Editorial Feature

Alternative Water Resources in Copper Leaching Procedures

Water is the most valuable and abundant resource on the globe, covering 71% of the Earth’s surface (oceans) and providing habitat to 97% of all living things. The oceans and other saline waterways constitute the world’s greatest water supply, accounting for 97.4% of all available water. This article looks at the use of alternative water resources in copper leaching processes in the Chilean mining industry. The research was published in Metals.

The remaining water (2.5%) largely (1.7%) corresponds to polar and glacier caps, which is why it is difficult to use. Traditional sources such as lakes, groundwater, and rivers account for only 0.8% of the total.

Freshwater is necessary for all living things. A human embryo’s body is made up of 97% water, a newborn’s body includes 80% water, and an adult’s body contains 60–65% water. If only the freshwater available on the planet is considered, the vast majority (68%) is encased in ice and glaciers, while the remaining 30% is entombed.

Freshwater supplies are presently under severe strain around the world as a result of rapid population expansion, quicker economic growth in certain countries, and improvements in people’s living conditions, all of which result in increased consumption of this resource. This is compounded by the fact that water is dispersed unevenly in practically every corner of the globe.

The Middle East and North Africa (MENA) region is an example of unequal distribution and reduced availability. This area is mostly deserting, receiving less than 1% of the world’s water.

The acid leaching of copper sulfide minerals using saltwater and wastewater from water desalination facilities is the subject of this study, which includes a bibliographic analysis based on the most recent scientific articles.

The goal of this paper is to highlight the major issues and obstacles that big-scale copper mining presents when using these water resources in significant quantities. The instance of Chile will be discussed in this document because it is the world’s greatest copper producer and the country with the most projects involving the use of seawater and wastewater in mining.

Discussion

Mining consumes a modest amount of water on a global scale. Even yet, it is usually a big water consumer on a local basis. Mining is Chile’s fourth-largest water user, accounting for 3% of total consumption. Freshwater scarcity in dry zones is a financial, ecological, and social issue.

In Chile, mining consumes the majority of the country’s water (51%) in the Antofagasta region, which is situated in the Atacama Desert, the country’s driest region. Due to a lack of freshwater resources, this condition causes tensions between mining firms and local populations.

In general, continental water consumption is predicted to reach 12.5 m3/s by 2030—a drop of 6% from 2020—as illustrated in Table 1.

As indicated in Figure 1, by 2030, seawater consumption might increase by 120% compared to 2020, with seawater accounting for 47% of the water required for copper mining on a national scale.

Distribution of water consumption according to mining process (MP: mineral processing; LX: leaching; SX: solvent extraction; EW: electrowinning; F&R: smelting and refining processes.

Figure 1. Distribution of water consumption according to mining process (MP: mineral processing; LX: leaching; SX: solvent extraction; EW: electrowinning; F&R: smelting and refining processes. Image Credit: Cochilco, 2015

Table 1. Projection of expected water consumption in copper mining. Source: Cochilco, 2015

Water (m3/seg) 2020 2021 2022 2023 2024 2025 2026 2027 2028 2029 2030
Continental water 13.3 12.8 12.9 13.2 13.4 12.9 12.4 12.6 12.3 12.3 12.5
Seawater 5 5.6 7.5 8.2 9.2 9.9 10.6 10.9 10.7 10.9 11
Total 18.3 18.4 20.4 21.4 22.6 22.8 23 23.5 23 23.2 23.5

 

Mineral concentration processes (MP) are predicted to consume 73% of continental water by 2030, followed by hydrometallurgical processes (5%), mine water and utilities (17%), and smelting and refining procedures (5%). This trend continues for saltwater, with mineral processing accounting for the majority of demand (90% by 2030) (Figure 1).

Presently, the use of seawater in manufacturing processes is a viable alternative to restricted water resources. Many mining companies are experimenting with using seawater in their operations. Some companies use it directly in their procedures, while others desalinate it before introducing it to their plants.

The steps outlined in Figure 2 are followed when using seawater in mining activities.

Geographic scheme of the Antofagasta region in Chile, mining activities and seawater collection system

Figure 2. Geographic scheme of the Antofagasta region in Chile, mining activities and seawater collection system. Image Credit: Cisternas, & Gálvez. 2018

Various research employing salt water for the dissolution of primary copper sulfides and secondary copper sulfides have been performed for leaching procedures. In general, all research agrees that integrating seawater into leaching processes has a favorable effect. This is primarily owing to the presence of chloride ions (~20 g/L) (Table 2).

Table 2. Reference composition of seawater. Source: Toro, et al., 2020

Solute g/kg of Solution
Na+ 10.78145
Mg2+ 1.28372
Ca2+ 0.41208
K+ 0.3991
Sr2+ 0.00795
Cl 19.35271
SO42− 2.71235
HCO3 0.10481
Br 0.06728
CO32− 0.01434
B(OH)4 0.00795
F 0.0013
OH 0.00014
B(OH)3 0.01944
CO2 0.00042
Total 35.16504

 

Due to the oxidizing potential of nitrate ions, the researchers tested the concentration of sodium nitrate in the system and found favorable results, increasing copper extraction from 27.9 to 80.2% in media based on saltwater and from 14.8 to 63.9% in media based on distilled water (Figure 3).

Chalcopyrite dissolution in the leach liquors using H2SO4 (1 M) + NaNO3 (0 or 1 M) in seawater- and water-based media (at 45 °C).

Figure 3. Chalcopyrite dissolution in the leach liquors using H2SO4 (1 M) + NaNO3 (0 or 1 M) in seawater- and water-based media (at 45 °C). Image Credit: Hernández, et al., 2018

In terms of acid concentration, Hernández et al. demonstrated that working with 0.5 M H2SO4 in seawater yields identical copper extractions to working with 1M H2SO4 in distilled water (Figure 4).

Furthermore, Castellón et al. show that ion oxidation rises with increased acidity levels in the leaching solution, owing to the generation of NOx gas over time. The creation of this gas, according to the researchers, allowed the system’s potential to be sustained at over 700 mV vs. Ag/AgCl, promoting chalcopyrite leaching (Figure 5).

 Chalcopyrite dissolution in the leach liquors with experimental conditions of NaNO3 (1 M), three days of leaching, 45 °C.

Figure 4. Chalcopyrite dissolution in the leach liquors with experimental conditions of NaNO3 (1 M), three days of leaching, 45 °C. Image Credit: Hernández, et al., 2018

Dissolution of chalcopyrite concentrate and averaged ORP (mV vs. Ag/AgCl) values over time (hours) for Series I at different concentrations of H2SO4 and NaNO3. (o) Test 1 (H2SO4 = 0.1 M and NaNO3 = 0.1 M); (?????•) Test 2 (H2SO4 = 0.1 M and NaNO3 = 0.5 M); (N) Test 3 (H2SO4 = 0.5 M and NaNO3 = 0.1 M); (•) Test 4 (H2SO4 = 0.5 M and NaNO3 = 0.5 M); (X) Test 5 (H2SO4 = 1.0 M and NaNO3 = 0.1 M); (_) Test 6 (H2SO4 = 0.5 M and NaNO3 = 0 M). (Test conditions: 94 h, P80 = 60.66 µm, 450 rpm and room temperature). The copper recoveries are shown with black dotted line in axis secondary and averaged ORP values are shown with red dotted line.

Figure 5. Dissolution of chalcopyrite concentrate and averaged ORP (mV vs. Ag/AgCl) values over time (hours) for Series I at different concentrations of H2SO4 and NaNO3. (o) Test 1 (H2SO4 = 0.1 M and NaNO3 = 0.1 M); (▪●◊∆◌•) Test 2 (H2SO4 = 0.1 M and NaNO3 = 0.5 M); (N) Test 3 (H2SO4 = 0.5 M and NaNO3 = 0.1 M); (•) Test 4 (H2SO4 = 0.5 M and NaNO3 = 0.5 M); (X) Test 5 (H2SO4 = 1.0 M and NaNO3 = 0.1 M); (_) Test 6 (H2SO4 = 0.5 M and NaNO3 = 0 M). (Test conditions: 94 h, P80 = 60.66 µm, 450 rpm and room temperature). The copper recoveries are shown with black dotted line in axis secondary and averaged ORP values are shown with red dotted line. Image Credit: Castellón, et al., 2020

Hernández et al., on the other hand, evaluated the effect of adding NaCl to the same amount of chloride as seawater in their studies for the leaching of a chalcopyrite concentrate in an acid medium using seawater and caliche salts (Figure 6a).

Furthermore, these systems have similar behavior in their potential redox values, as seen in Figure 6b. This is in line with Toro et al.'s investigations of chalcocite leaching in an acid media using seawater. When dealing with seawater and 20 g/L chloride, the researchers received comparable findings (Figure 7).

(a) Comparison of copper extraction (%) curve when seawater and water with 20 g/L Cl- were used as water sources in the leach solution. (b) Redox potential (mV) versus time (h) when seawater and water with 20 g/L Cl- were used as a source of water in the leach solution. Experimental conditions: [NaNO3] = [H2SO4] = 0.7 M, 45 °C and sample A.

Figure 6. (a) Comparison of copper extraction (%) curve when seawater and water with 20 g/L Cl were used as water sources in the leach solution. (b) Redox potential (mV) versus time (h) when seawater and water with 20 g/L Cl were used as a source of water in the leach solution. Experimental conditions: [NaNO3] = [H2SO4] = 0.7 M, 45 °C and sample A. Image Credit: Hernández, et al., 2020

Comparison between the use of seawater and synthetic chloride (20 g/L) for the dissolution of chalcocite in an acid medium (T = 25 °C, H2SO4 = 0.5 mol/L).

Figure 7. Comparison between the use of seawater and synthetic chloride (20 g/L) for the dissolution of chalcocite in an acid medium (T = 25 °C, H2SO4 = 0.5 mol/L). Image Credit: Toro, et al., 2019

There are now 14 water desalination facilities linked to mining operations (Table 3), with more planned in the future (Table 4).

Table 3. Land registry of desalination plants and seawater impulsion systems in copper mining in operation. Source: Cochilco, 2015

Mine Desalination Capacity (L/s) Seawater Use Capacity (L/s) Length of Water Transport Pipes (km)
Michilla 75 23 -
Planta J.A. Moreno (Taltal) - 15 -
Las Cenizas (Taltal) 9 12 7
Mantos de la Luna 20 5 8
Pampa Camarones - 25 12
Centinela 50 1500 145
Cap Minería 600 - 120
Escondida (Planta Coloso) 525 - 180
Antucoya 20 280 145
Candelaria 300 - 110
Mantoverde 120 - 42
Sierra Gorda - 1315 142
Escondida EWS 2500 - 180
Candelaria 700 - 110

 

Table 4. Future projects of desalination plants and seawater impulsion systems in copper mining. Source: Altaley, 2021

Mine Desalination Capacity (L/s) Seawater Use capacity (L/s) Length of Water
Transport Pipes (km)
Start-Up Year
Los Pelambres 400 - 150 2021
Spence Growth Option 800 (1600
potential)
- 154 2021
MantoVerde Add 260 to
current capacity
- 42 2022
ENAPAC (Múltiples mineras de la zona
norte de Chile)
2630 - - 2022
Quebrada Blanca 850 (1200
potential)
- 160 2023
CODELCO (Chuquicamata,
Radomiro Tomic y
Ministro Hales)
840 (1956
potential)
- 160 2023
Santo Domingo 30 400 112 2024
COLLAHUASI 525 (1050
potential)
- 195 2024
Diego de Almagro - 315 61 2025
Centinela - 1650 145 2025
El Abra 500 - - 2027
Nueva Unión 700 - - 2028

 

Desalination procedures produce brine, which is a waste product that is returned to the sea in vast quantities and has greater chemical element content (Table 5). Furthermore, brine is denser than seawater. As a result, it cannot combine with the sea and decants at the ocean’s bottom.

 

Table 5. Composition of wastewater from desalination plants used in previous studies. Source: Toro, et al., 2022

Previous Research [5] [57]
Compound Concentration (g/L) Concentration (g/L)
Fluoride (F) 0.002 0.002
Calcium (Ca2+) 0.8 0.4
Magnesium (Mg2+) 2.65 2.29
Sodium (Na+) 20.85 19.77
Potassium (K+) 0.82 0.75
Bicarbonate (HCO3) 1.1 0.236
Chloride (Cl) 39.16 36.07
Calcium carbonate (CaCO3) 13 10

 

Table 6. Comparison between previous investigations for the dissolution of copper sulfide minerals in an acid medium using wastewater. Source: Toro, et al., 2022

Research Mineral Leaching Agent Parameters Cu Extraction (%) Reference
Influence of seawater and discard brine on the dissolution of copper ore and copper concentrate Copper Oxides
(Atacamite and
Chrysocolla),
Chalcopyrite
Concentrate,
Chalcopyrite Mineral
H2SO4, NaCl, Discard salts Chloride concentration,
cure time, potential
redox variation in the
leaching solution
92 [49]
Leaching of Pure Chalcocite in a Chloride Media Using Sea Water and Wastewater Chalcocite H2SO4,
NaCl
Chloride concentration,
acid concentration
67.75 [26]
Leaching of Pure Chalcocite in a Chloride Media Using Wastewater at High Temperature Chalcocite H2SO4,
NaCl
Acid concentration,
chloride concentration,
temperature
97 [50]
Caliche and Seawater, Sources of Nitrate and Chloride Ions to Chalcopyrite Leaching in Acid Media Chalcopyrite H2SO4, NaNO3, NaCl Temperature, solid/
liquid ratio, chloride
concentration, particle
size, nitrate
concentration, acid
concentration, cure
time
92.3 [57]
Dissolution of pure chalcopyrite with manganese nodules and wastewater Chalcopyrite H2SO4, NaCl,
MnO2
stirring speed, acid concentration, MnO2 concentration, potential variation in the leaching solution 77 [5]
Leaching Chalcopyrite with High MnO2 and Chloride Concentrations Chalcopyrite H2SO4, MnO2 Particle size, temperature 71 [25]
Use of Seawater/Brine and Caliche’s Salts as Clean and Environmentally Friendly Sources of Chloride and Nitrate Ions for Chalcopyrite Concentrate Leaching Chalcopyrite concentrate H2SO4, caliche
salts
Acid concentration,
nitrate concentration,
chloride concentration,
temperature, cure time
90.6 [56]
Leaching of Pure Chalcocite with Reject Brine and MnO2 from Manganese Nodules Chalcocite H2SO4, NaCl,
MnO2
chloride concentration,
acid concentration,
potential redox
variation in the leaching
solution, MnO2
concentration
71 [58]

 

As a result, using saltwater or wastewater does not enhance oxidized mineral leaching. In contrast, the scientists found that while working with 100 days of curing and subsequent leaching in columns for a chalcopyrite mineral, wastewater (43%) outperforms saltwater (37%) in 80 days of irrigation in their trials.

Employing nitrate ions as an oxidizing agent, the authors examined the use of distilled water, salt water, and wastewater to leach chalcopyrite, with wastewater yielding the highest copper extractions (Figure 8).

Copper extraction (%) versus time (h) when different dissolvents were used: distilled water (water), seawater, and brine. Experimental conditions: [NaNO3] = 0.7 M, [H2SO4] = 0.7 M, -150 + 75 µm, S/L ratio 2 g/L, 45 °C, 350 rpm, sample A.

Figure 8. Copper extraction (%) versus time (h) when different dissolvents were used: distilled water (water), seawater, and brine. Experimental conditions: [NaNO3] = 0.7 M, [H2SO4] = 0.7 M, −150 + 75 µm, S/L ratio 2 g/L, 45 °C, 350 rpm, sample A. Image Credit: Hernández, et al., 2020

The authors claim that when working with high chloride concentrations, it is feasible to dissolve chalcopyrite at room temperature and avoid passivation (Figure 9). According to the researchers, it is possible to keep the voltage consistent between 580 and 650 mV using these operational conditions, resulting in 77% Cu extraction (Figure 10).

Furthermore, an examination of the residues collected revealed that no contaminating elements, such as stable elemental sulfur, were formed, and that other elements present, such as MgO and CaSO4, had no effect on the extraction of Cu (Figure 11).

Effect of the MnO2/CuFeS2 ratio on Cu extraction (25 °C, CuFeS2 size: -47 + 38 m, MnO2 size: -75 + 53 m, 1 mol/L H2SO4 and 39.16 g/L of chloride).

Figure 9. Effect of the MnO2/CuFeS2 ratio on Cu extraction (25 °C, CuFeS2 size: −47 + 38 m, MnO2 size: −75 + 53 m, 1 mol/L H2SO4 and 39.16 g/L of chloride). Image Credit: Toro, et al., 2019

Effect of the potential in the solution of Cu at different ratios of MnO2/CuFeS2.

Figure 10.  Effect of the potential in the solution of Cu at different ratios of MnO2/CuFeS2. Image Credit: Toro, et al., 2019

X-ray powder diffraction patterns for the residue mineral after being leached with wastewater at 25 °C in a time of 90 min. CuFeS2 size: -47 + 38 µm, MnO2 size: -75 + 53 µm, MnO2/CuFeS2 to 5/1 and 39.16 g/L chloride).

Figure 11. X-ray powder diffraction patterns for the residue mineral after being leached with wastewater at 25 °C in a time of 90 min. CuFeS2 size: −47 + 38 μm, MnO2 size: −75 + 53 μm, MnO2/CuFeS2 to 5/1 and 39.16 g/L chloride). Image Credit: Toro, et al., 2019

Finally, the researchers discovered that when chalcocite is leached in a chlorinated system, it dissolves rapidly (exponentially) until 50% of the Cu is extracted, which is attributable to the creation of covellite, which has slower dissolving kinetics.

The researchers found that adding MnO2 to the system at low concentrations enhances the extraction of Cu from Cu2S in a short period of time, which is relevant in continual leaching processes (Table 7).

Table 7. Comparison of chalcocite dissolution with reject brine and the effect of MnO2. Source: Toro, et al., 2022

Experimental Conditions and Results [26] [58]
Temperature (°C) 25 25
Particle size of Cu2S (um) −147 + 104 −147 + 104
H2SO4 concentration (mol/L) 0.5 0.5
MnO2/Cu2S ratio (w/w) - 0.25:1
Dissolution in seawater after 4 h (%) 32.8 35.6
Dissolution in reject brine after 4 h (%) 36 40
Dissolution in seawater after 48 h (%) 63.4 64.7
Dissolution in reject brine after 48 h (%) 64.6 66.2

 

Conclusion

There are many projects for desalination plants and systems of seawater impulsion to feed mining activities by the year 2030, depending on the behavior of saltwater projection in mining processes. The use of fresh water in major copper mining operations by government organizations is also restricted. As a result, it is reasonable to predict that the use of seawater and wastewater in mining will continue to expand in the coming years.

On the other hand, wastewater from desalination plants has shown good outcomes for the dissolution of copper from sulfide minerals in recent research, which is due to the fact that it has a higher concentration of chloride ions than seawater (roughly double), allowing the system to operate at higher redox potential values.

As a result, it can be stated that wastewater from water desalination plants can be used in heap leaching procedures for copper sulfide minerals as long as the expense of transporting the wastewater from the desalination plants to the mining locations can be sustained.

Journal Reference:

Toro, N., Gálvez, E., Robles, P., Castillo, J., Villca, G., Salinas-Rodríguez, E. (2022) Use of Alternative Water Resources in Copper Leaching Processes in Chilean Mining Industry—A Review. Metals, 12(3), p. 445. Available Online: https://www.mdpi.com/2075-4701/12/3/445/htm.

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Laura Thomson

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Laura Thomson

Laura Thomson graduated from Manchester Metropolitan University with an English and Sociology degree. During her studies, Laura worked as a Proofreader and went on to do this full-time until moving on to work as a Website Editor for a leading analytics and media company. In her spare time, Laura enjoys reading a range of books and writing historical fiction. She also loves to see new places in the world and spends many weekends walking with her Cocker Spaniel Millie.

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