywords:
Calcareous bornite
Leaching kinetic model
Ammoniaammonium sulfate solution
Sodium persulfate

a b s t r a c t
The leaching process of copper from calcareous bornite using sodium persulfate as an oxidant in ammoniacal
solution was investigated. The effects of agitation speed, leaching temperature, concentration of ammonia
and ammonium sulfate, and dosage of sodium persulfate on the leaching rate of copper from bornite ore were
determined. The results indicate that the leaching rate is nearly independent of agitation above 400 rpm and
increases with increasing temperature, concentration of ammonia and ammonium sulfate and dosage of sodium
persulfate. The leaching kinetics was analyzed by a new variant of the shrinking core model (SCM) in which
both the interfacial transfer and the diffusion across the product layer affect the leaching rate, and its apparent
activation energy was found to be 15.6 kJ/mol.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Due to the continuous decrease in the high-grade copper ore
deposits and the stringent requirement of environmental protection,
the traditional metal recovery processes based on roasting have become
less desirable (Rodrguez et al., 2003). The hydrometallurgical method
has been more practically acceptable because there is no production of
SO2 gas. Bornite is often found in copper-ore bodies with other minerals
such as chalcopyrite and chalcocite. It ranks in economic importance
after chalcopyrite and chalcocite. The leaching behavior of bornite was
investigated in acid leaching process (Arce and Gonzlez, 2002;
Dutrizac et al., 1970; Pesic and Olson, 1984; Price, 1981) and bioleaching
process (Bevilaqua et al., 2006, 2010; Denise et al., 2009; Wang et al.,
2008).
Ammonia, as an effective lixiviant, has been extensively used
in copper, nickel and cobalt industries for many years due to its
inherent advantages over alternative reagents. One advantage is that
the basic leaching solution alleviates corrosion problems encountered
in the acidic systems. Another advantage is that ammonia leaching
minimizes the major wasteful components such as iron, which can be
removed as insoluble oxy/hydroxyl compounds during the leaching
process.
Oxidative-ammonia leaching, with oxygen as oxidant, was widely
used in the processing of sulde ores, especially chalcopyrite, sphalerite,
and pyrite (Beckstead and Miller, 1977; Bell et al., 1995; Ghosh et al.,
Corresponding author at: College of Physics and Mechanical & Electrical Engineering,
Jishou University, Jishou 416000, PR China.
0304-386X/$ see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.hydromet.2014.01.011

2003; Park et al., 2007; Rao and Ray, 1998; Rao et al., 1993; Reilly
and Scott, 1984). Most of the oxidation reactions of suldes in ammoniacal solution take place slowly in the presence of O2 or air at low
temperature, and hence the oxidative leaching of sulde ores in
ammoniacal solution is generally processed under high pressure and
temperature.
The dissolution kinetics of bornite ore was investigated in acidied
ferric chloride solutions (Pesic and Olson, 1983). It was found that
bornite was leached in two stages of reaction with the rst stage
being more rapid than the second one. The dissolution reaction in the
rst stage was electrochemical and was mixed kinetics-controlled and
the reaction in the second stage was controlled by diffusion through
the product layer. The leaching kinetics of bornite ore was also
performed in acidied ferric sulfate solution (Dutrizac et al., 1970).
However, the leaching kinetics of bornite in ammoniacal solution has
not been reported in any papers.
Our previous work (Liu, 2012) indicated that calcareous bornite
could not be extracted effectively in ammoniacal solution in the
presence of O2 or air at low temperature. Hence, effective extraction of
copper from the calcareous bornite in ammoniacal solution becomes
our focus.
Persulfate is well known as an efcient oxidizing agent (Francis et al.,
2012; Reed et al., 2005). It has been used academically as a leaching
agent for the recovery of metals in alkaline solutions (Li et al., 2009;
Reed et al., 2005). In the present study, the effects of stirring speed,
temperature, dosage of persulfate, and concentration of ammonia and
ammonium sulfate on the leaching of calcareous bornite with persulfate
as oxidizing agent in ammoniacal solution are interpreted.

Z.X. Liu et al. / Hydrometallurgy 144145 (2014) 8690

2. Experimental
2.1. Materials and analysis
The calcareous bornite ore was taken from Tang Dan, Yunnan
province, China. It contained 30.79% Cu, 12.00% Ca, 6.48% Mg, 13.62%
Fe, 15.00% S, 0.32% Mn, 0.20% Zn, 0.08% Cr and 0.17% Al. The X-ray
diffraction (XRD) pattern of the raw ore was shown in Fig. 1. The XRD
patterns were recorded on a Rigaku Miniex diffractometer with Cu
K X-ray radiation at 35 kV and 20 mA. As can be seen from Fig. 1, the
raw ore contains the crystalline phases of bornite (49.5%), chalcopyrite
(10.3%) and dolomite (40.2%). The contents of copper, calcium, iron,
magnesium and so on were determined by a ame atomic absorption
spectrophotometer.

87

solution with the addition of sodium persulfate can be explained in

terms of a synergetic mechanism involving complexing and oxidizing
reactions. The unambiguous characteristic of the dissolution process of
suldes requires an additional study. Probably, these reactions can be
written as follows:
2

Cu5 FeS4 18:5S2 O8 55NH3 19H2 O NH4 2 SO4

2
2

5CuNH3 4 FeOH3 42SO4 37NH4

2CuFeS2 17S2 O8

46NH3 22H2 O
2

2.2. Experimental procedure

2FeOH3 n3H2 OFe2 O3 nH2 O:

After the raw bornite ore was crushed and ground to less than
0.090 mm, it was sieved to the four size fractions (0.0000.037,
0.0370.050, 0.0500.075 and 0.0750.090 mm). Experiments were
performed on the ore with 0.037 mm fraction unless otherwise
stated.
In each experiment, a ask containing 500 cm3 of ammoniacal
solution with the desired concentration was submerged in a tank, the
temperature of which was kept constant at 0.5 C.
When the required temperature was reached, 2 g of the sample ore
together with a certain amount of sodium persulfate was added into the
ask when the stirring was started. The leaching was carried out for 3 h
during which 2-cm3 samples were taken for the determination of Cu
concentration using a ame atomic absorption spectrophotometer,
and then 2-cm3 fresh lixiviant was added into the reactor to keep the
volume of solution constant. The leached residues were ltered, washed
with 0.1% (mass fraction) ammonia solution and dried for the analysis
of XRD and SEMEDS.

3.1. Effect of parameters

3. Results and discussion

The effect of stirring speed, concentration of ammonia and ammonium sulfate and dosage of sodium persulfate on the low-grade oxide
copper/zinc ore containing sulde ore was investigated in our previous
study. It has been shown that persulfate in ammoniacal solution can
oxidize the metallic ions of low valence in suldes to ions of high
valence which can form readily soluble complexes with ammonia in
the leaching solution. The enhanced leaching of the ore in ammonia

Fig. 1. XRD patterns of the bornite ore and the leached residue.

The effect of agitation on the copper leaching from bornite ore was
studied in the range from 100 to 600 rpm. An adequate suspension of
the solid particles was observed at 400 rpm and the copper dissolution
was independent of the agitation speed above this speed. Therefore,
in the subsequent experiments agitation was maintained at 500 rpm
to eliminate the effect of agitation as a variable.
The leaching was carried out in the temperature range of 303.15
333.15 K for an initial concentration of 2.0 mol/dm3 ammonia and
1.0 mol/dm3 ammonium sulfate with a dosage of 0.050 mol/g sodium
persulfate. The effect of temperature on the extraction of copper is
shown in Fig. 2. It is indicated that the extraction of copper increases
with temperature. The extraction of copper rises from 82.7 to 90.3%
when temperature increases from 303.15 to 333.15 K.
The effect of sodium persulfate dosage (npersulfate) on the extraction
of copper was investigated at 313.15 K. Not surprisingly, the extraction
of copper increases with the increase of sodium persulfate dosage
as given in Fig. 3. But when the sodium persulfate dosage is over
0.050 mol/g, the effect of sodium persulfate dosage on the extraction
of copper is moderate and the extraction of copper is almost the same.
The effects of concentration of ammonia and ammonium sulfate on
the extraction of copper were investigated as shown in Fig. 4. Fig. 4(a)
indicates that the extraction of copper is 77.8% and 88.1% when the
concentrations of ammonia are 1.0 mol/dm3 and 2.5 mol/dm3, respectively. It is also observed that the extraction of copper remains almost
the same when the concentration of ammonia is above 2.0 mol/dm3
ammonia. Fig. 4(b) shows that the extraction of copper increases from
80.9% to 90.3% when the concentration of ammonia sulfate is increased

Fig. 2. Effect of temperature on the extraction of copper.

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Z.X. Liu et al. / Hydrometallurgy 144145 (2014) 8690

sulfur was produced. The results of chemical analysis agree well with
the XRD results. All these results indicate that bornite is dissolved
more easily than primary chalcopyrite in ammoniaammonium sulfate
solution with sodium persulfate.
The SEMEDS of the residue after the bornite ore was leached for 2 h
is shown in Fig. 5. The micrograph of the residue presents a porous
surface due to the dissolution of copper and sulfur. The SEMEDS
of the residue shows that calcium and iron assemble onto the mineral
surface and remain as an ash layer. However, this mineral surface is
not covered completely by calcium (dolomite) and iron (hematite)
and there are many pores in aggregated particles.
3.3. Kinetics analysis

Fig. 3. Effect of sodium persulfate dosage on the extraction of copper.

from 0.5 mol/dm3 to 1.5 mol/dm3. The extraction of copper is about

the same when the concentration of ammonium sulfate is above
1.5 mol/dm3. Ammoniaammonium sulfate solution is a buffer solution
with pH between 8.30 and 10.80 which is optimal for the formation of
stable copper complex Cu(NH3)2+
(Knkl et al., 1994).
4
3.2. XRD and morphology of the leaching residues
The XRD patterns of the residue on the leaching conditions
(temperature 313.15 K, 2.0 mol/L NH3 H2O, 1.0 mol/L (NH4)2SO4,
0.050 mol/g Na2 S2 O 8) are presented in Fig. 1. As is seen from
Fig. 1, there are crystalline phases of dolomite, chalcopyrite, sulfur,
ferric oxide and copper sulde in the residues when the ore is
leached for 0.5 h and 1.0 h, respectively. However, copper sulde
was not identied in the residue when the ore is leached for
3.0 h. The results of chemical analysis indicate that 88% Cu in the
bornite ore was dissolved and Fe was almost remained. If sulfur
in the ore was oxidized completely into SO24 , the content of sulfur
in the residue after leaching for 3 h should be about 2.0% when the
extraction of copper was 88.0%. However, the content of sulfur in
the residue was detected to be 4.8%, which indicates that elemental

The leaching process of copper from bornite ore is a solidliquid

multi-phase reaction, and the leaching reaction occurs on the interface
of two phases. The most common kinetic model for solidliquid reaction
is the shrinking unreacted core model (SCM) (Levenspiel, 1972).
When the chemical process is the rate-controlling step, the integral
rate equation can be expressed as follows (Levenspiel, 1972):
1=3

11x

Kct

where x is the fraction reacted; Kc is the chemical rate constant; and t is

the reaction time.
If the reaction rate is controlled by the diffusion through the solid
layer consisting of insoluble core around the unreacted core, the integral
rate expression can be written as follows (Levenspiel, 1972):
2=3

12=3x1x

KDt

where KD is the pore diffusion rate constant.

According to Eqs. (4) and (5), when the leaching rate is controlled by
the chemical reaction, the plot of [1 (1 x)1/3] vs. time is a straight
line with a slope Kc. Similarly, the plot of [1 2/3x (1 x)2/3] vs.
time is a straight line with a slope KD.
For the kinetic analysis in this work, the shrinking core models with
chemical reaction and diffusion through product layer as the ratecontrolling steps, Eqs. (4) and (5), were evaluated. 1 (1 x)1/3 and
1 2/3x (1 x)2/3 were plotted with respect to the leaching time
and then the dependency of these models on the kinetic data was
evaluated using the correlation coefcient (R2) in Table 1. The slopes

Fig. 4. Effects of concentration of ammonia and ammonium sulfate on the extraction of copper (a) ammonia; (b) ammonium sulfate.

Z.X. Liu et al. / Hydrometallurgy 144145 (2014) 8690

89

Table 1
Correlation coefcients (R2) of three kinetic models at different leaching temperatures.
Leaching
temperature (K)

Kinetic expression
1 (1 x)1/3

1 2x/3 (1 x)2/3

1/3ln(1 x) +
(1 x)1/3 1

303.15
313.15
323.15
333.15

0.8645
0.7846
0.7992
0.7804

0.9491
0.9084
0.9198
0.9059

0.9925
0.9893
0.9947
0.9941

of these plots were the apparent rate constants (Kc and KD). The correlation coefcients (R2) for the SCM with chemical reaction and diffusion
as the rate-controlling steps were both below 0.94. It indicates that
both kinetic models could not illustrate clearly the leaching behavior
of bornite. Hence, in the present work a new variant of the SCM
(Dickinson and Heal, 1999), based on both the interface transfer and diffusion across the product layer being the rate-controlling step of the
solidliquid reaction, was employed to describe the leaching process.
The integral rate expression can be presented as follows:
1=3

1=3 ln 1x1 1x

Kt

where K is the apparent rate constant.

According to the model Eq. (6), a plot of 1/3ln(1 x) +(1
x) 1/3 1 vs. time is shown in Fig. 6 and the correlation coefcients (R2) are listed in Table 1. All the correlation coefcients are over
0.989. It is indicated that the model Eq. (6) can be used to describe properly the leaching process of bornite in ammoniacal solution.
The variation of reaction rate with temperature is commonly
described using the empirical Arrhenius law:
K k0 expEa=RT

where k0, Ea, and R are the pre-exponential factor, the apparent activation energy and universal gas constant, respectively. The estimation of
the apparent activation energy and the pre-exponential (frequency)
factor (k0) is based on the logarithmic form of the Arrhenius law:
ln K ln k0 Ea=RT :

Using the apparent rate constants obtained by the application of

Eq. (6), a plot of lnK vs. T1 (Arrhenius plot) was shown in Fig. 7 and
the activation energy was calculated as 15.6 kJ/mol.
The activation energy (15.6 kJ/mol) for the leaching process of
bornite ore is close to the activation energy (15 kJ/mol) of malachite
dissolution (Bingl et al., 2005) controlled by the mixing control

Fig. 5. SEMEDS of the residue (condition: 313.15 K, 2.0 mol/L NH3 H2O, 1.0 mol/L
(NH4)2SO4, 0.050 mol/g Na2S2O8, leaching time 2 h).
Fig. 6. Plot of 1/3ln(1 x) 1 + (1 x)1/3 vs. time at different temperatures.

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Z.X. Liu et al. / Hydrometallurgy 144145 (2014) 8690

(Construct Program of the Key Discipline in Hunan Province, China,

JSU071301).
References

Fig. 7. Arrhenius plot for leaching of copper.

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product layer were the rate-controlling step of the reaction.
4. Conclusions
The dissolution kinetics of copper from bornite ore was investigated
in ammoniacal solution with sodium persulfate. It was observed that
the main parameters were determined as leaching time, temperature,
concentration of ammonia/ammonium sulfate and dosage of sodium
persulfate in the experiments.
It was found that the agitation speed above 400 rpm was sufcient
to eliminate the effect of agitation speed on the leaching rate. The
extraction of copper was increased with increasing temperature,
concentration of ammonia and ammonium sulfate and dosage of sodium persulfate. SEMEDS analysis shows that calcium (dolomite) and
iron (hematite) assemble onto the solid particles and remain as an
ash layer.
The dissolution kinetics of bornite in ammoniacal solution
with sodium persulfate is controlled by the interface transfer
and diffusion across the product layer of dolomite and hematite
which both affect the reaction rate. This model equation is given
as 1/3ln(1 x) 1 + (1 x) 1/3 = Kt. The apparent activation
energy was found to be 15.6 kJ/mol.
Acknowledgment
The study was supported by the NSFC (Natural Science Fund
Council, China, 2007CB61301), the HEFC (Hunan Education Fund
Committee, China, 10C1095), the JSUFC (Jishou University Fund
Committee, jsdxxcfxbskyxm201205 and 2012KCB05) and the CPKDHP

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