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Hydrometallurgy
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Article history: The objective of this work is to investigate the use of seawater to recover potassium and nitrate from the
Received 31 May 2012 waste tails of SQM operations. The use of seawater as an alternative to fresh water is an attractive option
Received in revised form 19 December 2012 for the resource-rich northern Chilean mines, especially for those operating in the Salar de Atacama Desert
Accepted 19 December 2012
where fresh water is scarce.
Available online 27 December 2012
In this study, the performance of four leaching agents was evaluated for recovering potassium and nitrate
Keywords:
from discarded salts: 1) freshwater; 2) seawater; 3) seawater saturated with chloride ions; and 4) seawater
Leaching of nitrates saturated with chloride, sulfate and magnesium ions. The tests were performed in columns loaded with the
Seawater same quantity of salt and irrigated at the same rate for a period of 152 hours. These tests showed that
Recovery of salts leaching with seawater provides nearly the same potassium and nitrate leaching efficiency as when fresh
Sodium nitrate water is used. However, leaching with seawater saturated with chloride, sulfate and magnesium ions yielded
Brine approximately 10% lower potassium and nitrate recoveries compared with the tests when seawater was used
alone. In contrast, the use of saturated seawater is expected to yield a geomechanically more stable heap be-
cause most of the chloride-, sulfate- and magnesium-containing salts will remain unleached.
© 2012 Elsevier B.V. All rights reserved.
1. Introduction the recovery of nitrate ions using leaching discarded salts with seawater
as a leaching agent.
The most important economic activity in Chile is mining, which is Among the scientific literature of interest, Padilla et al. (2008),
concentrated in the northern part of the country. The main mineral who worked on the optimization of technologies for heap leaching
products are copper and saline systems (caliche mineral), composed applied to minerals, such as copper, gold and zinc, which can be ex-
mainly of natural nitrates (Chong et al., 2007). The region is a desert tended to caliche and waste dumps. They conducted an analysis to
with scarce freshwater resources; therefore, the mining sector requires determine whether these criteria present the best conditions from
research and the identification of alternative sources of water. One al- an economic point of view. The authors examined the variables of
ternative is seawater, which can be substitute for the limited freshwater leaching time and heap height for a copper treatment plant. The re-
resources in the region. sults of the study showed that heap height and operational time are
Sodium nitrate has diverse applications, such as in the production of interactive factors and that the maximum recovery is not necessarily
fertilizers, explosives and food preservatives and as a raw material for the best measurement of operational efficiency, based on economic
obtaining potassium nitrates and other compounds (Wisniak and considerations. To model the system, it is assumed that there is a sim-
Garces, 2001). Sodium nitrate is a nonrenewable resource that has ple heap with a known mineral, that the mineral is discharged with
been exploited in the north of Chile since the beginning of the last cen- an impregnation volume after leaching is completed, that the mineral
tury. Valencia et al. (2008) provide details on the history of nitrate min- mass discharged is the same as the mineral fed into the system, and
ing and the processing of caliche mineral. that each heap behaves as a simple reactor.
In the processes to obtain sodium nitrate, solar ponds are generally Valencia et al. (2008) studied the leaching of caliche in columns and
used to concentrate this salt (see Fig. 1). Discarded salts (also called determined the recovery of nitrate and magnesium at different layer
harvested salts) are also obtained in this process, which still contain a heights of the mineral. They analyzed the effect of time and the irriga-
significant amount of nitrate ions to be recovered. This study evaluated tion ratio and obtained empirical kinetic expressions. They used a sim-
ple mathematical model to represent the leaching process that shows a
good adjustment to predict the nitrate and magnesium concentrations.
Taboada et al. (2012) provided data on the solubility and the phys-
⁎ Corresponding author. Tel.: +56 55 637345; fax: +56 55 637109.
E-mail addresses: Mauricio.torres@sqm.com (M.A. Torres),
ical–chemical properties of sodium nitrate and caliche in seawater at
Gabriel.meruane@sqm.com (G.E. Meruane), tgraber@uantof.cl (T.A. Graber), different concentrations and temperatures from studies of processes
pamela.gutierrez@uantof.cl (P.C. Gutiérrez), mtaboada@uantof.cl (M.E. Taboada). similar to those studied in this article.
0304-386X/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.hydromet.2012.12.008
M.A. Torres et al. / Hydrometallurgy 133 (2013) 100–105 101
Fig. 1. Solar pond evaporation process. Fig. 2. General scheme of the tests in minicolumns.
102 M.A. Torres et al. / Hydrometallurgy 133 (2013) 100–105
Table 1
Salt composition at leaching.
H2O Na+ K+ Mg+2 Ca+ Cl− SO42− NO3− ClO4− H3BO3 Total
Salt pond 7.9 28.9 2.6 1.9 0.06 39.0 14.6 4.6 0.05 0.50 100.0
Table 2
Composition of leaching agents.
H2O Na+ K+ Mg+2 Ca+ Cl− SO42− NO3− ClO4− H3BO3 Total
M1. Freshwater 99.9 0.0 0.0 0.0 0.01 0.0 0.0 0.0 0.00 0.01 100.0
M2. Seawater 96.5 1.1 0.0 0.1 0.04 1.9 0.3 0.0 0.00 0.01 100.0
M3. Seawater + NaCl 73.7 10.1 0.0 0.1 0.04 15.8 0.3 0.0 0.00 0.01 100.0
M4. Seawater + NaCl + MgSO4 68.1 7.3 0.0 2.6 0.04 10.7 11.2 0.0 0.00 0.04 100.0
salts in the original solution. For example, for a leaching time of Fig. 9 shows the behavior of the density in samples of the output so-
151.5 hours, the extraction percentages of nitrates are 94% and 93%, lution taken from the columns for the four experiments. It can be ob-
respectively, and for potassium, they are 96% and 94%, respectively. served that the density as a function of the concentration expressed as
In general, the other species follow the same tendency (see Figs. 5 grams of total dissolved salts behaves in a linear fashion.
and 6). In these tests (M1 and M2), the mechanical sustainability
was affected by the dissolution of the salts in the columns. 3.2. Adjustment of the leaching kinetics
In the M3 test (seawater saturated with sodium chloride ions), we
achieved the objective of not leaching the Cl − ion but at the same The equation used to adjust the experimental data (Padilla et al.,
time decreased the recovery of the NO3− to approximately 88% and 2008) is:
potassium to 83% for a leaching time of 151.5 hours (see Fig. 7).
With respect to the M4 test (leaching with seawater saturated h i
−kðt−θÞn
with sulfate, chloride and magnesium ions), the same effect was E ¼ E∞ 1−e ð1Þ
obtained for the Cl − ion and the SO42− and Mg +2 species. Here, the
NO3− recovery falls to 85%. In this case, the recovery of the K + ion,
in contrast to the behavior in the M1, M2 and M3 tests, falls to 68%,
all for a leaching time of 151.5 hours (see Fig. 8). In contrast, with
the M1 and M2 tests, the mechanical sustainability of the M3 and
M4 tests was not affected by the dissolution of the salts in the col-
umns as a result of leaching with saturated solutions.
As a result of these tests, it can be concluded that the greater the
quantity of salts in the leaching solution, the more the extraction of
ions decreases, but the leaching heap remains more stable, precisely
because of the non-dissolution of the salts that are saturated in the
feeder solution. In this manner, the recovery of nitrates using seawa-
ter is viable in the cases studied, and the recovery of potassium is vi-
able in columns 2 and 3.
The detailed results for each of the tests can be observed in
Tables 4–7. The tables show an increase in density of the feeder solu-
tion from values below 1 when freshwater is the leaching agent up to
values close to 1.3 g⋅cm −3 when seawater is used.
Fig. 3. Size distribution of harvested salt particles. Fig. 4. a. Scheme of the work. b. Equipment used.
M.A. Torres et al. / Hydrometallurgy 133 (2013) 100–105 103
Table 3
Operational parameters.
M1 M2 M3 M4
2
m
f obj ¼ ∑i¼1 Eexp;i −Eec;i ð2Þ
The experimental data and the data obtained from Eq. (1) were
compared with the deviation function defined by:
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1 2
m Fig. 7. Experimental data (points) and adjustment of leaching (lines) with seawater
d¼ ∑ E −Eec;i ð3Þ
m i¼1 exp;i saturated in sodium chloride.
Table 8 shows the results of the adjustment with Eq. (1) for all of
the experiments, with a mean correlation coefficient of 0.996 and a 4. Conclusions
mean deviation of 0.089%, indicating a good adjustment of the exper-
imental data. Figs. 5 to 8 present the experimental extraction data It is possible to leach certain types of salts with seawater,
with points and the adjustments obtained with Eq. (1) with solid obtaining recovery rates of nitrates and potassium above 80%, which
lines. is attractive from an economic point of view.
In Table 8, we can note that for each leached ion, the kinetic pa- Leaching, whether with freshwater or seawater, is largely the re-
rameter k decreases from columns 1 to 4, that is, it decreases using sult of the dissolution of the salts in the heap, which from an opera-
seawater and then by saturating the seawater in Cl −, SO4−2 and tional point of view could be a serious problem for the mechanical
Mg +2 ions, which lower the leaching capacity. sustainability of the heap. In contrast, leaching with solutions saturated
The parameter n does not change substantially, except nitrate and with Cl−, SO4−2 and Mg+2 results in a more mechanically sustainable
potassium leaching that increases significantly for seawater saturated heap. The recovery of potassium or nitrate decreases by approximately
with Cl − and even more when saturated with Cl −, SO4−2 and Mg +2. 10% compared with tests using unsaturated seawater or freshwater.
100
90
80
K
70
% Extraction
SO4
60
NO3
50
Mg
40 Cl
30 Equation 1
20
10
0
0 20 40 60 80 100 120 140 160
time (h)
Fig. 5. Experimental data (points) and adjustment by Eq. (1) of leaching (lines) with Fig. 8. Experimental data (points) and adjustment of leaching (lines) with seawater
freshwater. saturated in sodium chloride, magnesium and sulfate.
104 M.A. Torres et al. / Hydrometallurgy 133 (2013) 100–105
Table 4 Table 6
M1 test results. Leaching with freshwater with a density of 0.998 g cm−3. M3 test results. Leaching with seawater saturated in Cl− with a density of 1.202 g cm−3.
Minicolumn 1 Accum. Output Extraction percent (%) LR Minicolumn 3 Accum. Output Extraction percent (%) LR
time (h) solution accum. time (h) solution accum.
Freshwater K+ Mg2 + Cl− SO42− NO3− Seawater + K+ Mg2+ Cl− SO42− NO3−
density (m3/Ton) density (m3/Ton)
NaCl
(g/cm−3) (g/cm−3)
The selective leaching obtained with a leaching solution saturated Eq. (1) agrees with the experimental data very well and has an av-
with ions favors the extraction of specific ions, improving the extrac- erage correlation coefficient of 0.996 and a deviation function of
tion process and equipment performance. 0.089%.
Table 7
Table 5 M4 test results. Leaching with seawater saturated in Cl−, SO42 − and Mg2+ with a den-
M2 test results: Leaching with seawater with a density of 1.023 g cm−3. sity of 1.293 g cm−3.
Minicolumn 2 Accum. Output Extraction percent (%) LR Minicolumn 4 Accum. Output Extraction percent (%) LR
time (h) solution accum. time (h) solution accum.
Seawater K+ Mg2+ Cl− SO42− NO3− Seawater+ K+ Mg2+ Cl− SO42 − NO3−
density (m3/Ton) density (m3/Ton)
NaCl + MgSO4
(g/cm−3) (g/cm−3)
Table 8
Parameters of Eq. (1) and adjustments.
and long term given the scarcity of freshwater in the Atacama Desert
and the strong growth of the mining industry in the region. However,
a considerable amount of research still needs to be performed to Gálvez, E.D., Moreno, L., Mellado, M.E., Ordóñez, J.I., Cisternas, L.A., in press. Heap
leaching of caliche minerals: Phenomenological and analytical models – Some
adapt these results to an industrial process. comparisons. Miner. Eng.
Moreno, P., Aral, H., Cuevas, J., Monardes, A., Adaro, M., Norgate, T., Bruckard, W., 2011.
The use of seawater as process water at Luces copper-molibdenum beneficiaton
Acknowledgments plant in Taltal (Chile). Miner. Eng. 24, 852–858.
Padilla, G., Cisternas, L., Cueto, Y., 2008. On the optimization of heap leaching. Miner.
Eng. 21, 673–678.
The authors are grateful for the funding provided by CONICYT Taboada, M.E., Hernández, P.C., Galleguillos, H.R., Flores, E.K., Graber, T.A., 2012. Behav-
through the FONDECYT Project N° 1100685 and CICITEM Project ior of sodium nitrate and caliche mineral in seawater: solubility and physicochem-
R04I1001. ical properties at different temperatures and concentrations. Hydrometallurgy
113–114, 160–166.
Valencia, J., Méndez, D., Cueto, J., Cisternas, L., 2008. Saltpeter extraction and modelling
of caliche mineral heap leaching. Hydrometallurgy 90, 103–114.
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J. Chem. Technol. 8 (5), 427–438.
Chong, G., Gajardo, A., Hartley, A.J., Moreno, T., 2007. Industrial minerals and rocks. The
Geology of Chile, p. 201.