A method for recovering copper or cobalt from copper oxide or cobalt oxide ores by water flotation using calcium and magnesium rich alkaline tailings

Abstract

The application discloses a method for floating copper oxide or cobalt copper oxide ore by using calcium and magnesium rich high alkaline tailing backwater, and belongs to the technical field of ore dressing. The method comprises the following steps: crushing, grinding and slurry adjusting of the copper oxide or cobalt copper oxide ore to obtain a slurry; adding copper and cobalt ore inhibitors (ammonium dithiocarbamate and amino sulfonate) and calcium and magnesium gangue mineral collectors into the slurry to perform reverse flotation, and the foam product is calcium and magnesium gangue minerals, and the tailing product is copper oxide or cobalt copper oxide concentrate; wherein, water used in the grinding, slurry adjusting and reverse flotation processes is calcium and magnesium rich high alkaline tailing backwater. The method not only improves the flotation recovery rate of the copper oxide or cobalt copper oxide ore, but also realizes direct and efficient use of the calcium and magnesium rich high alkaline tailing backwater, and has good industrial application value and environmental friendliness.

Description

Technical Field

[0001] This invention relates to a mineral processing method, and more particularly to a method for flotation of copper oxide or copper-cobalt oxide ore using calcium- and magnesium-rich, highly alkaline tailings water, belonging to the field of mineral processing technology. Background Technology

[0002] Copper and cobalt are both important metallic elements, widely used in electronics, construction, and the development of new technologies. With the decreasing availability of easily beneficiated sulfide copper-cobalt ores, low-grade and difficult-to-beneficiate oxidized copper-cobalt ores have become crucial metallic resources. Low-grade oxidized copper-cobalt ores have complex compositions, fine grain sizes, high oxidation rates, and are often closely associated with calcium and magnesium carbonate minerals such as calcite and dolomite. Furthermore, existing "sulfide-xanthate" or direct fatty acid flotation processes result in low copper-cobalt recovery rates, low separation efficiency, and high leaching acid consumption, making the effective development and utilization of these ores particularly challenging.

[0003] In existing industrial production, mineral processing plants generally adopt a closed-loop water circulation system consisting of flotation, concentrate smelting, tailings concentration, tailings water recycling, and smelting water reuse. On the one hand, calcium and magnesium carbonate minerals in the ore continuously dissolve during grinding, slurry preparation, and flotation; on the other hand, the addition of large amounts of calcium oxide and magnesium oxide during smelting to adjust the solution pH results in tailings and smelting water typically being rich in calcium and magnesium ions. However, existing technologies typically address this type of highly alkaline, calcium- and magnesium-rich recycled water with the following issues: first, direct reuse deteriorates flotation efficiency and indicators; second, partial discharge of recycled water or replenishment with fresh water leads to serious environmental pollution and water swelling problems; and third, pretreatment with chelating agents or softeners, or separate utilization, results in complex processes and high operating costs. Therefore, how to achieve stable and efficient flotation of copper oxide or copper-cobalt oxide ore under the conditions of calcium- and magnesium-rich, highly alkaline tailings reclaimed water has become a key technical problem that urgently needs to be solved in the current mineral processing field. It is of great significance for the efficient utilization of copper and cobalt resources, water conservation and emission reduction, and green and low-carbon development. Summary of the Invention

[0004] To address the problems of low recovery rates and ineffective utilization of calcium- and magnesium-rich, highly alkaline tailings reclaimed water in existing flotation techniques for copper oxide or copper-cobalt oxide, the present invention aims to provide a mineral processing method that enables efficient flotation of copper oxide or copper-cobalt oxide under calcium- and magnesium-rich, highly alkaline tailings reclaimed water conditions. This method not only improves the flotation recovery rate of copper oxide or copper-cobalt oxide but also enables the direct and efficient utilization of calcium- and magnesium-rich, highly alkaline tailings reclaimed water, demonstrating significant industrial application value and environmental friendliness.

[0005] To achieve the above-mentioned technical objectives, the present invention provides a method for flotation of copper oxide or copper-cobalt oxide ore using calcium- and magnesium-rich, highly alkaline tailings. This method includes the following steps:

[0006] 1) The raw copper oxide or copper-cobalt oxide ore is crushed, ground, and prepared into a slurry;

[0007] 2) Add copper-cobalt ore inhibitor and calcium-magnesium gangue mineral collector to the slurry and perform reverse flotation. The froth product is calcium-magnesium gangue mineral, and the tailings product is copper oxide or copper-cobalt oxide concentrate.

[0008] in,

[0009] The water used in the grinding, pulping, and reverse flotation processes is calcium- and magnesium-rich, highly alkaline tailings recycled water;

[0010] The copper-cobalt ore inhibitor contains ammonium dithiocarbamate and aminosulfonate.

[0011] The key to this invention lies in the use of special ammonium dithiocarbamate and aminosulfonate as inhibitors for copper-cobalt ore. These inhibitors exhibit strong selective inhibition of valuable minerals such as malachite, azurite, and cobaltite in copper oxide or copper-cobalt oxide ores. Based on this, a calcium-magnesium gangue mineral collector is used in conjunction, and the calcium and magnesium ions in the calcium-magnesium-rich, highly alkaline tailings reclaimed water are utilized to enhance the adsorption of the calcium-magnesium gangue mineral collector on the surface of the gangue minerals. This widens the flotation difference between copper oxide or copper-cobalt oxide and calcium-magnesium gangue minerals, enabling efficient separation of valuable minerals from gangue minerals. The main mechanism involved in this invention is that the combined inhibitor of ammonium dithiocarbamate and aminosulfonate works through a synergistic mechanism of "metal site targeted adsorption - surface hydration layer reconstruction." Ammonium dithiocarbamate contains high electron density -CSS... - The fixative groups can preferentially recognize and directionally adsorb Cu exposed on the surfaces of minerals such as malachite, azurite, and cobaltite. 2+ or Co 3+ Active sites participate in coordination reactions via disulfide atoms, forming stable inner-layer complexes. Meanwhile, aminosulfonate molecules contain both hydrophilic amino groups and sulfonic acid groups, enabling them to undergo outer-layer complexation adsorption in malachite, azurite, and cobaltite, significantly increasing the hydrophilicity of the mineral surface and promoting the formation of a continuous and stable hydration film structure. Due to the lack of highly active metal sites on the surface of calcium magnesium carbonate minerals, their coordination complexation ability with ammonium dithiocarbamate and aminosulfonate-containing inhibitors is weak. Furthermore, under the conditions of calcium-magnesium-rich, highly alkaline tailings reclaimed water, the large amount of Ca present in the solution... 2+ and Mg 2+Competitively occupying adsorption sites on the surface of calcium and magnesium carbonate minerals provides favorable conditions for collector adsorption, further amplifying the difference in floatability between valuable minerals and gangue minerals. Therefore, under the conditions of highly alkaline tailings reclaimed water rich in calcium and magnesium, the combined inhibitor of ammonium dithiocarbamate and aminosulfonate exhibits a significant synergistic effect, constructing a stable inner-outer layer coupled inhibition structure on the mineral surface, thereby effectively blocking collector adsorption and achieving selective inhibition of valuable minerals such as malachite, azurite, and cobaltite.

[0012] As a preferred embodiment, the concentrations of calcium and magnesium ions in the calcium- and magnesium-rich, highly alkaline tailings reclaimed water are both 200–3000 mg / L, and the pH is 8.0–12.5. The calcium and magnesium ions in the reclaimed water can activate calcium- and magnesium carbonate minerals, thereby enhancing the collecting effect of the calcium- and magnesium gangue mineral collector on these minerals. Therefore, if the concentrations of calcium and magnesium ions in the reclaimed water are too low, the activation of calcium- and magnesium carbonate minerals will not be achieved, while if the concentrations are too high, excessive collector consumption will occur.

[0013] As a preferred embodiment, the aminosulfonate has the following molecular structure:

[0014] ;

[0015] in,

[0016] R is a C1~C3 alkane chain or benzene ring;

[0017] M represents a monovalent cation. M is further preferably a common monovalent cation such as sodium ion or potassium ion.

[0018] As a preferred embodiment, the copper-cobalt ore inhibitor is composed of ammonium dithiocarbamate and aminosulfonate in a mass percentage ratio of 60-70%:30-40%. The ratio of ammonium dithiocarbamate to aminosulfonate is optimized based on their synergistic inhibition mechanism and selective regulation of copper oxide or copper-cobalt oxide. If the proportion of ammonium dithiocarbamate is too high, it will lead to non-selective inhibition and low mineral separation efficiency; if the proportion of ammonium dithiocarbamate is too low, its complexation and coordination ability on the surface of copper-cobalt minerals will be insufficient, resulting in a poorer inhibition effect. Aminosulfonate mainly synergistically regulates the hydrophilicity of the mineral surface; if its proportion is too high, it will be difficult to achieve deep inhibition of copper oxide or copper-cobalt minerals; if its proportion is too low, it will be difficult to form an effective synergistic inhibition system with ammonium dithiocarbamate, leading to a decrease in the stability of the hydrophilic layer.

[0019] As a preferred embodiment, the calcium-magnesium gangue mineral collector includes at least one of sodium oleate, sodium stearate, metal-fatty acid, benzoic acid, and salicylic acid. These collectors are common calcium-magnesium gangue mineral collectors. Metal-fatty acid compounds include, for example, calcium-oleic acid, magnesium-oleic acid, zinc-oleic acid, aluminum-oleic acid, and lead-oleic acid.

[0020] As a preferred embodiment, the reverse flotation includes a roughing process and a sweeping process.

[0021] As a preferred option, the reagent system for the roughing process is as follows: 400-1000 g / t of copper-cobalt ore inhibitor and 600-1200 g / t of calcium-magnesium gangue mineral collector;

[0022] As a preferred embodiment, the reagent regime for scavenging is as follows: 200-500 g / t of copper-cobalt ore inhibitor and 300-600 g / t of calcium-magnesium gangue mineral collector.

[0023] As a preferred embodiment, the copper grade in the copper oxide or copper-cobalt oxide ore is 0.5% to 3.0%, and the calcium and magnesium grades are both greater than 5%.

[0024] As a preferred embodiment, the grinding process achieves a mass ratio of 60% to 80% for particles with a fineness of -0.074 mm.

[0025] As a preferred embodiment, the slurry preparation is performed to achieve a slurry concentration of 20-45 wt%.

[0026] Compared with the prior art, the beneficial technical effects of the present invention are as follows:

[0027] (1) The copper-cobalt ore inhibitor used in the flotation process of copper oxide or copper-cobalt oxide of the present invention contains ammonium dithiocarbamate and aminosulfonate. It has stable inhibition performance and high selectivity on copper-cobalt minerals such as malachite, azurite and hydrocobaltite, has little impact on calcium magnesium carbonate minerals, has good separation effect, low dosage, low cost, low toxicity and strong process adaptability.

[0028] (2) The method for flotation of copper oxide or copper-cobalt oxide ore of the present invention adopts a direct reverse flotation process to selectively remove calcium magnesium carbonate gangue minerals such as dolomite and calcite, breaking through the traditional process mode of copper oxide or copper-cobalt oxide ore mainly based on forward flotation. Compared with existing flotation processes, the present invention significantly improves the recovery effect of copper and cobalt minerals, effectively alleviates the problem of low recovery rate of useful minerals in high calcium magnesium systems, and also achieves efficient separation of useful minerals from calcium magnesium carbonate gangue minerals. The process is simple, the reagent system is stable, the reagent dosage is small, and the cost is low, showing good prospects for industrial application.

[0029] (3) This invention directly utilizes calcium- and magnesium-rich, highly alkaline tailings reclaimed water as flotation water, reducing the consumption of new water resources and the discharge of tailings wastewater, and avoiding secondary pollution problems generated during traditional reclaimed water treatment. Simultaneously, the composite inhibitors and collectors used exhibit good adaptability and selectivity in the calcium- and magnesium-rich system, effectively reducing reagent dosage and its potential environmental risks to water bodies and tailings. This method achieves efficient recycling of tailings water resources and clean operation of the flotation process, demonstrating good environmental friendliness and sustainable application prospects. Attached Figure Description

[0030] Figure 1 The above are flotation flowcharts for Embodiments 1 and 2 of the present invention. Detailed Implementation

[0031] The following specific embodiments are intended to further illustrate the content of the present invention, rather than to limit the scope of protection of the claims of the present invention.

[0032] Unless otherwise specified, all pharmaceutical products used in the following specific examples are commercially available products.

[0033] Example 1

[0034] In this embodiment, the raw ore sample was a copper oxide ore with a copper grade of 1.33% and a calcium grade of 5.65%. The main copper mineral in the ore was malachite, and the associated gangue minerals were mainly quartz, dolomite, and calcite. The flotation water used was tailings return water from the concentrator, with a pH of 10.8 and a calcium content of 5.65%. 2+ The concentration is approximately 1540 mg / L, Mg 2+ The concentration is approximately 1710 mg / L. The flotation test procedure is as follows: Figure 1 As shown, the specific experimental steps are as follows:

[0035] (1) Grinding and slurry preparation: The raw ore is crushed and ground to make the ore have a mass fraction of -0.074 mm particles of 70%, and the slurry mass concentration is controlled at 30%.

[0036] (2) Flotation operation: In the roughing operation, add 600g / t of copper-cobalt ore inhibitor (60% ammonium dithiocarbamate: 40% sodium 3-amino-1-propylsulfonate) and 800g / t of collector sodium oleate, and float for 5 min; in the scavenging operation, add 200g / t of copper-cobalt ore inhibitor (60% ammonium dithiocarbamate: 40% sodium 3-amino-1-propylsulfonate) and 400g / t of collector sodium oleate, and float for 3 min; the foam from the two flotation operations is mixed together to form the final tailings, and the underflow is the final concentrate.

[0037] Comparative Example 1

[0038] Compared with Example 1, the difference is that only a single dithiocarbamate inhibitor is added in the roughing and scavenging operations, while the other conditions and parameters are the same as in Example 1.

[0039] Comparative Example 2

[0040] Compared with Example 1, the difference is that only a single sodium 3-amino-1-propylsulfonate inhibitor was added in the roughing and scavenging operations, while the other conditions and parameters were the same as in Example 1.

[0041] Comparative Example 3

[0042] Compared with Example 1, the difference is that the flotation device used is clean water, while the other conditions and parameters are the same as in Example 1.

[0043] Comparative Example 4

[0044] Compared with Example 1, the difference is that no useful mineral complex inhibitor is added in the roughing and scavenging operations, while the other conditions and parameters are the same as in Example 1.

[0045] Comparative Example 5

[0046] Compared with Example 1, the difference lies in the use of the existing positive flotation process. In the roughing operation, 1200 g / t of sodium hydrosulfide and 1000 g / t of butyl xanthate collector are added sequentially, and No. 2 oil is used as the frother, with flotation lasting 5 minutes. In the scavenging operation, 400 g / t of sodium hydrosulfide and 500 g / t of butyl xanthate collector are added sequentially, with flotation lasting 3 minutes. All other conditions and parameters are the same as in Example 1.

[0047] Comparative Example 6

[0048] Compared to Example 1, the difference lies in that, without reusing tailings water from the concentrator, i.e., using clean water for flotation, and employing a positive flotation process, 1200 g / t of sodium hydrosulfide, 1000 g / t of butyl xanthate collector, and No. 2 oil as the frother are added sequentially during the roughing operation, with flotation lasting 5 minutes; and 400 g / t of sodium hydrosulfide and 500 g / t of butyl xanthate collector are added sequentially during the scavenging operation, with flotation lasting 3 minutes. All other conditions and parameters are the same as in Example 1.

[0049]

[0050] As shown in Table 1, under the conditions of calcium- and magnesium-rich, highly alkaline tailings reclaimed water, this invention significantly improves copper recovery and effectively reduces calcium enrichment in the concentrate by adding copper mineral inhibitors to synergistically and selectively inhibit valuable minerals such as malachite and using sodium oleate collectors to enhance the reverse flotation separation of calcium-bearing gangue minerals. Compared with single inhibitors, reverse flotation processes without inhibitors, existing forward flotation processes, and flotation processes without reclaimed water, this invention demonstrates significant advantages in terms of technical effectiveness, process adaptability, and resource utilization efficiency.

[0051] Example 2

[0052] In this embodiment, the raw ore sample was a copper-cobalt oxide ore with a copper grade of 1.81%, a cobalt grade of 0.14%, a calcium grade of 7.85%, and a magnesium grade of 6.19%. The main minerals in the ore were malachite, azurite, and cobaltite, with associated gangue minerals mainly consisting of quartz and dolomite. The flotation water used was tailings return water from the concentrator, with a pH of 11.2 and a Ca content of [missing information]. 2+ The concentration is approximately 2010 mg / L, Mg 2+ The concentration is approximately 1934 mg / L. The flotation test procedure is as follows: Figure 1 As shown, the specific experimental steps are as follows:

[0053] (1) Grinding and slurry preparation: The raw ore is crushed and ground to make the ore have a mass fraction of -0.074mm particles of 75%, and the slurry mass concentration is controlled at 33%.

[0054] (2) Flotation operation: In the roughing operation, add 800g / t of composite inhibitor (70% ammonium dithiocarbamate: 30% sodium 3-aminobenzenesulfonate) and 800g / t of collector sodium oleate in sequence, and float for 5min; in the scavenging operation, add 200g / t of composite inhibitor (70% ammonium dithiocarbamate: 30% sodium 3-aminobenzenesulfonate) and 400g / t of collector sodium oleate in sequence, and float for 3min; the foam from the two flotation operations is mixed together to form the final tailings, and the underflow is the final concentrate.

[0055] Comparative Example 7

[0056] Compared with Example 2, the difference is that only a single dithiocarbamate inhibitor was added in the roughing and scavenging operations, while the other conditions and parameters were the same as in Example 2.

[0057] Comparative Example 8

[0058] Compared with Example 2, the difference is that only a single sodium 3-aminobenzenesulfonate inhibitor was added in the roughing and scavenging operations, while the other conditions and parameters were the same as in Example 2.

[0059] Comparative Example 9

[0060] Compared with Example 2, the difference is that the flotation device used is clean water, while the other conditions and parameters are the same as in Example 2.

[0061] Comparative Example 10

[0062] Compared to Example 2, the difference lies in the use of an existing positive flotation process. In the roughing operation, 1200 g / t of sodium hydrosulfide and 1000 g / t of amyl xanthate / benzohydroxyxamic acid (mass ratio 1:1) were added sequentially, with No. 2 oil as the frother, and flotation was performed for 5 minutes. In the scavenging operation, 400 g / t of sodium hydrosulfide and 500 g / t of amyl xanthate / benzohydroxyxamic acid (mass ratio 1:1) were added sequentially, and flotation was performed for 3 minutes. All other conditions and parameters were the same as in Example 2.

[0063]

[0064] As shown in Table 2, under the conditions of calcium- and magnesium-rich, highly alkaline tailings reclaimed water, this invention significantly improves copper-cobalt recovery and effectively reduces the enrichment of acid-consuming gangue minerals in the concentrate by adding a copper-cobalt ore depressant to synergistically and selectively inhibit valuable minerals such as malachite, azurite, and cobaltite, and by enhancing the reverse flotation separation of calcium-bearing gangue minerals with a collector. Compared with single depressants, flotation using clean water, and existing direct flotation processes, this invention demonstrates significant advantages in terms of technical effectiveness, process adaptability, and resource utilization efficiency.

Claims

1. A method for flotation of copper oxide or copper-cobalt oxide ore using calcium- and magnesium-rich, highly alkaline tailings, characterized in that: Includes the following steps: 1) The raw copper oxide or copper-cobalt oxide ore is crushed, ground, and prepared into a slurry; 2) Add copper-cobalt ore inhibitor and calcium-magnesium gangue mineral collector to the slurry and perform reverse flotation. The froth product is calcium-magnesium gangue mineral, and the tailings product is copper oxide or copper-cobalt oxide concentrate. in, The water used in the grinding, pulping, and reverse flotation processes is calcium- and magnesium-rich, highly alkaline tailings recycled water; The copper-cobalt ore inhibitor comprises ammonium dithiocarbamate and aminosulfonate. The aminosulfonate has the following molecular structure: ； in, R is a C1~C3 alkane chain or benzene ring; M represents a monovalent cation.

2. The method for flotation of copper oxide or copper-cobalt oxide ore using calcium-magnesium-rich, highly alkaline tailings water according to claim 1, characterized in that: The calcium and magnesium ion concentrations in the reflux water of the calcium- and magnesium-rich alkaline tailings are both 200-3000 mg / L, and the pH is 8.0-12.

5.

3. The method for flotation of copper oxide or copper-cobalt oxide ore using calcium- and magnesium-rich, highly alkaline tailings water according to claim 1, characterized in that: The copper-cobalt ore inhibitor is composed of ammonium dithiocarbamate and aminosulfonate in a mass percentage ratio of 60-70%:30-40%.

4. The method for flotation of copper oxide or copper-cobalt oxide ore using calcium-magnesium-rich, highly alkaline tailings water according to claim 1, characterized in that: The calcium magnesium gangue mineral collector includes at least one of sodium oleate, sodium stearate, metal-fatty acid, benzohydroxyxamic acid, and salicylic acid.

5. A method for flotation of copper oxide or copper-cobalt oxide ore using calcium-magnesium-rich, highly alkaline tailings water according to claim 1, 2, or 4, characterized in that: The reverse flotation process includes one roughing process and one sweeping process.

6. The method for flotation of copper oxide or copper-cobalt oxide ore using calcium- and magnesium-rich, highly alkaline tailings water according to claim 5, characterized in that: The reagent system for roughing is as follows: 400-1000 g / t of copper-cobalt ore inhibitor and 600-1200 g / t of calcium-magnesium gangue mineral collector; The reagent regimen for the scavenging process is as follows: 200-500 g / t of copper-cobalt ore inhibitor and 300-600 g / t of calcium-magnesium gangue mineral collector.

7. The method for flotation of copper oxide or copper-cobalt oxide ore using calcium- and magnesium-rich, highly alkaline tailings water according to claim 1, characterized in that: The copper grade in the copper oxide or copper-cobalt oxide ore is 0.5% to 3.0%, and the calcium and magnesium grades are both greater than 5%.

8. A method for flotation of copper oxide or copper-cobalt oxide ore using calcium- and magnesium-rich, highly alkaline tailings water according to claim 1, characterized in that: The grinding process aims to achieve a particle size distribution of -0.074 mm with a mass ratio of 60% to 80%.

9. The method for flotation of copper oxide or copper-cobalt oxide ore using calcium-magnesium-rich, highly alkaline tailings water according to claim 1, characterized in that: The slurry is prepared to achieve a slurry concentration of 20-45 wt%.

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