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Original Article
a r t i c l e i n f o a b s t r a c t
Article history: This study was performed in two phases of work. In the first stage, alkaline leaching of
Received 17 October 2016 lead and zinc from an Iranian low-grade oxide ore was examined and the influence of the
Accepted 7 March 2017 operating variables including stirring speed, leaching temperature, NaOH concentration and
Available online xxx liquid to solid ratio was determined experimentally. The optimum condition was found to be
NaOH concentration of 4 M, liquid to solid ratio of 20 ml/g, temperature of 80 ◦ C and a stirring
Keywords: speed of 500 rpm for lead and 400 rpm for zinc, in the range of investigated parameters.
Alkaline leaching Under these conditions, the highest recovery of lead and zinc was obtained to be 72.15
Kinetics modeling and 85.52%, respectively. In the second stage, the dissolution kinetics of lead and zinc was
Shrinking core models evaluated by the shrinking core models. The finding reveals that diffusion through the fluid
Low-grade ore film was the leaching kinetics rate controlling step of lead and zinc. The activation energy
Recovery was found to be 13.6 kJ/mol for lead and 13.92 kJ/mol for zinc. Equations representing the
leaching kinetics of lead and zinc were achieved to be 1 − (1 − x)2/3 = 0.7272 × e(−13.6/(8.314×T)) × t
and 1 − (1 − x)2/3 = 0.9686 × e(−13.92/(8.314×T)) × t, respectively.
© 2017 Published by Elsevier Editora Ltda. on behalf of Brazilian Metallurgical, Materials
and Mining Association. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
∗
Corresponding author.
E-mails: azizi.asghar22@yahoo.com, aazizi@shahroodut.ac.ir (A. Azizi).
http://dx.doi.org/10.1016/j.jmrt.2017.03.005
2238-7854/© 2017 Published by Elsevier Editora Ltda. on behalf of Brazilian Metallurgical, Materials and Mining Association. This is an
open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article in press as: Seyed Ghasemi SM, Azizi A. Alkaline leaching of lead and zinc by sodium hydroxide: kinetics modeling. J
Mater Res Technol. 2017. http://dx.doi.org/10.1016/j.jmrt.2017.03.005
JMRTEC-266; No. of Pages 8
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The required ore samples were obtained from the Irankuh ZnCO3 + 4OH− → Zn(OH)4 2− + CO3 2− (3)
district (Goshfil mine tailings), which is located about 20 km
southwest of the city of Isfahan in Iran. The samples were 3.2. Effect of liquid to solid (L/S) ratio
crushed and then ground to less than 150 m. The phases of
sample were characterized by XRD, which the main phases of The phase ratio of liquid to solid is another important factor
lead and zinc identified from the XRD pattern included smith- to influence the contact chance of hydroxyl ions with lead and
sonite (ZnCO3 ) and cerussite (PbCO3 ). The main chemical zinc oxides. These experiments were carried out in 4 M NaOH
composition of samples was characterized by X-ray fluores- solution for 90 min at 70 ◦ C with stirring of 500 rpm. The exper-
cence. The results showed that the sample contained 5.91% imental data for different L/S ratios ranging from 10 to 25 ml/g
ZnO and 5.32% PbO [21]. are illustrated in Fig. 2. As observed, the recovery of lead and
zinc enhanced with increasing L/S ratio from 10 to 20 ml/g.
2.2. Experimental procedure However, further increase the L/S ratio to 25 ml/g, the leach-
ing rate is reduced. Thus, L/S ratio of 20 is found to be optimal.
The dissolution process was carried out in a beaker of 500 ml, According to Rao et al. [22], a higher L/S ratio is expected to
which heated a hot plate, equipped with a digital controlled reduce the viscosity of the slurry by facilitating better mix-
magnetic stirrer and a thermometer for temperature control. A ing, contributing to the reduction in diffusional mass transfer
series of sodium hydroxide solution with concentration from resistance. This phenomenon also can be understood from the
0.5 to 4 M were prepared as leaching agent and put into the mass transportation equilibrium between ZnO and PbO and
beaker. According to the desired liquid to solid (L/S) ratio, 3 g the coordination ions Zn(OH)4 2− and Pb(OH)4 2− in the leaching
of solid was added into the sodium hydroxide solution. Then solution.
solutions were mixed using a magnetic stirrer with a certain
speed at the required temperature. When the dissolution pro- 3.3. Effect of stirring speed
cess finished, the sample was filtered and the liquid phase was
analyzed with AAS for the content of lead and zinc. The leach- The effect of stirring speed on the dissolution performance of
ing rate of Pb and Zn was calculated according to the following lead and zinc samples was evaluated by regulating the stirring
formula: speed to 200, 300, 400 and 500 rpm at 70 ◦ C, NaOH concentra-
CM × V tion of 4 M, and L/S ratio of 20 ml/g. Fig. 3 demonstrates that the
R= × 100 (1) stirring speed has an appreciable effect on the dissolution of
C0 × M
lead and zinc. It can be seen that, after 90 min of dissolution,
where R is the leaching recovery percentage of metal (Pb or the leaching fraction of lead increases from 53.65 to 80.92%
Zn); CM (g/L) is the concentration of metal ion (Pb or Zn) in when the stirring speed increased from 200 to 500 rpm. It is
the leach liquor; V (L) is the leach liquor volume; C0 (%) is the also observed that, the stirring speed of 400 rpm is beneficial
metals content of Pb and Zn in oxide ore sample and M (g) is for the extraction of zinc to bring mineral particles into ade-
the mass of the Pb and Zn oxide ore. quate contact with NaOH solution. According to Zhang et al.
Please cite this article in press as: Seyed Ghasemi SM, Azizi A. Alkaline leaching of lead and zinc by sodium hydroxide: kinetics modeling. J
Mater Res Technol. 2017. http://dx.doi.org/10.1016/j.jmrt.2017.03.005
JMRTEC-266; No. of Pages 8
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100 100
0.5 M 0.5 M
90 1M 90 1M
2M 2M
80 4M 80 4M
Pb recovery (%)
Zn recovery (%)
70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 20 40 60 80 100 0 20 40 60 80 100
Leaching time (min) Leaching time (min)
Fig. 1 – Effect of NaOH concentration on the leaching recovery of lead and zinc at temperature of 70 ◦ C, L/S ratio of 20 ml/g
and stirring speed of 500 rpm.
[14], increasing the stirring speed promotes reactants diffu- 80 ◦ C. According to Rao et al. [22], with enhancing the leaching
sion from bulk solution to mineral surface and improves the temperature, the energy available for atomic and molecu-
leaching rate. lar collisions increases. In addition, mass transfer coefficient,
reaction constant and diffusivity are all improved with the
development of temperature. Thus, it can be found that a high
3.4. Effect of temperature enough temperature is necessary to activate the reagent and
accelerate the reaction of hydroxyl ions with lead and zinc
In order to investigate the effect of temperature on the disso- oxides in the alkaline leaching.
lution of low-grade lead and zinc oxide ore, temperature was
varied from 50 ◦ C to 80 ◦ C and experiments were performed
at NaOH concentration of 4 M and L/S ratio of 20 ml/g with 3.5. Kinetic modeling
stirring speed of 500 rpm for lead and 400 rpm for zinc. The
variation in the leaching ratio with various temperatures is Leaching kinetics plays an important role in the extraction of
shown in Fig. 4. It can be seen that, with increasing the tem- metals and compounds in an economical way. According to
perature from 50 ◦ C to 80 ◦ C, the leached zinc increases from Wang et al. [23], it can be concluded that the leaching process
49.28% to 72.15% after 90 min. It is also observed that the zinc in NaOH solution involves: (i) transport of NaOH from the bulk
leaching rate by NaOH is only 60.32% at 50 ◦ C, but quickly solution to the particle surface, (ii) diffusion of NaOH through
enhances to 85.52% when the temperature is increased to the solid residual layer from the particle surface to the surface
100 100
L/S = 10 ml/g L/S = 10 ml/g
90 L/S = 15 ml/g 90 L/S = 15 ml/g
80 L/S = 20 ml/g 80 L/S = 20 ml/g
Pb recovery (%)
Zn recovery (%)
30 30
20 20
10 10
0 0
0 20 40 60 80 100 0 20 40 60 80 100
Leaching time (min) Leaching time (min)
Fig. 2 – Effect of L/S ratio on the leaching recovery of lead and zinc at temperature of 70 ◦ C, NaOH concentration of 4 M and
stirring speed of 500 rpm.
Please cite this article in press as: Seyed Ghasemi SM, Azizi A. Alkaline leaching of lead and zinc by sodium hydroxide: kinetics modeling. J
Mater Res Technol. 2017. http://dx.doi.org/10.1016/j.jmrt.2017.03.005
JMRTEC-266; No. of Pages 8
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4 j m a t e r r e s t e c h n o l . 2 0 1 7;x x x(x x):xxx–xxx
100 100
200 rpm 200 rpm
90 300 rpm 90 300 rpm
80 400 rpm 80 400 rpm
Pb recovery (%)
Zn recovery (%)
500 rpm 500 rpm
70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 20 40 60 80 100 0 20 40 60 80 100
Leaching time (min) Leaching time (min)
Fig. 3 – Effect of stirring speed on the leaching recovery of lead and zinc at temperature of 70 ◦ C, NaOH concentration of 4 M
and L/S ratio of 20 ml/g.
of unreacted core, (iii) reaction between NaOH and low-grade For surface chemical reaction control :
oxide ore on the surface of the unreacted core (Eqs. (2) and 1/3
1 − (1 − x) =k×t (6)
(3)), (iv) diffusion of the resultants through the solid residual
layer from the reaction interface to the particle surface, and
(v) transport of the resultants from the particle surface to the where x is the fractional conversion of lead and zinc, t is
bulk solution. The reactions occurring during the leaching pro- the reaction time (min) and k is the apparent rate constant
cess are typically heterogeneous [24] and the relevant kinetics (min−1 ). The overall rate of dissolution is controlled by the
follows the shrinking core model which was described by Lid- slowest of these sequential steps.
dell in detail [25]. The following expressions can be used to Values of Eqs. (4)–(6) versus the reaction time were plotted
describe the leaching process kinetics [3,26]: to determine the kinetic parameters and leaching rate control-
ling step, which the results are shown in Figs. 5 and 6. Leaching
For diffusion control through the fluid film : experiments were carried out at temperatures ranging from 50
2/3 to 80 ◦ C in steps of 10 ◦ C at NaOH concentration of 4 M and L/S
1 − (1 − x) =k×t (4)
ratio of 20 ml/g with a stirring speed of 400 rpm for zinc and
500 rpm for lead.
From the slopes of the straight lines the apparent rate
For solid product diffusion control :
constants, k, were evaluated, which the rate constants calcu-
2/3
1 − 3(1 − x) + 2(1 − x) = k × t (5) lated and their correlation coefficients are given in Figs. 5 and 6
100 100
50 °C 50 °C
90 60 °C 90 60 °C
80 70 °C 80 70 °C
80 °C 80 °C
Pb recovery (%)
Zn recovery (%)
70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 20 40 60 80 100 0 20 40 60 80 100
Leaching time (min) Leaching time (min)
Fig. 4 – Effect of temperature on the leaching recovery of lead and zinc at NaOH concentration of 4 M, stirring speed of
400 rpm for zinc and 500 rpm for lead and L/S ratio of 20 ml/g.
Please cite this article in press as: Seyed Ghasemi SM, Azizi A. Alkaline leaching of lead and zinc by sodium hydroxide: kinetics modeling. J
Mater Res Technol. 2017. http://dx.doi.org/10.1016/j.jmrt.2017.03.005
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0.8 0.4
50 °C 50 °C
0.7 60 °C 60 °C
Y80 = 0.0072x - 0.0529
70 °C R2 = 0.9786 70 °C Y80 = 0.0034x - 0.0544
0.3 R2 = 0.8988
0.6 80 °C 80 °C
1–3(1–x)2/3+2(1–x)
1–(1–x)2/3
0.5
0.2
Y70 = 0.0036x - 0.0261
R2 = 0.9815
Y50 = 0.0026x - 0.0233
0.1 R2 = 0.9664
Y60 = 0.0029x - 0.0226
R2 = 0.9824
0
0 20 40 60 80 100
Leaching time (min)
Fig. 5 – Plot of the shrinking core models vs. leaching time at different temperatures for the dissolution reactions of lead
with NaOH solution.
and Table 1. As seen, the highest R2 values obtain for the fluid to distinguish between these two reaction models. Addition-
film diffusion and the surface chemical reaction. On the other ally, in leaching processes, dissolution ratio directly depends
hand, due to the small difference between surface chemical on the activation energy, which can be calculated based on the
reaction control and liquid film diffusion control, it is difficult Arrhenius equation (k = A × e−Ea /R×T ). Based on the Arrhenius
Table 1 – Apparent rate constant (k) for kinetic models and correlation coefficient values.
Metal Temperature (◦ C) Diffusion through the liquid film Diffusion through the product layer Surface chemical reaction
Please cite this article in press as: Seyed Ghasemi SM, Azizi A. Alkaline leaching of lead and zinc by sodium hydroxide: kinetics modeling. J
Mater Res Technol. 2017. http://dx.doi.org/10.1016/j.jmrt.2017.03.005
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1 0.6
50 °C 50 °C
0.9
60 °C 60 °C
0.5
0.8 70 °C Y80 = 0.0083x + 0.046 70 °C
R2 = 0.9711 Y80 = 0.0056x - 0.0534
80 °C 80 °C
1–3(1–x)2/3+2(1–x)
0.7 R2 = 0.9736
0.4
1–(1–x)2/3
0.6
Y70 = 0.0077x + 0.0275 Y70 = 0.0046x - 0.0492
0.5 R2 = 0.9773 0.3 R2 = 0.9613
0.4 Y60 = 0.0029x - 0.032
0.2 R2 = 0.9559
0.3
Y50 = 0.0055x - 0.044
0.2 R2 = 0.9854
0.1
0.1 Y60 = 0.0061x + 0.0191 Y50 = 0.0022x - 0.0295
R2 = 0.9853 R2 = 0.9248
0 0
0 20 40 60 80 100 0 20 40 60 80 100
Leaching time (min) Leaching time (min)
0.6
50 °C
60 °C
0.5
70 °C Y80 = 0.0055x + 0.0075
80 °C R2 = 0.9886
0.4
1–(1–x)1/3
0.2
Y50 = 0.0032x - 0.0085
R2 = 0.9852
0.1
Y60 = 0.0037x + 0.0021
R2 = 0.9915
0
0 20 40 60 80 100
Leaching time (min)
Fig. 6 – Plot of the shrinking core models vs. leaching time at different temperatures for the dissolution reactions of zinc
with NaOH solution.
activation energy theory, Arrhenius equation was plotted as the Arrhenius plot of lead dissolution in NaOH solution based
Ln (k) vs. (1/T) for each temperature and the activation ener- on the film diffusion model is shown in Fig. 7. It has been
gies were calculated from the slopes of straight lines where previously stated that the typical activation energy for a chem-
the slope is −Ea /R. The values of activation energies calcu- ically controlled process is greater than 40 kJ/mol, while the
lated from Arrhenius plot are shown in Table 2. For example, activation energy of a diffusion controlled process is usually
Table 2 – Values of activation energies calculated for leaching process of lead and zinc from low-grade oxide ores in
sodium hydroxide solution.
Kinetic equations Metal Arrhenius equation coefficients
Please cite this article in press as: Seyed Ghasemi SM, Azizi A. Alkaline leaching of lead and zinc by sodium hydroxide: kinetics modeling. J
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5.8
Conflicts of interest
5.6
The authors declare no conflicts of interest.
5.4
5.2 Acknowledgement
-Ln(k)
Please cite this article in press as: Seyed Ghasemi SM, Azizi A. Alkaline leaching of lead and zinc by sodium hydroxide: kinetics modeling. J
Mater Res Technol. 2017. http://dx.doi.org/10.1016/j.jmrt.2017.03.005
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Please cite this article in press as: Seyed Ghasemi SM, Azizi A. Alkaline leaching of lead and zinc by sodium hydroxide: kinetics modeling. J
Mater Res Technol. 2017. http://dx.doi.org/10.1016/j.jmrt.2017.03.005