Flotation activator and intensified flotation method for high-calcium-magnesium and low-grade oxidized copper-cobalt ore

Abstract

This invention relates to the field of mineral processing, specifically to a flotation activator and enhanced flotation method for high-calcium-magnesium, low-grade copper-cobalt oxide ores. In the flotation activator, the mass ratio of sulfiding agent to ammonium thiosulfate is 40-50:30-40, and the mass ratio of ammonium thiosulfate to sulfite is 30-40:10-20. This invention fully utilizes the synergistic effect between the compound reagents, employing sulfiding agent, ammonium thiosulfate, and sulfite as flotation activators to achieve continuous activation and controllable regulation of the sulfidation process of copper-cobalt oxide minerals, significantly improving the stability and activity of the sulfidation film on the surface of copper-cobalt oxide minerals. Sulfite can weakly coordinate with the active sites of copper and cobalt on the surface through its sulfur-oxygen organic groups, lowering the energy barrier of the sulfidation reaction and helping to improve the stability of the sulfidation film. Simultaneously, its strong reducing properties regulate the sulfidation reaction process, reducing the non-selective oxidation and consumption of the sulfiding agent, making it particularly suitable for high-calcium-magnesium copper-cobalt ores.

Description

Technical Field

[0001] This invention relates to the field of mineral processing, specifically to a flotation activator and flotation method for high-calcium-magnesium, low-grade oxidized copper-cobalt ore. Background Technology

[0002] Copper and cobalt are widely used in defense, battery electronics, construction, metallurgy, and many other fields. Copper-cobalt oxide ores are an important type of non-ferrous metal resource, widely distributed in regions such as the copper-cobalt belt in Central Africa. Among them, high-calcium-magnesium low-grade copper-cobalt oxide ores suffer from low ore grade, fine-grained valuable minerals, and complex gangue mineral composition, making it difficult to effectively recover valuable minerals and severely restricting resource development and utilization. Moreover, these ores usually contain a large amount of acid-consuming calcium-magnesium carbonate minerals such as dolomite and calcite, which not only seriously affect the selectivity of flotation reagents but also lead to a significant increase in acid consumption during subsequent hydrometallurgical processes, thus restricting their efficient industrial utilization.

[0003] Currently, the main beneficiation methods for copper-cobalt oxide ores include direct flotation, sulfide flotation, and combined beneficiation and metallurgical processes. Among these, sulfide flotation is widely used due to its relatively mature process and versatile equipment. This method involves adding sulfiding agents such as sodium sulfide or sodium hydrosulfide to the slurry to form a sulfide film on the surface of copper-cobalt oxide minerals such as malachite and cobaltite, which is then used in conjunction with xanthate collectors for flotation recovery. However, in high-calcium, low-grade systems, existing sulfide flotation processes face many problems; the sulfiding agent exhibits poor reaction stability in the slurry, suffers from high non-selective consumption, and the sulfidation process is difficult to control, often resulting in problems such as "over-sulfidation" or "under-sulfidation." This leads to uneven, unstable, and low-bonding-strength sulfide films on the surface of copper-cobalt oxide minerals, thereby weakening the effective adsorption of subsequent collectors. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the above-mentioned defects of the prior art and provide a flotation activator and enhanced flotation method for high-calcium magnesium low-grade oxidized copper-cobalt ore that improves flotation index and reduces acid consumption; The technical solution adopted by the present invention to solve its technical problem is as follows: a flotation activator for high-calcium-magnesium low-grade oxidized copper-cobalt ore, comprising a sulfiding agent, ammonium thiosulfate and sulfite ester; The mass ratio of the sulfiding agent to ammonium thiosulfate is 40~50:30~40; The mass ratio of ammonium thiosulfate to sulfite is 30-40:10-20.

[0005] Preferably, the vulcanizing agent includes at least one of sodium sulfide and sodium hydrosulfide.

[0006] Preferably, the chemical formula of the sulfite is R-OS(=O)OR′, wherein R and R′ are each independently selected from one of alkyl, aryl, cycloalkyl, alkenyl, and alkynyl groups.

[0007] Preferably, the copper grade in the high-calcium-magnesium low-grade oxidized copper-cobalt ore is 0.5wt%~2.0wt%, the cobalt grade is 0.05wt%~0.3wt%, and the calcium and magnesium grades are both greater than 5wt%.

[0008] Preferably, 500g to 1500g of flotation activator is used per ton of high-calcium-magnesium, low-grade copper-cobalt oxide ore.

[0009] Preferably, the slurry is added before the collector is added to it.

[0010] Based on the same inventive concept, this invention also provides an enhanced flotation method for high-calcium-magnesium low-grade copper-cobalt oxide ore. The high-calcium-magnesium low-grade copper-cobalt oxide ore is ground and slurry is prepared to obtain raw ore slurry. After adding the flotation activator, a collector is added to carry out enhanced flotation to obtain a concentrate enriched with valuable elements.

[0011] Preferably, the solid content of the raw ore slurry is 20wt%~40wt%, and the particles with a diameter of less than 0.074mm account for 60wt%~90wt% of the solids in the raw ore slurry.

[0012] Preferably, the collector includes one or more of xanthate collectors, thiocarbonate collectors, and sulfonic acid collectors.

[0013] Preferably, the collector used is 500g / t to 1500g / t per ton of high-calcium-magnesium, low-grade copper-cobalt oxide ore.

[0014] Preferably, the collector is a combination of xanthate collectors, thiocarbonates, and sulfonic acid collectors in a mass ratio of 45~55:20~30:10~25.

[0015] Preferably, the xanthate collector includes at least one of butyl xanthate and pentyl xanthate.

[0016] Preferably, the thiocarbonate includes at least one of sodium thiocarbonate, potassium thiocarbonate, sodium thiocarbonate, or a derivative of potassium thiocarbonate.

[0017] Preferably, the sulfonic acid collector has the chemical formula RS(=O)2-OM, where R is C 10 ~C 12 The alkyl group, where M is Na or K.

[0018] Preferably, a foaming agent is also added.

[0019] Preferably, the enhanced flotation is carried out in one stage or in two or more stages.

[0020] The flotation activator of this invention is composed of a sulfiding agent, ammonium thiosulfate, and sulfite, wherein the sulfiding agent contains S 2- or HS - As a preferred reactant, it can form initial copper-cobalt sulfide active sites on the surface of copper-cobalt oxide minerals; ammonium thiosulfate, through its NH4+... + The complexation with surface copper-cobalt sites makes the sulfide layer more dense and stable; the sulfite, through its organic sulfur-oxygen functional groups, can weakly coordinate with surface copper sites, lowering the energy barrier of the sulfide reaction and improving the stability of the sulfide film. At the same time, through its strong reducing properties, it regulates the sulfide reaction process, reducing the non-selective oxidation and consumption of the sulfiding agent. The synergistic effect of these three factors results in the formation of a uniform, stable and highly active sulfide layer on the surface of copper-cobalt oxide minerals, thereby improving the flotation activity of copper-cobalt oxide minerals.

[0021] The present invention has the following beneficial effects: (1) This invention makes full use of the synergistic effect between compound reagents, and uses sulfiding agent, ammonium thiosulfate and sulfite as flotation activators to achieve continuous activation and controllable adjustment of the sulfidation process of copper-cobalt oxide minerals, significantly improving the stability and activity of the sulfidation film on the surface of copper-cobalt oxide minerals such as malachite and cobaltite, so that copper-cobalt oxide minerals have better selectivity in flotation, and can improve flotation indicators and reduce acid consumption; (2) Compared with inorganic sulfites, the sulfite provided by the present invention can reduce the energy barrier of the sulfidation reaction by weakly coordinating its sulfur-oxygen organic groups with the copper-cobalt active sites on the surface, which helps to improve the stability of the sulfidation film. At the same time, it can reduce the non-selective oxidation and consumption of the sulfiding agent by regulating the sulfidation reaction process through its strong reducing properties, which is especially suitable for high calcium-magnesium copper-cobalt ores.

[0022] In addition to the objectives, features, and advantages described above, the present invention has other objectives, features, and advantages. The invention will now be described in further detail with reference to the accompanying drawings. Attached Figure Description

[0023] The accompanying drawings, which form part of this application, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings: Figure 1 This is a flow chart of the flotation process in Embodiment 1 of the present invention; Figure 2 This is a comparison chart of the leaching acid consumption results of Example 1 and Comparative Examples 1-4 of the present invention. Detailed Implementation

[0024] To make the objectives, solutions, and beneficial technologies of this invention clearer, the invention will be further described in detail below with reference to embodiments and accompanying drawings. It should be noted that the embodiments described in this specification are merely illustrative of the invention and are not intended to limit the invention.

[0025] For simplicity, this paper only explicitly discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form an undefined range; and any lower limit can be combined with other lower limits to form an undefined range, just as any upper limit can be combined with any other upper limit to form an undefined range. Furthermore, although not explicitly stated, every point or individual value between the endpoints of a range is included within that range. Therefore, each point or individual value can serve as its own lower or upper limit and be combined with any other point or individual value, or with other lower or upper limits, to form an undefined range.

[0026] In this description, it should be noted that, unless otherwise stated, "above" and "below" include the stated number, "multiple" in "one or more" means two or more, and "more than" in "one or more" means two or more.

[0027] An embodiment of the present invention provides a flotation activator for high-calcium-magnesium, low-grade oxidized copper-cobalt ore, comprising a sulfiding agent, ammonium thiosulfate, and sulfite ester; The mass ratio of the sulfiding agent to ammonium thiosulfate is 40~50:30~40; The mass ratio of ammonium thiosulfate to sulfite is 30-40:10-20.

[0028] The flotation activator contains a sulfiding agent, which also serves to sulfide the copper-cobalt oxide minerals.

[0029] In embodiments of the present invention, the sulfiding agent includes at least one of sodium sulfide and sodium hydrosulfide.

[0030] In an embodiment of the present invention, the chemical formula of the sulfite is R-OS(=O)OR′, wherein R and R′ are each independently selected from one of alkyl, aryl, cycloalkyl, alkenyl, and alkynyl groups.

[0031] In some embodiments of the present invention, the sulfite is dimethyl sulfite and phenylsulfite.

[0032] In an embodiment of the present invention, the copper grade in the high-calcium-magnesium low-grade oxidized copper-cobalt ore is 0.5wt%~2.0wt%, the cobalt grade is 0.05wt%~0.3wt%, and the calcium and magnesium grades are both greater than 5wt%.

[0033] In some embodiments of the present invention, the useful minerals in the high-calcium-magnesium low-grade copper-cobalt oxide ore include one or more of malachite, azurite, and cobaltite, and the gangue minerals include one or more of quartz, dolomite, and calcite; the oxidation rate of the high-calcium-magnesium low-grade copper-cobalt oxide ore is greater than 90 wt%.

[0034] In an embodiment of the present invention, 500g to 1500g of flotation activator is used per ton of high-calcium-magnesium low-grade copper-cobalt oxide ore.

[0035] In embodiments of the present invention, the flotation activator is added to the pulp before the collector is added. The flotation activator enhances the flotation activity of copper-cobalt oxide minerals, thereby improving the effectiveness of subsequent flotation.

[0036] This invention provides an enhanced flotation method for high-calcium-magnesium, low-grade copper-cobalt oxide ore. The high-calcium-magnesium, low-grade copper-cobalt oxide ore is ground and slurry prepared to obtain a raw ore slurry. After adding the aforementioned flotation activator, a collector is added for enhanced flotation to obtain a concentrate enriched with valuable elements. During the enhanced flotation process, the sulfidated copper-cobalt oxide minerals float with high efficiency and selectivity, thereby achieving effective separation of valuable copper-cobalt minerals from high-calcium-magnesium gangue minerals.

[0037] In an embodiment of the present invention, the solid content of the raw ore slurry is 20wt%~40wt%, and the particles with a diameter of less than 0.074mm account for 60wt%~90wt% of the solids in the raw ore slurry.

[0038] In embodiments of the present invention, the collector includes one or more of xanthate collectors, thiocarbonate collectors, and sulfonic acid collectors.

[0039] Traditional xanthate collectors, while possessing some collecting ability for sulfidated copper-cobalt oxide minerals, exhibit significantly reduced selectivity under conditions of fine-grained valuable mineral inclusions. This results in severe gangue entrainment and a decline in concentrate grade, hindering efficient separation of valuable minerals from calcium-magnesium gangue minerals. Consequently, downstream wet leaching acid consumption increases, significantly raising production costs. Based on the flotation activator of this invention, optimizing the collector formulation can further enhance flotation performance. In the compound collector system composed of xanthate collectors, thiocarbonates, and sulfonic acid collectors, the xanthate collector exhibits directional adsorption and collection of sulfidated copper-cobalt oxide minerals; thiocarbonates improve the activity of mineral surface sites, enhancing the targeted adsorption of xanthate collectors on mineral surfaces and inhibiting their non-selective adsorption on calcium-magnesium gangue mineral surfaces; sulfonic acid collectors, through their synergistic collection of fixative groups and long-chain hydrophobic groups, regulate the hydrophobic structure of the interface, stabilizing and enhancing the hydrophobic layer thickness, and improving the adhesion probability of particles and bubbles and the ore-carrying capacity.

[0040] By using xanthate-based collectors, thiocarbonate and sulfonic acid-based collectors as compound collectors, the hydrophobic layer thickness and bubble carrying capacity are steadily enhanced through the effects of strengthening targeted adsorption collection and regulating the hydrophobic structure of the interface. This can significantly improve the flotation selectivity and recovery rate of copper-cobalt oxide minerals and achieve effective separation from calcium-magnesium gangue minerals.

[0041] First, a compound activator (sulfiding agent, ammonium thiosulfate, and sulfite) is used to regulate the surface activity of copper-cobalt minerals and enhance the stability of the sulfidation film. Then, a compound collector (xanthate collector, thiocarbonate, and sulfonic acid collector) is added to target the adsorption of sulfidated copper-cobalt oxide minerals and improve the overall hydrophobicity of the minerals, enabling efficient separation and recovery of valuable minerals from calcium-magnesium gangue minerals. Through the synergistic effect of the compound activator and collector, non-selective consumption and dosage of reagents are reduced, improving the flotation separation effect of copper-cobalt oxide ores, achieving enhanced flotation of copper-cobalt oxide minerals, reducing acid consumption in wet leaching, and providing a simple and low-cost process. This solves the problem of economically and efficiently recovering complex copper-cobalt oxide ores with high calcium and magnesium content and low grade, and has good industrial applicability.

[0042] In embodiments of the present invention, the collector used is 500g / t to 1500g / t per ton of high-calcium-magnesium low-grade copper-cobalt oxide ore.

[0043] In embodiments of the present invention, the collector is a combination of xanthate collectors, thiocarbonates, and sulfonic acid collectors in a mass ratio of 45~55:20~30:10~25.

[0044] In embodiments of the present invention, the xanthate collector includes at least one of butyl xanthate and pentyl xanthate.

[0045] In embodiments of the present invention, the thiocarbonate includes at least one of sodium thiocarbonate, potassium thiocarbonate, sodium thiocarbonate, or a derivative of potassium thiocarbonate.

[0046] In an embodiment of the present invention, the sulfonic acid collector has the chemical formula RS(=O)2-OM, where R is C 10 ~C 12 The alkyl group, where M is Na or K.

[0047] In some embodiments of the present invention, the sulfonic acid collector is sodium dodecyl sulfonate.

[0048] In embodiments of the present invention, a frother is also added to enhance flotation.

[0049] In some embodiments of the present invention, the foaming agent is 2 # Oil.

[0050] In embodiments of the present invention, enhanced flotation is performed in one stage or in two or more stages.

[0051] In some embodiments of the present invention, the enhanced flotation is divided into two stages. The tailings obtained from the first stage flotation are subjected to the second stage flotation, and the tailings obtained from the second stage flotation are the final tailings. The concentrates obtained from the first stage flotation and the second stage flotation are the final concentrates.

[0052] Example The following embodiments describe the disclosure of this invention in more detail. These embodiments are merely illustrative and not intended to limit the scope of protection of this invention, as various modifications and variations will be apparent to those skilled in the art within the scope of this disclosure. Unless otherwise stated, all parts, percentages, and ratios reported in the following embodiments are based on weight. Unless otherwise stated, all reagents used in the embodiments are available commercially or synthesized using conventional methods and are ready for use without further processing. Unless otherwise stated, the instruments used in the embodiments are available commercially.

[0053] Example 1 A high-calcium, low-magnesium, oxidized copper-cobalt ore deposit (1) in the Democratic Republic of Congo has the following composition: copper grade 1.06 wt%, cobalt grade 0.13 wt%, calcium grade 7.22 wt%, and magnesium grade 6.15 wt%. The main valuable minerals are malachite and cobaltite, while the gangue minerals are mainly quartz and dolomite. The oxidation rate is greater than 90 wt%. Flotation experiments were conducted on the deposit, and the leaching and recovery of the resulting concentrate were analyzed. The flotation process is as follows: Figure 1 As shown, the specific steps are as follows: (1) Grinding and pulp preparation: After crushing, the high-calcium-magnesium low-grade copper-cobalt oxide ore 1 is ground and prepared into raw ore pulp; the solid content of the raw ore pulp is 33wt%, and the particles with a diameter of less than 0.074mm account for 65wt% of the solids in the raw ore pulp; (2) Flotation operation: The flotation in this embodiment is divided into two roughing stages. The tailings obtained from roughing stage I are subjected to roughing stage II. The tailings obtained from roughing stage II are the final tailings. The concentrates obtained from roughing stage I and roughing stage II are the final concentrates. In the roughing process, the following additives are added sequentially: a compound activator (sodium hydrosulfide 40 wt%, ammonium thiosulfate 40 wt%, dimethyl sulfite 20 wt%) 800 g / t of raw ore; a compound collector (pentyl xanthate 50 wt%, sodium thiocarbonate 30 wt%, sodium dodecyl sulfonate 20 wt%) 800 g / t of raw ore; and a frother (2... # 10g / t of raw ore (oil), flotation time 5min; In the roughing stage II, 200 g / t of the raw ore was added sequentially with a compound activator (40 wt% sodium hydrosulfide, 40 wt% ammonium thiosulfate, and 20 wt% dimethyl sulfite) and 400 g / t of the raw ore with a compound collector (50 wt% pentyl xanthate, 30 wt% sodium thiocarbonate, and 20 wt% sodium dodecyl sulfonate). The flotation was then carried out for 5 min. (3) Leaching operation: The concentrate is leached at room temperature for 6 hours, with a liquid-to-solid ratio (L / Kg) of 4:1, a final pH of 1.6, and concentrated sulfuric acid as the leaching agent.

[0054] Comparative Example 1 The only difference between this comparative example and Example 1 is that the activator in both roughing operations is replaced with a single sodium hydrosulfide, the collector is replaced with a single pentyl xanthate, and the total amount of activator and collector remains unchanged; the other conditions and parameters are the same as in Example 1.

[0055] Comparative Example 2 The only difference between this comparative example and Example 1 is that the activator in both roughing operations is replaced with a single ammonium thiosulfate, the collector is replaced with a single pentyl xanthate, and the total amount of activator and collector remains unchanged; the other conditions and parameters are the same as in Example 1.

[0056] Comparative Example 3 The only difference between this comparative example and Example 1 is that the activator in both roughing operations is replaced with dimethyl sulfite, the collector is replaced with pentyl xanthate, and the total amount of activator and collector remains unchanged; the other conditions and parameters are the same as in Example 1.

[0057] Comparative Example 4 The only difference between this comparative example and Example 1 is that the activator added in both roughing operations is changed to sodium hydrosulfide and sodium thiosulfate (mass ratio 1:1), the collector is changed to a single pentyl xanthate, and the total amount of activator and collector remains unchanged; the other conditions and parameters are the same as in Example 1.

[0058] The flotation test recovery results of Example 1 and Comparative Examples 1-4 are shown in Table 1. As can be seen from Table 1, although the concentrate yield of the comparative examples is higher or lower than that of Example 1, the copper and cobalt recovery rates are significantly lower than those of Example 1. Using the technical solution of the present invention, the copper and cobalt recovery rates are all above 80%, which is significantly higher than that of Comparative Examples 1-4, and truly realizes the efficient utilization of difficult-to-process high-calcium-magnesium low-grade copper and cobalt resources.

[0059] Acid consumption in leaching operations of Examples 1 and Comparative Examples 1-4 is as follows: Figure 2 As shown; by Figure 2It can be seen that the total acid consumption of the concentrate obtained by using the technical solution of the present invention is lower than that of the total acid consumption of the concentrate obtained by comparative examples 1 to 4. This indicates that compared with the comparative examples, the concentrate of the embodiment has a lower acid-consuming gangue component, better flotation selectivity, and also reduces production costs.

[0060] Table 1. Recovery results of flotation tests in Example 1 and Comparative Examples 1-4 Example 2 A high-calcium, low-grade copper-cobalt oxide ore, known as "2," in the Democratic Republic of Congo has the following composition: copper grade 1.12%, cobalt grade 0.14%, calcium grade 8.05%, and magnesium grade 6.84%. The main valuable minerals are malachite, azurite, and a small amount of cobaltite. The gangue minerals are mainly quartz, dolomite, and calcite. The oxidation rate is greater than 90%. Flotation experiments were conducted on the ore, and the resulting concentrate was leached to assess recovery. The specific steps are as follows: (1) Grinding and slurry preparation: After crushing, the high-calcium magnesium low-grade copper-cobalt oxide ore 2 is ground and slurry prepared to obtain raw ore slurry; the solid content of the raw ore slurry is 35wt%, and the particles with a diameter of less than 0.074mm account for 75wt% of the solids in the raw ore slurry; (2) Flotation operation: The flotation in this embodiment is divided into two roughing stages. The tailings obtained from roughing stage I are subjected to roughing stage II. The tailings obtained from roughing stage II are the final tailings. The concentrates obtained from roughing stage I and roughing stage II are the final concentrates. In the roughing process (I), 1000 g / t of raw ore is added sequentially as follows: a compound activator (sodium sulfide 50 wt%, ammonium thiosulfate 35 wt%, methyl phenylsulfite 15 wt%), a compound collector (butyl xanthate 50 wt%, sodium thiocarbonate 30 wt%, sodium dodecyl sulfonate 20 wt%), and a frother (2... # 10g / t of raw ore (oil), flotation time 5min; In the roughing stage II, 300 g / t of raw ore was added sequentially with a compound activator (sodium sulfide 50 wt%, ammonium thiosulfate 35 wt%, methyl phenylsulfite 15 wt%) and a compound collector (butyl xanthate 50 wt%, sodium thiocarbonate 30 wt%, sodium dodecyl sulfonate 20 wt%), and flotation was carried out for 5 min. (3) Leaching operation: The concentrate is leached at room temperature for 6 hours, with a liquid-to-solid ratio (L / Kg) of 4:1, a final pH of 1.6, and concentrated sulfuric acid as the leaching agent.

[0061] Example 3 Unlike Example 2, the compound activator was added to the two roughing operations and adjusted to contain 50 wt% sodium sulfide, 40 wt% ammonium thiosulfate, and 10 wt% vinyl sulfite. The other conditions and parameters were the same as in Example 2.

[0062] Comparative Example 5 The only difference between this comparative example and Example 2 is that the activator added in both roughing operations is changed to sodium sulfide and ammonium sulfite (mass ratio 1:1), and the collector is changed to butyl xanthate and benzohydroxyxamic acid (mass ratio 1:1). The total amount of activator and collector remains unchanged. All other conditions and parameters are the same as in Example 2.

[0063] Comparative Example 6 The only difference between this comparative example and Example 2 is that the activator added in both roughing operations is changed to sodium sulfide, ammonium sulfite and sodium sulfite (mass ratio 4:4:2), and the collector is changed to pentyl xanthate and benzoyl hydroxamic acid (mass ratio 1:1). The total amount of activator and collector remains unchanged. All other conditions and parameters are the same as in Example 2.

[0064] Comparative Example 7 The only difference between this comparative example and Example 2 is that the collector in both roughing operations was changed to conventional pentyl xanthate, while the type and amount of activator and the total amount of collector remained unchanged; the other conditions and parameters were the same as in Example 2.

[0065] The flotation test recovery results of Examples 2-3 and Comparative Examples 5-7 are shown in Table 2. As can be seen from Table 2, although the concentrate yield of the comparative examples is similar to that of Examples 2-3, the copper and cobalt recovery rates are significantly lower than those of the examples. Using the technical solution of the present invention, the copper and cobalt recovery rates are all above 80%, which truly realizes the efficient utilization of difficult-to-process high-calcium-magnesium low-grade copper and cobalt resources.

[0066] Table 2. Recovery results of flotation tests in Examples 2-3 and Comparative Examples 5-7

Claims

1. A flotation activator for high-calcium-magnesium, low-grade oxidized copper-cobalt ore, characterized in that, Including sulfiding agents, ammonium thiosulfate, and sulfites; The mass ratio of the sulfiding agent to ammonium thiosulfate is 40~50:30~40; The mass ratio of ammonium thiosulfate to sulfite is 30-40:10-20.

2. The flotation activator for high-calcium-magnesium, low-grade oxidized copper-cobalt ore according to claim 1, characterized in that, The vulcanizing agent includes at least one of sodium sulfide and sodium hydrosulfide; The chemical formula of the sulfite is R-OS(=O)OR′, wherein R and R′ are each independently selected from one of alkyl, aryl, cycloalkyl, alkenyl, and alkynyl groups.

3. The flotation activator for high-calcium-magnesium, low-grade oxidized copper-cobalt ore according to claim 1, characterized in that, The high-calcium-magnesium low-grade oxidized copper-cobalt ore has a copper grade of 0.5wt%~2.0wt%, a cobalt grade of 0.05wt%~0.3wt%, and both calcium and magnesium grades are greater than 5wt%.

4. The flotation activator for high-calcium-magnesium, low-grade oxidized copper-cobalt ore according to any one of claims 1 to 3, characterized in that, For every ton of high-calcium-magnesium, low-grade copper-cobalt oxide ore, 500g to 1500g of flotation activator should be used.

5. The flotation activator for high-calcium-magnesium, low-grade oxidized copper-cobalt ore according to any one of claims 1 to 3, characterized in that, Add the collector to the slurry before using it.

6. An enhanced flotation method for high-calcium-magnesium, low-grade oxidized copper-cobalt ore, characterized in that, High-calcium-magnesium, low-grade oxidized copper-cobalt ore is ground and slurry is prepared to obtain raw ore slurry; after adding the flotation activator as described in any one of claims 1 to 5, a collector is added to carry out enhanced flotation to obtain a concentrate enriched with valuable elements.

7. The enhanced flotation method for high-calcium-magnesium, low-grade copper-cobalt oxide ore according to claim 6, characterized in that, The solid content of the raw ore slurry is 20wt%~40wt%, and the particles with a diameter of less than 0.074mm account for 60wt%~90wt% of the solids in the raw ore slurry. The collector includes one or more of xanthate collectors, thiocarbonate collectors and sulfonic acid collectors; For every ton of high-calcium-magnesium, low-grade oxidized copper-cobalt ore, the corresponding collector usage is 500g / t to 1500g / t.

8. The enhanced flotation method for high-calcium-magnesium, low-grade copper-cobalt oxide ore according to claim 7, characterized in that, The collector is a combination of xanthate collectors, thiocarbonates, and sulfonic acid collectors in a mass ratio of 45~55:20~30:10~25; The xanthate collector includes at least one of butyl xanthate and pentyl xanthate; The thiocarbonate includes at least one of sodium thiocarbonate, potassium thiocarbonate, sodium thiocarbonate or a derivative of potassium thiocarbonate. The sulfonic acid collector has the chemical formula RS(=O)2-OM, where R is C 10 ~C 12 The alkyl group, where M is Na or K.

9. The enhanced flotation method for high-calcium-magnesium, low-grade oxidized copper-cobalt ore according to any one of claims 6 to 8, characterized in that, Foaming agents are also added.

10. The enhanced flotation method for high-calcium-magnesium, low-grade oxidized copper-cobalt ore according to any one of claims 6 to 8, characterized in that, Enhanced flotation can be carried out in one stage or in two or more stages.

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