Method for combined mineral processing and metallurgy of high-calcium magnesium copper cobalt ore

Abstract

The present invention provides a method for the combined beneficiation and smelting of high-calcium magnesium copper cobalt ore. The method includes: performing first flotation on the high-calcium magnesium copper cobalt ore to obtain a rough concentrate of copper cobalt sulfide and a tailing of rough selection of copper cobalt sulfide; adding a reducing agent to the rough concentrate of copper cobalt sulfide for roasting, obtaining roasted slag and then performing atmospheric pressure leaching to obtain an atmospheric pressure leaching solution and an atmospheric pressure leaching residue; adding a sulfiding agent to the tailing of rough selection of copper cobalt sulfide for sulfidation, and then adding a second collector for second flotation to obtain a rough concentrate of copper cobalt oxide and a tailing of rough selection of copper cobalt oxide; performing magnetic separation on the tailing of rough selection of copper cobalt oxide to obtain a magnetic concentrate of cobalt oxide; finally, mixing the atmospheric pressure leaching residue, the rough concentrate of copper cobalt oxide and the magnetic concentrate of cobalt oxide for oxygen pressure leaching to obtain an oxygen pressure leaching solution and an oxygen pressure leaching residue. The present invention adopts the process of sulfur-first and oxygen-second flotation enrichment - combined atmospheric pressure and oxygen pressure leaching to efficiently leach copper and cobalt in the high-calcium magnesium copper cobalt ore. The process is simple, the cost is relatively low, and the recovery rates of copper and cobalt are relatively high.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrometallurgy, and in particular, to a method for the combined beneficiation and smelting of high-calcium-magnesium copper-cobalt ore. Background Art

[0002] High-calcium-magnesium copper-cobalt ore refers to ore with an oxidation rate of 10-90% and the content of CaO and MgO in gangue minerals approaching or exceeding 10%. Its characteristics are high ore oxidation rate and large calcium and magnesium content, including sandstone-type ore. The sandstone-type high-calcium-magnesium copper-cobalt ore mainly contains the following components: chalcocite, bornite, covellite, etc. existing in the form of copper sulfide ore; malachite, chrysocolla, cuprite, etc. existing in the form of copper oxide ore; cobalt thiospinel, etc. existing in the form of cobalt sulfide ore; cobalt-bearing dolomite, cobalt clinoptilolite, etc. existing in the form of cobalt oxide ore; and the gangue minerals are mainly siltstone, quartz, dolomite, etc. The copper in high-calcium-magnesium copper-cobalt ore is mainly in the form of copper sulfide, and the cobalt is mainly in the form of cobalt oxide ore. Its composition is relatively complex, and the content of copper-cobalt sulfide ore is relatively high. It is difficult to obtain an ideal leaching rate during direct leaching. In addition, due to the presence of minerals such as dolomite with high calcium and magnesium content in the gangue, the acid consumption is high during direct acid leaching, and the production cost is high.

[0003] Chinese application CN 114054201 A discloses a beneficiation method for high-calcium-magnesium sulfur-oxygen mixed copper-cobalt ore. Through a step-by-step flotation process, sulfide concentrate and oxidized rough concentrate are obtained, and most of the calcium-magnesium gangue minerals are separated at the same time. The obtained copper-cobalt oxide rough concentrate enters the next hydrometallurgical copper smelting process, which can reduce the amount of ore to be treated and the acid consumption in hydrometallurgical leaching, achieving the purpose of saving resources and reducing costs. However, it only treats the copper-cobalt oxide rough concentrate obtained by flotation, and the comprehensive copper recovery rate is only 85.12%, and the comprehensive cobalt recovery rate is only 73.93%, and the copper-cobalt recovery rate is relatively low. Chinese application CN 114950712 A discloses a combined treatment process for comprehensively recovering copper and cobalt. Cobalt-copper ore and single cobalt ore are respectively produced with sulfide copper concentrate, copper oxide concentrate, flotation cobalt concentrate, and magnetic separation cobalt concentrate through flotation and magnetic separation. The sulfide copper concentrate enters hydrometallurgical leaching after roasting, and the copper oxide concentrate, flotation cobalt concentrate, and magnetic separation cobalt concentrate directly enter hydrometallurgical leaching. However, it does not further recover the hydrometallurgical leaching residue of the sulfide copper concentrate, and the hydrometallurgical leaching adopts atmospheric pressure leaching. Due to the presence of sulfur, the leaching rates of Cu and Co are still relatively low.

[0004] At present, there are mainly three types of process routes for treating high-calcium, magnesium, copper and cobalt ores, namely pyrometallurgy, acid leaching, and flotation. The pyrometallurgical treatment process is mainly the matte smelting-copper matte converting process, which has problems such as large investment, high smelting cost, high environmental protection pressure, and high copper content in the slag. When treating high-calcium, magnesium, copper and cobalt ores by acid leaching, there are disadvantages such as high acid consumption and high production cost. At the same time, a large amount of refractory copper and cobalt sulfide ores in the ore will be discarded in the tailings, which is not conducive to the comprehensive recovery of copper and cobalt. The flotation method mainly has the ore dressing process of "copper-cobalt bulk flotation", but there are problems such as low recovery rate of copper and cobalt oxide ores and high calcium and magnesium content in the concentrate. The high-calcium and magnesium concentrate will reduce the quality of the concentrate and increase the subsequent smelting difficulty. Summary of the Invention

[0005] The main object of the present invention is to provide a method for the combined beneficiation and smelting of high-calcium, magnesium, copper and cobalt ores to solve the problems of high process cost and low recovery rate of copper and cobalt during the treatment of high-calcium, magnesium, copper and cobalt ores in the prior art.

[0006] To achieve the above object, according to one aspect of the present invention, a method for the combined beneficiation and smelting of high-calcium, magnesium, copper and cobalt ores is provided, including the following steps: Step S1, adding water to the high-calcium, magnesium, copper and cobalt ore to obtain a pulp, adding a first collector to the pulp, and performing first flotation to obtain a rough concentrate of copper and cobalt sulfide and a tailing of rough selection of copper and cobalt sulfide; Step S2, adding a reducing agent to the rough concentrate of copper and cobalt sulfide and performing roasting to obtain roasted slag and flue gas; Step S3, adding water and sulfuric acid to the roasted slag and performing atmospheric pressure leaching, and separating solid and liquid to obtain an atmospheric pressure leaching solution and an atmospheric pressure leaching residue; Step S4, adding a sulfiding agent to the tailing of rough selection of copper and cobalt sulfide for sulfidation, and then adding a second collector to perform second flotation to obtain a rough concentrate of copper and cobalt oxide and a tailing of rough selection of copper and cobalt oxide; Step S5, performing magnetic separation on the tailing of rough selection of copper and cobalt oxide to obtain a magnetic concentrate of cobalt oxide and a tailing of magnetic separation of cobalt oxide; Step S6, mixing the atmospheric pressure leaching residue, the rough concentrate of copper and cobalt oxide and the magnetic concentrate of cobalt oxide, adding water and sulfuric acid, and performing oxygen pressure leaching, and separating solid and liquid to obtain an oxygen pressure leaching solution and an oxygen pressure leaching residue.

[0007] Further, in step S1, the solid content of the pulp is 20-40%; preferably, step S1 further includes the following steps: grinding the high-calcium, magnesium, copper and cobalt ore to obtain a ground ore material, and then adding water to the ground ore material to obtain a pulp; in the ground ore material, the weight ratio of particles with a particle size ≤ 0.074 mm is 65-85%.

[0008] Further, in step S1, the first collector includes one or more of ethyl xanthate, butyl xanthate, amyl xanthate, and ethyl thionocarbamate, and the addition amount is 50 - 300 g / t; and / or the stirring time of the first flotation is 1 - 5 min, and the flotation time is 2 - 10 min; preferably, a regulator, the first collector, and the first foaming agent are sequentially added to the pulp for the first flotation; wherein, the regulator includes one or more of CaO, Ca(OH)2, and CaCO3 to adjust the pH of the pulp to 7 - 10, and the first foaming agent includes pine oil and / or No. 2 oil, and the addition amount is 20 - 50 g / t.

[0009] Further, in step S2, the reducing agent includes one or more of sodium carbonate, sodium sulfate, and sodium chloride; and / or the weight ratio of the copper-cobalt sulfide rougher concentrate to the reducing agent is 1:(0.2 - 0.5); and / or the roasting temperature is 400 - 600 °C, and the time is 2 - 4 h; preferably, step S2 further includes the following steps: adding water to the flue gas to produce acid to obtain sulfuric acid, and returning the sulfuric acid to atmospheric pressure leaching and / or oxygen pressure leaching.

[0010] Further, in step S3, the acid-to-ore ratio of atmospheric pressure leaching is 180 - 280 kg / t, the liquid-to-solid ratio is (3 - 5):1, and the stirring speed is 300 - 600 r / min; and / or the temperature of atmospheric pressure leaching is 25 - 90 °C, the time is 60 - 240 min, and the pH of the leaching end liquor is 0.8 - 2.5.

[0011] Further, in step S4, the sulfiding agent includes Na2S and / or NaHS, and the addition amount is 1000 - 3000 g / t; and / or the second collector includes one or more of ethyl xanthate, butyl xanthate, amyl xanthate, potassium amyl xanthate, and sodium amyl xanthate, and the addition amount is 500 - 2000 g / t; and / or the sulfiding time is 30 - 80 min; and / or the stirring time of the second flotation is 2 - 6 min, and the flotation time is 2 - 10 min; preferably, a sulfiding agent is added to the copper-cobalt sulfide rougher tailings for sulfiding, and then the second collector, the second foaming agent, and the inhibitor are sequentially added for the second flotation; wherein, the second foaming agent includes pine oil and / or No. 2 oil, and the addition amount is 20 - 50 g / t, and the inhibitor includes sodium hexametaphosphate and / or carboxymethyl cellulose, and the addition amount is 40 - 200 g / t.

[0012] Further, in step S5, the background magnetic field intensity of magnetic separation is 0.3 - 2.0 T; preferably, magnetic separation includes magnetic rougher separation, magnetic cleaning, and magnetic scavenging performed in sequence.

[0013] Further, in step S6, the acid-to-ore ratio for oxygen pressure leaching is 180 - 220 kg / t, the liquid-to-solid ratio is (6 - 10):1, and the stirring speed is 600 - 800 r / min; and / or the temperature for oxygen pressure leaching is 160 - 220 °C, the time is 0.8 - 2 h, the oxygen partial pressure is 0.3 - 0.8 Mpa, and the pH of the leaching end solution is 1.2 - 2.0.

[0014] Further, in step S6, first, the atmospheric pressure leaching residue is subjected to third flotation to obtain an enriched copper-cobalt sulfide leaching residue; then, the enriched copper-cobalt sulfide leaching residue, the rough concentrate of copper-cobalt oxide, and the magnetic concentrate of cobalt oxide are mixed, water and sulfuric acid are added, and oxygen pressure leaching is carried out.

[0015] Further, by weight percentage, in the high-calcium-magnesium copper-cobalt ore, the Cu content is 0.5 - 5 wt.%, the Co content is 0.1 - 1 wt.%, the MgO content is 8 - 15 wt.%, the CaO content is 9 - 16 wt.%, and the S content is 0.2 - 0.6 wt.%.

[0016] Applying the technical solution of the present invention, a process of sulfur-first and oxygen-second flotation enrichment - combined atmospheric pressure and oxygen pressure leaching is adopted for the efficient leaching of copper and cobalt in the high-calcium-magnesium copper-cobalt ore. First, through flotation and magnetic separation processes, the rough concentrates of copper-cobalt sulfide, copper-cobalt oxide, and magnetic cobalt concentrate are obtained. Then, the copper-cobalt sulfide concentrate is roasted and leached under atmospheric pressure to obtain a copper-cobalt leaching solution and a leaching residue containing un-leached copper-cobalt sulfide. Finally, oxygen pressure leaching is carried out on the leaching residue, the copper-cobalt oxide concentrate, and the magnetic cobalt concentrate to obtain a copper-cobalt leaching solution with a high metal recovery rate. The process of the present invention is simple, the cost is low, and the copper-cobalt recovery rate is high. Description of the Drawings

[0017] The specification drawings forming a part of this application are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention. In the drawings:

[0018] Figure 1 Shows the process flow chart of the combined beneficiation and smelting of high-calcium-magnesium copper-cobalt ore according to Embodiment 1 of the present invention;

[0019] Figure 2 Shows the process flow chart of the combined beneficiation and smelting of high-calcium-magnesium copper-cobalt ore according to Embodiment 2 of the present invention. Detailed Embodiments

[0020] It should be noted that, without conflict, the embodiments in this application and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the drawings and in combination with the embodiments.

[0021] Term Explanation:

[0022] Dosage of the reagent: The ratio of the weight of the reagent used (in g) to the weight of the ore to be treated (in t).

[0023] Acid-ore ratio: The ratio of the weight of the acid solution used (in kg) to the weight of the material to be leached (in t) in the leaching process.

[0024] Liquid-solid ratio: The ratio of the weight of the liquid to the weight of the solid material in the ore pulp in the leaching process.

[0025] As described in the background art of the present invention, in the prior art, there are problems of high process cost and low recovery rates of copper and cobalt during the treatment of high-calcium, magnesium, copper, and cobalt ores. To solve the above problems, in a typical embodiment of the present invention, a method for the combined beneficiation and smelting of high-calcium, magnesium, copper, and cobalt ores is provided, including the following steps: Step S1, adding water to the high-calcium, magnesium, copper, and cobalt ore to obtain an ore pulp, adding a first collector to the ore pulp, and performing a first flotation to obtain a rough concentrate of copper and cobalt sulfide and a tailing of copper and cobalt sulfide rough selection; Step S2, adding a reducing agent to the rough concentrate of copper and cobalt sulfide and performing roasting to obtain a roasted slag and flue gas; Step S3, adding water and sulfuric acid to the roasted slag and performing atmospheric pressure leaching, and obtaining an atmospheric pressure leaching solution and an atmospheric pressure leaching residue after solid-liquid separation; Step S4, adding a sulfiding agent to the tailing of copper and cobalt sulfide rough selection for sulfidation, and then adding a second collector to perform a second flotation to obtain a rough concentrate of copper and cobalt oxide and a tailing of copper and cobalt oxide rough selection; Step S5, performing magnetic separation on the tailing of copper and cobalt oxide rough selection to obtain a magnetic concentrate of cobalt oxide and a tailing of cobalt oxide magnetic separation; Step S6, mixing the atmospheric pressure leaching residue, the rough concentrate of copper and cobalt oxide, and the magnetic concentrate of cobalt oxide, adding water and sulfuric acid, and performing oxygen pressure leaching, and obtaining an oxygen pressure leaching solution and an oxygen pressure leaching residue after solid-liquid separation.

[0026] In the prior art, when treating high-calcium, magnesium, copper, and cobalt ores, a combined beneficiation and smelting process with multiple flotations is usually adopted. The multiple flotation processes will cause a large loss of metal elements and reduce the metal recovery rate. For high-calcium, magnesium, copper, and cobalt ores, the present invention adopts a process of sulfur-first and oxygen-second flotation enrichment - combined atmospheric pressure and oxygen pressure leaching for the efficient leaching of copper and cobalt. Only the rough selection of copper and cobalt sulfide concentrate, copper and cobalt oxide concentrate, and cobalt concentrate is carried out, and the beneficiation process is simple with less metal loss.

[0027] Specifically, first add water to the high-calcium, magnesium, copper, and cobalt ore to prepare an ore pulp, and then add a first collector to perform a first flotation. The collector can chemically adsorb on the surfaces of copper sulfide and cobalt sulfide minerals, making them hydrophobic, so as to adsorb the copper and cobalt sulfide ore on the bubbles and rough-select and float it out to obtain a rough concentrate of copper and cobalt sulfide and a tailing of copper and cobalt sulfide rough selection, and then treat the two separately.

[0028] Subsequently, a reducing agent is added to the rougher concentrate of copper-cobalt sulfide for sulfidation roasting. During this process, the reducing agent converts the metal sulfides in the rougher concentrate of copper-cobalt sulfide into soluble salts, which are more easily dissolved in the acidic leaching solution, thereby improving the leaching efficiency of the metal, and reducing sulfur dioxide to sulfates (such as copper sulfate and cobalt sulfate), thus reducing the escape of sulfur dioxide and playing a role in sulfur fixation. Water and sulfuric acid are added to the obtained roasted slag for atmospheric leaching. Based on the acidic leaching principle, the soluble copper and cobalt obtained from the roasted slag are dissolved into the solution through chemical reactions to preliminarily recover the copper and cobalt in the rougher concentrate of copper-cobalt sulfide. After solid-liquid separation, an atmospheric leaching solution and an atmospheric leaching slag are obtained. Moreover, due to the small amount of the atmospheric leaching slag, the processing volume of subsequent processes can be greatly reduced. It should be noted that since there are unoxidized sulfides in the roasted slag of the rougher concentrate of copper-cobalt sulfide and they cannot be recovered during the atmospheric leaching process, directly sending them to the tailings pond will cause copper and cobalt losses. Therefore, in the present invention, they are further subjected to oxygen pressure leaching treatment for secondary recovery to improve the copper and cobalt recovery rate.

[0029] A sulfiding agent is added to the rougher tailings of copper-cobalt sulfide for sulfidation. The sulfiding agent can convert calcium and magnesium ions into insoluble sulfides. Then, a second collector is added for the second flotation. The second collector can selectively combine with copper-cobalt minerals to remove most of the acid-consuming gangue containing calcium and magnesium in the rougher tailings of copper-cobalt sulfide, discard carbonate minerals such as dolomite, and reduce the adverse effects of these minerals on the subsequent leaching process, obtaining a rougher concentrate of copper-cobalt oxide and a rougher tailings of copper-cobalt oxide. Sulfidation and the second flotation can significantly reduce the acid consumption of the leaching process, lower the production cost, and improve the economic benefits. Subsequently, the rougher concentrate of copper-cobalt oxide is directly sent to oxygen pressure leaching without the need for further beneficiation, which can significantly reduce copper and cobalt losses; after direct oxygen pressure leaching, the copper and cobalt recovery rate is high and the acid consumption is low.

[0030] The rougher tailings of copper-cobalt oxide still contain a small amount of cobalt, but it is wrapped by limonite and is difficult to leach directly. Therefore, the rougher tailings of copper-cobalt oxide are subjected to magnetic separation. Based on the magnetic difference between limonite and cobalt, a strong magnetic field will attract magnetic substances such as limonite, while non-magnetic substances such as cobalt will be excluded, thereby realizing the recovery of a small amount of cobalt in the tailings and obtaining a magnetic concentrate of cobalt oxide and a magnetic tailings of cobalt oxide. Finally, the obtained magnetic concentrate of cobalt oxide is also subjected to oxygen pressure leaching to achieve a high comprehensive recovery rate of copper and cobalt.

[0031] Compared with atmospheric pressure leaching, in the present invention, the atmospheric pressure leaching residue, the rough concentrate of copper oxide cobalt ore, and the magnetic separation concentrate of cobalt oxide ore are mixed, and water and sulfuric acid are added to an autoclave together, and oxygen is introduced simultaneously for oxygen pressure leaching. During this process, oxygen can act as a strong oxidant to replace sulfuric acid, reducing the consumption of sulfuric acid; and high pressure can increase the solubility of oxygen, directly oxidizing metal sulfides to form sulfates, thereby reducing sulfuric acid consumption; the oxygen pressure condition can more effectively dissolve metals, reducing the residue of metals in the leaching residue. Thus, while reducing the sulfuric acid consumption, the leaching rates of copper and cobalt are significantly increased, and the loss of metals in the high-calcium-magnesium copper-cobalt ore is greatly reduced.

[0032] In summary, the present invention adopts a process of sulfur-first and oxygen-second flotation enrichment - combined atmospheric pressure and oxygen pressure leaching to efficiently leach copper and cobalt from high-calcium-magnesium copper-cobalt ore. First, the rough sulfide copper-cobalt concentrate, copper oxide cobalt concentrate, and magnetic separation cobalt concentrate are obtained through flotation and magnetic separation processes. Then, the sulfide copper-cobalt concentrate is roasted and leached under atmospheric pressure to obtain a copper-cobalt leaching solution and a leaching residue containing un-leached sulfide copper-cobalt. Finally, the leaching residue, copper oxide cobalt concentrate, and magnetic separation cobalt concentrate are subjected to oxygen pressure leaching to obtain a copper-cobalt leaching solution with a high metal leaching rate. The process of the present invention is simple, with a relatively low cost, and a relatively high recovery rate of copper and cobalt. The comprehensive recovery rate of cobalt is ≥96%, and the comprehensive recovery rate of copper is ≥97%.

[0033] In a preferred embodiment, in step S1, the solid content of the pulp is 20 - 40%; this can reduce the liquid treatment amount in the subsequent leaching process, thereby reducing energy consumption and wastewater treatment costs, while improving the fluidity and stability of the pulp, being conducive to the uniform distribution and collecting effect of flotation reagents, and further improving the recovery efficiency of copper and cobalt. Preferably, step S1 further includes the following steps: grinding the high-calcium-magnesium copper-cobalt ore to obtain ground ore material, and then adding water to the ground ore material to obtain pulp; in the ground ore material, the weight ratio of particles with a particle size ≤0.074 mm is 65 - 85%.

[0034] By optimizing the particle size of the ground ore material to make it uniform and small, the copper-cobalt minerals can be more fully dissociated from gangue, which is conducive to the efficient collection of copper-cobalt minerals in the subsequent flotation process and reduces the negative impact of undissociated minerals on metal recovery. Moreover, by controlling the grinding fineness, the concentrate grade can be significantly improved, the ore amount in the subsequent treatment stage can be reduced, the overall process cost can be further reduced, the ore treatment process can be optimized from the source, energy consumption, material consumption, and treatment costs can be effectively reduced, and at the same time, the recovery rates of copper and cobalt can be further improved.

[0035] For the purpose of significantly improving the recovery efficiency of copper and cobalt in the raw material high-calcium magnesium copper cobalt ore while reducing the use cost of reagents and energy consumption, in a preferred embodiment, in step S1, the first collector includes one or more of ethyl xanthate, butyl xanthate, amyl xanthate and ethyl thionocarbamate (Z-200), and the addition amount is 50-300 g / t; and / or the stirring time of the first flotation is 1-5 min, and the flotation time is 2-10 min; preferably, a regulator, the first collector and the first foaming agent are sequentially added to the pulp for the first flotation; wherein, the regulator includes one or more of CaO, Ca(OH)2 and CaCO3 to adjust the pH of the pulp to 7-10, and the first foaming agent includes pine oil and / or No. 2 oil, and the addition amount is 20-50 g / t.

[0036] Among the first collectors of the above types, their specific chemical structures can form a stable hydrophobic film on the surface of copper-cobalt sulfide minerals, significantly enhancing the hydrophobicity of the minerals, so as to more effectively separate copper-cobalt minerals from gangue during the flotation process. Controlling the addition amount within the above range can further improve the collection effect, while reducing the cost increase and reagent waste caused by excessive addition. During the flotation process, the stirring time within the above range can make the reagent distribution more uniform while maintaining lower energy consumption, and the flotation time within the above range can further improve the recovery rate while maintaining higher processing efficiency. By optimizing the stirring time and flotation time, it is more conducive to effectively reducing energy consumption while enabling the minerals to fully contact and selectively separate.

[0037] The above regulators can create an alkaline environment more conducive to the flotation of copper-cobalt minerals, reduce the interference of harmful minerals, and improve the flotation selectivity. The above foaming agents can not only promote the formation and stability of bubbles, but also further enhance the contact between minerals and reagents, which is more conducive to improving the flotation efficiency and recovery rate.

[0038] In a preferred embodiment, in step S2, the reducing agent includes one or more of sodium carbonate, sodium sulfate and sodium chloride; and / or the weight ratio of the copper-cobalt rough concentrate to the reducing agent is 1:(0.2-0.5); and / or the roasting temperature is 400-600 °C and the time is 2-4 h. These types of reducing agents can promote the redox reaction of copper-cobalt sulfide minerals at a lower roasting temperature to generate metal salts that are easily leached by acid. This can not only increase the solubility of metals, but also have a sulfur fixation effect, reducing the emission of sulfur dioxide during the roasting process, which is beneficial to environmental protection and the subsequent recycling of acid.

[0039] Limiting the weight ratio of the copper-cobalt rough concentrate to the reducing agent within the above range is more conducive to promoting the full contact and reaction between the reducing agent and metal sulfides, reducing incomplete conversion caused by insufficient reducing agent or the additional costs and possible increase in slag volume brought about by excessive reducing agent, and achieving a balance between economy and efficiency. Controlling the roasting temperature and time is conducive to achieving efficient conversion of metal sulfides, promoting appropriate decomposition of sulfides, increasing the leaching rate of metals, and at the same time reducing excessive oxidation of minerals at high temperatures or the formation of insoluble by-products (such as metal oxides), thereby better controlling energy consumption and reducing production costs.

[0040] Preferably, step S2 further includes the following steps: adding water to the flue gas to produce sulfuric acid, and returning the sulfuric acid to atmospheric pressure leaching and / or oxygen pressure leaching. Further recycling the sulfur dioxide generated during the roasting of the copper-cobalt rough concentrate to produce acid and returning it to the atmospheric pressure leaching and oxygen pressure leaching processes can further reduce environmental pollution, save resources and production costs.

[0041] The present invention also significantly improves the economy and environmental friendliness of the treatment of high-calcium-magnesium copper-cobalt ore as raw material and at the same time increases the metal recovery rate by optimizing the leaching parameters. In a preferred embodiment, in step S3, the acid-to-ore ratio for atmospheric pressure leaching is 180 - 280 kg / t, the liquid-to-solid ratio is (3 - 5):1, and the stirring speed is 300 - 600 r / min; and / or the temperature for atmospheric pressure leaching is 25 - 90 °C, the time is 60 - 240 min, and the pH of the leaching end liquor is 0.8 - 2.5.

[0042] By optimizing the acid-to-ore ratio and liquid-to-solid ratio for atmospheric pressure leaching, the acid consumption during the leaching process can be effectively controlled, reducing the cost increase and environmental pollution caused by excessive acid addition. At the same time, a lower liquid-to-solid ratio can further reduce the liquid volume in the subsequent treatment stage, reducing energy consumption and treatment costs. Increasing the stirring speed can accelerate the mass transfer between the pulp and the acid solution, increase the leaching rate, shorten the leaching time, and enhance the treatment efficiency.

[0043] Setting the leaching temperature and time within the above range is more conducive to promoting the full dissolution of copper-cobalt minerals, increasing the metal recovery rate, and at the same time reducing energy waste and equipment loss caused by high temperatures, taking into account the balance between the reaction rate and energy consumption. Within the above pH range of the leaching end liquor, it is more conducive to the stable existence of metal ions in an acidic environment and can also reduce the risk of secondary precipitation, creating favorable conditions for subsequent treatment.

[0044] In a preferred embodiment, in step S4, the vulcanizing agent includes Na2S and / or NaHS, and the addition amount is 1000 - 3000 g / t; and / or the second collector includes one or more of ethyl xanthate, butyl xanthate, amyl xanthate, potassium amyl xanthate and sodium amyl xanthate, and the addition amount is 500 - 2000 g / t; and / or the vulcanizing time is 30 - 80 min; and / or the stirring time of the second flotation is 2 - 6 min, and the flotation time is 2 - 10 min; preferably, a vulcanizing agent is added to the copper-cobalt rougher tailings for vulcanization, and then a second collector, a second frother and an inhibitor are sequentially added for the second flotation; wherein, the second frother includes pine oil and / or No. 2 oil, and the addition amount is 20 - 50 g / t, and the inhibitor includes sodium hexametaphosphate and / or carboxymethyl cellulose, and the addition amount is 40 - 200 g / t.

[0045] The above vulcanizing agent can not only effectively activate copper-cobalt minerals and improve the collection efficiency of subsequent flotation, but also reduce the cost increase and possible inhibitory effects caused by excessive addition. Controlling the addition amount of the second collector within the above range is more conducive to promoting the selective collection of copper-cobalt minerals, reducing the mixing of associated gangue, thereby reducing the amount of ore in the subsequent treatment stage, reducing the consumption of energy and reagents, and effectively reducing the overall production cost. Optimizing the vulcanizing time is beneficial to making the vulcanization reaction proceed more fully, strengthening the surface modification of minerals and the adsorption of reagents, and providing conditions for subsequent efficient flotation. Optimizing the stirring time and flotation time in the second flotation is beneficial to making the reagents contact the minerals more fully, while controlling unnecessary energy consumption, reducing the damage or over-activation of minerals during long-term stirring, and further improving the quality of concentrate and the metal recovery rate.

[0046] The addition of the above second frother can promote the formation of bubbles, increase the attachment opportunity between minerals and bubbles, and improve the flotation efficiency. The use of the above inhibitor is beneficial to controlling the flotation of harmful gangue and reducing the loss of copper and cobalt during flotation, thereby further improving the copper-cobalt recovery rate.

[0047] To recover more fully and specifically the trace cobalt encapsulated in limonite in the copper-cobalt oxide rougher tailings, while effectively removing non-magnetic gangue, improving the cobalt recovery rate and reducing the subsequent treatment cost, in a preferred embodiment, in step S5, the background magnetic field intensity of magnetic separation is 0.3 - 2.0 T; preferably, magnetic separation includes magnetic rougher separation, magnetic cleaning and magnetic scavenging carried out in sequence. The above high-gradient magnetic separation has better selectivity, can effectively separate weakly magnetic cobalt oxide minerals, reduce the mixing of strongly magnetic gangue, and reduce the amount of ore and energy consumption in subsequent treatment.

[0048] More preferably, the background magnetic field intensity for rough magnetic separation is 1.2 - 1.5 T, the background magnetic field intensity for fine magnetic separation is 0.9 - 1.1 T, and the background magnetic field intensity for scavenging magnetic separation is 0.75 - 0.85 T. Under the above rough magnetic separation conditions, most of the cobalt magnetic minerals can be initially captured; the intensity of fine magnetic separation is used to further improve the concentrate grade, remove the entrained non-magnetic minerals, and achieve high-purity recovery of cobalt; the above scavenging magnetic separation conditions are more conducive to recovering the micro-magnetic cobalt minerals that may be lost in rough magnetic separation and fine magnetic separation, reducing resource waste, and further improving the overall recovery rate of cobalt. The specific classified magnetic separation process can not only effectively recover the cobalt resources in the copper-cobalt oxide roughing tailings, reduce the cost of direct leaching, but also improve the grade of cobalt concentrate, laying a solid foundation for subsequent low-cost and high-efficiency metal extraction.

[0049] In a preferred embodiment, in step S6, the acid-to-ore ratio for oxygen pressure leaching is 180 - 220 kg / t, the liquid-to-solid ratio is (6 - 10):1, and the stirring speed is 600 - 800 r / min; and / or the temperature of oxygen pressure leaching is 160 - 220 °C, the time is 0.8 - 2 h, the oxygen partial pressure is 0.3 - 0.8 Mpa, and the pH of the leaching end liquor is 1.2 - 2.0. The precise control of the acid-to-ore ratio and the liquid-to-solid ratio can promote the full contact between the acid solution and the ore material, accelerate the dissolution of copper and cobalt metals, reduce excessive acid consumption at the same time, lower the cost and reduce environmental pollution.

[0050] When the temperature, time, and oxygen partial pressure of oxygen pressure leaching are within the above ranges, it is conducive to providing an ideal thermodynamic and kinetic environment for oxidative leaching. The above temperature can accelerate the oxidation reaction rate, and the sufficient oxygen supply under high pressure is conducive to the full oxidation of refractory metal sulfides and oxides, promoting the dissolution of metal ions, especially having a significant leaching effect on the residual copper-cobalt sulfide and copper-cobalt oxide ore after pretreatment. Controlling the pH of the leaching end liquor to be an acidic environment is conducive to the stable existence of copper and cobalt metal ions, improving the leaching rate of metals and the separation and purification efficiency in the subsequent process. The above oxygen pressure leaching conditions can, on the one hand, increase the solubility and leaching rate of metals in complex high-calcium-magnesium copper-cobalt ore, and on the other hand, are conducive to reducing unnecessary side reactions and resource waste, taking into account both cost and environmental protection while increasing the recovery rate of copper and cobalt.

[0051] Flotation of atmospheric pressure leaching residue can further reduce the amount of residue that needs to be subjected to oxygen pressure leaching. In a preferred embodiment, in step S6, the atmospheric pressure leaching residue is first subjected to a third flotation to obtain a concentrated copper-cobalt sulfide leaching residue; then the concentrated copper-cobalt sulfide leaching residue, the rough concentrate of copper-cobalt oxide, and the magnetic concentrate of cobalt oxide are mixed, water and sulfuric acid are added, and oxygen pressure leaching is carried out. Through the enrichment treatment of the atmospheric pressure leaching residue by the third flotation, non-metallic minerals and low-value components therein can be effectively removed, the amount of ineffective ore during oxygen pressure leaching can be reduced, the use of acid solution and oxygen can be saved, and the cost can be reduced. During the mixed oxygen pressure leaching of the concentrated copper-cobalt sulfide leaching residue with the rough concentrate of copper-cobalt oxide and the magnetic concentrate of cobalt oxide, the synergistic effect of different forms of copper-cobalt minerals can be utilized to improve the leaching efficiency and recovery rate of metals. Especially for the remaining copper-cobalt sulfide minerals, under high temperature, high pressure and strong oxidation environment, oxygen pressure leaching can achieve more thorough metal dissolution and significantly improve the recovery efficiency of copper-cobalt sulfide.

[0052] More preferably, the third flotation includes: first adding water to adjust the solid content of the pulp to 25-35%, then adding a supplementary regulator to adjust the pH of the feed liquid to 7-9, and then successively adding a supplementary collector and a supplementary frother to carry out the third flotation. Further preferably, the supplementary regulator includes one or more of CaO, Ca(OH)2 and CaCO3, the supplementary collector includes one or more of ethyl xanthate, butyl xanthate, amyl xanthate and ethyl thionocarbamate, and the addition amount is 40-60 g / t, the supplementary frother includes pine oil and / or No. 2 oil, and the addition amount is 10-30 g / t; and / or the stirring time of the third flotation is 1-5 min, and the flotation time is 2-10 min.

[0053] The above conditions are conducive to further accelerating the reaction between metal minerals and reagents, improving the selectivity and efficiency during the flotation process, reducing metal loss, and improving the purity of the concentrate. Thus, through pretreatment enrichment and precise control of flotation conditions, the recovery rate of copper and cobalt can be significantly improved, the oxygen pressure leaching process can be optimized, and the cost can be reduced.

[0054] In a preferred embodiment, by weight percentage, in the high-calcium magnesium copper cobalt ore, the Cu content is 0.5 - 5 wt.%, the Co content is 0.1 - 1 wt.%, the MgO content is 8 - 15 wt.%, the CaO content is 9 - 16 wt.%, and the S content is 0.2 - 0.6 wt.%. For the ore within this composition range, due to the high proportions of CaO and MgO, direct acid leaching will consume a large amount of acid solution, resulting in a significant increase in processing costs. At the same time, the Cu in the ore generally exists mainly as sulfides, the Co generally exists in the form of oxides, and the S content is moderate, which can provide a more ideal material basis for the "sulfur first then oxygen" flotation and the "atmospheric pressure - oxygen pressure" combined leaching of the present invention. For the ore with high CaO and MgO contents, the present invention effectively removes these acid-consuming gangue through processes such as flotation and leaching, thereby reducing the consumption of the collector and the acid consumption in the subsequent acid leaching process, saving costs, achieving the comprehensive recovery of copper and cobalt resources, and having a higher overall metal recovery rate.

[0055] Typically but not limitedly, in step S1, the addition amount of the first collector is 50 g / t, 100 g / t, 150 g / t, 200 g / t, 250 g / t, 300 g / t or a range value composed of any two of these values.

[0056] Typically but not limitedly, in step S2, the weight ratio of the copper cobalt sulfide rougher concentrate to the reducing agent is 1:0.2, 1:0.3, 1:0.4, 1:0.5 or a range value composed of any two of these values.

[0057] Typically but not limitedly, in step S2, the roasting temperature is 400 °C, 450 °C, 500 °C, 550 °C, 600 °C or a range value composed of any two of these values, and the time is 2 h, 2.5 h, 3 h, 3.5 h, 4 h or a range value composed of any two of these values.

[0058] Typically but not limitedly, in step S4, the addition amount of the sulfiding agent is 1000 g / t, 1500 g / t, 2000 g / t, 2500 g / t, 3000 g / t or a range value composed of any two of these values.

[0059] Typically but not limitedly, in step S4, the addition amount of the second collector is 500 g / t, 1000 g / t, 1500 g / t, 2000 g / t or a range value composed of any two of these values.

[0060] Typically but not limitedly, in step S4, the sulfiding time is 30 min, 40 min, 50 min, 60 min, 70 min, 80 min or a range value composed of any two of these values.

[0061] Typically but not limitedly, in step S5, the background magnetic field intensity for magnetic separation is 0.3 T, 0.5 T, 1.0 T, 1.5 T, 2.0 T, or a range value composed of any two of these values.

[0062] Typically but not limitedly, in step S6, the temperature for oxygen pressure leaching is 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C, or a range value composed of any two of these values; the time is 0.8 h, 1.0 h, 1.2 h, 1.5 h, 1.8 h, 2 h, or a range value composed of any two of these values; and the oxygen partial pressure is 0.3 Mpa, 0.4 Mpa, 0.5 Mpa, 0.6 Mpa, 0.7 Mpa, 0.8 Mpa, or a range value composed of any two of these values.

[0063] The following further describes the present application in detail with specific embodiments, which should not be construed as limiting the scope claimed by the present application.

[0064] Example 1

[0065] The process flow chart is shown in Figure 1 .

[0066] A method for the combined beneficiation and smelting of high-calcium-magnesium-copper-cobalt ore; by weight percentage, in the high-calcium-magnesium-copper-cobalt ore, the Cu content is 3.21 wt.%, the Co content is 0.23 wt.%, the MgO content is 10.93 wt.%, the CaO content is 12.31 wt.%, and the S content is 0.47 wt.%; the method includes the following steps:

[0067] Step S1, grind the high-calcium-magnesium-copper-cobalt ore to obtain ground ore (the weight ratio of particles with a particle size ≤ 0.074 mm is 75%), then add water to the ground ore to obtain a pulp (the solid content is 30%), sequentially add a regulator (CaO, adjust the pH of the pulp to 8), a first collector (amyl xanthate, the addition amount is 100 g / t), and a first foaming agent (terpineol, the addition amount is 30 g / t) to the pulp, and perform the first flotation (the stirring time is 2 min, and the flotation time is 3 min) to obtain a rough concentrate of copper-cobalt sulfide and a tailing of copper-cobalt sulfide rough selection;

[0068] Step S2, add a reducing agent (sodium carbonate, the weight ratio of the copper-cobalt sulfide rough concentrate to the reducing agent is 1:0.3) to the copper-cobalt sulfide rough concentrate, perform roasting (the temperature is 500 °C, and the time is 2 h) to obtain roasted slag and flue gas; add water to the flue gas to produce sulfuric acid, and return the sulfuric acid to atmospheric pressure leaching and oxygen pressure leaching;

[0069] Step S3: Add water and sulfuric acid to the calcined slag for atmospheric pressure leaching (acid-to-ore ratio is 280 kg / t, liquid-to-solid ratio is 4:1, stirring speed is 500 r / min, temperature is 80 °C, time is 120 min, pH of the leaching end liquor is 0.8). After solid-liquid separation, an atmospheric pressure leaching solution and an atmospheric pressure leaching residue are obtained;

[0070] Step S4: Add a sulfiding agent (NaHS, addition amount is 2000 g / t) to the copper-cobalt sulfide rougher tailings for sulfidation (time is 60 min), then successively add a second collector (potassium amyl xanthate, addition amount is 1500 g / t), a second frother (pine oil, addition amount is 30 g / t), and an inhibitor (sodium hexametaphosphate, addition amount is 80 g / t) for second flotation (stirring time is 2 min, flotation time is 3 min) to obtain copper-cobalt oxide rougher concentrate and copper-cobalt oxide rougher tailings;

[0071] Step S5: Conduct magnetic rougher separation (background magnetic field intensity is 1.3 T), magnetic cleaning (background magnetic field intensity is 1.0 T), and magnetic scavenging (background magnetic field intensity is 0.8 T) on the copper-cobalt oxide rougher tailings successively to obtain cobalt oxide magnetic separation concentrate and cobalt oxide magnetic separation tailings;

[0072] Step S6: Conduct third flotation on the atmospheric pressure leaching residue, including successively adding water (adjust the solid content of the pulp to 30%), supplementary regulator (CaO, adjust the pH of the pulp to 8), supplementary collector (amyl xanthate, addition amount is 50 g / t), and supplementary frother (pine oil, addition amount is 20 g / t) for third flotation (stirring time is 2 min, flotation time is 3 min) to obtain enriched copper-cobalt sulfide leaching residue; Mix the enriched copper-cobalt sulfide leaching residue, copper-cobalt oxide rougher concentrate, and cobalt oxide magnetic separation concentrate, add water and sulfuric acid for oxygen pressure leaching (acid-to-ore ratio is 200 kg / t, liquid-to-solid ratio is 8:1, stirring speed is 800 r / min, temperature is 200 °C, time is 1 h, oxygen partial pressure is 0.4 Mpa, pH of the leaching end liquor is 1.4). After solid-liquid separation, an oxygen pressure leaching solution and an oxygen pressure leaching residue are obtained.

[0073] Example 2

[0074] The process flow chart is shown in Figure 2 。

[0075] A method for the combined beneficiation and smelting of high-calcium-magnesium copper-cobalt ore; The composition of the high-calcium-magnesium copper-cobalt ore is the same as that in Example 1; The method includes the following steps:

[0076] Step S1: Grind the high-calcium-magnesium-copper-cobalt ore to obtain ground ore (the weight percentage of particles with a particle size ≤ 0.074 mm is 75%). Then add water to the ground ore to obtain pulp (solid content is 30%). Sequentially add a regulator (CaO, to adjust the pH of the pulp to 8), a first collector (amyl xanthate, addition amount is 100 g / t), and a first frother (pine oil, addition amount is 30 g / t) to the pulp, and perform the first flotation (stirring time is 2 min, flotation time is 3 min) to obtain a rough concentrate of copper-cobalt sulfide and a tailing of copper-cobalt sulfide rough selection;

[0077] Step S2: Add a reducing agent (sodium carbonate, 40 g, the weight ratio of the copper-cobalt sulfide rough concentrate to the reducing agent is 1:0.3) to the copper-cobalt sulfide rough concentrate, and perform roasting (temperature is 500 °C, time is 2 h) to obtain roasted slag and flue gas; Add water to the flue gas to produce acid to obtain sulfuric acid, and return the sulfuric acid to atmospheric pressure leaching and oxygen pressure leaching;

[0078] Step S3: Add water and sulfuric acid to the roasted slag, and perform atmospheric pressure leaching (acid-to-ore ratio is 280 kg / t, liquid-to-solid ratio is 4:1, stirring speed is 500 r / min, temperature is 80 °C, time is 120 min, the pH of the leaching end liquor is 0.8). After solid-liquid separation, obtain an atmospheric pressure leaching solution and an atmospheric pressure leaching residue;

[0079] Step S4: Add a sulfiding agent (NaHS, addition amount is 2000 g / t) to the copper-cobalt oxide rough selection tailing, perform sulfidation (time is 60 min), then sequentially add a second collector (potassium amyl xanthate, addition amount is 1500 g / t), a second frother (pine oil, addition amount is 30 g / t), and an inhibitor (sodium hexametaphosphate, addition amount is 80 g / t), and perform the second flotation (stirring time is 2 min, flotation time is 3 min) to obtain a rough concentrate of copper-cobalt oxide and a tailing of copper-cobalt oxide rough selection;

[0080] Step S5: Perform magnetic rough selection (background magnetic field intensity is 1.3 T), magnetic cleaning (background magnetic field intensity is 1.0 T), and magnetic scavenging (background magnetic field intensity is 0.8 T) on the copper-cobalt oxide rough selection tailing in sequence to obtain a magnetic separation concentrate of cobalt oxide and a magnetic separation tailing of cobalt oxide;

[0081] Step S6: Mix the atmospheric pressure leaching residue, the copper-cobalt oxide rough selection concentrate, and the cobalt oxide magnetic separation concentrate, add water and sulfuric acid, and perform oxygen pressure leaching (acid-to-ore ratio is 200 kg / t, liquid-to-solid ratio is 8:1, stirring speed is 800 r / min, temperature is 200 °C, time is 1 h, oxygen partial pressure is 0.4 Mpa, the pH of the leaching end liquor is 1.4). After solid-liquid separation, obtain an oxygen pressure leaching solution and an oxygen pressure leaching residue.

[0082] Example 3

[0083] The difference from Example 1 is that in step S1, the high-calcium-magnesium-copper-cobalt ore is ground to obtain ground ore (the weight ratio of particles with a particle size ≤ 0.074 mm is 65%), then water is added to the ground ore to obtain pulp (solid content is 40%), a regulator (Ca(OH)2, adjusting the pH of the pulp to 7), a first collector (ethyl xanthate, addition amount is 50 g / t), and a first frother (terpineol oil, addition amount is 20 g / t) are sequentially added to the pulp, and the first flotation is carried out (stirring time is 5 min, flotation time is 10 min) to obtain a rough concentrate of copper-cobalt sulfide and a tailing of rough selection of copper-cobalt sulfide.

[0084] Example 4

[0085] The difference from Example 1 is that in step S1, the high-calcium-magnesium-copper-cobalt ore is ground to obtain ground ore (the weight ratio of particles with a particle size ≤ 0.074 mm is 85%), then water is added to the ground ore to obtain pulp (solid content is 20%), a regulator (CaCO3, adjusting the pH of the pulp to 10), a first collector (butyl xanthate, addition amount is 300 g / t), and a first frother (No. 2 oil, addition amount is 50 g / t) are sequentially added to the pulp, and the first flotation is carried out (stirring time is 1 min, flotation time is 2 min) to obtain a rough concentrate of copper-cobalt sulfide and a tailing of rough selection of copper-cobalt sulfide.

[0086] Example 5

[0087] The difference from Example 1 is that in step S2, a reducing agent (sodium sulfate, the weight ratio of the rough concentrate of copper-cobalt sulfide to the reducing agent is 1:0.2) is added to the rough concentrate of copper-cobalt sulfide, and roasting is carried out (temperature is 400 °C, time is 4 h) to obtain roasted slag and flue gas; the flue gas is added with water to produce acid to obtain sulfuric acid, and the sulfuric acid is returned to atmospheric pressure leaching and oxygen pressure leaching.

[0088] Example 6

[0089] The difference from Example 1 is that in step S2, a reducing agent (sodium chloride, the weight ratio of the rough concentrate of copper-cobalt sulfide to the reducing agent is 1:0.5) is added to the rough concentrate of copper-cobalt sulfide, and roasting is carried out (temperature is 600 °C, time is 2 h) to obtain roasted slag and flue gas; the flue gas is added with water to produce acid to obtain sulfuric acid, and the sulfuric acid is returned to atmospheric pressure leaching and oxygen pressure leaching.

[0090] Example 7

[0091] The difference from Example 1 is that in step S3, water and sulfuric acid are added to the roasted slag for atmospheric pressure leaching (acid-ore ratio is 180 kg / t, liquid-solid ratio is 4:1, stirring speed is 300 r / min, temperature is 25 °C, time is 240 min, the pH of the leaching end liquor is 2.5), and after solid-liquid separation, an atmospheric pressure leaching solution and an atmospheric pressure leaching residue are obtained.

[0092] Example 8

[0093] The difference from Example 1 is that in step S3, water and sulfuric acid are added to the calcined slag for atmospheric leaching (acid-to-ore ratio is 280 kg / t, liquid-to-solid ratio is 4:1, stirring speed is 600 r / min, temperature is 90 °C, time is 60 min, pH of the leaching end liquor is 0.8). After solid-liquid separation, an atmospheric leaching solution and atmospheric leaching slag are obtained.

[0094] Example 9

[0095] The difference from Example 1 is that in step S4, a sulfiding agent (Na2S, addition amount is 1000 g / t) is added to the copper-cobalt sulfide rougher tailings for sulfidation (time is 80 min), and then a second collector (amyl xanthate, addition amount is 500 g / t), a second frother (pine oil, addition amount is 20 g / t), and an inhibitor (sodium hexametaphosphate, addition amount is 40 g / t) are added in sequence for second flotation (stirring time is 6 min, flotation time is 10 min), obtaining copper-cobalt oxide rougher concentrate and copper-cobalt oxide rougher tailings.

[0096] Example 10

[0097] The difference from Example 1 is that in step S4, a sulfiding agent (NaHS, addition amount is 3000 g / t) is added to the copper-cobalt sulfide rougher tailings for sulfidation (time is 30 min), and then a second collector (sodium amyl xanthate, addition amount is 2000 g / t), a second frother (No. 2 oil, addition amount is 50 g / t), and an inhibitor (carboxymethyl cellulose, addition amount is 200 g / t) are added in sequence for second flotation (stirring time is 2 min, flotation time is 2 min), obtaining copper-cobalt oxide rougher concentrate and copper-cobalt oxide rougher tailings.

[0098] Example 11

[0099] The difference from Example 1 is that in step S5, the copper-cobalt oxide rougher tailings are sequentially subjected to magnetic rougher separation (background magnetic field intensity is 1.2 T), magnetic cleaning separation (background magnetic field intensity is 0.9 T), and magnetic scavenging separation (background magnetic field intensity is 0.75 T) to obtain cobalt oxide magnetic separation concentrate and cobalt oxide magnetic separation tailings.

[0100] Example 12

[0101] The difference from Example 1 is that in step S5, the copper-cobalt oxide rougher tailings are sequentially subjected to magnetic rougher separation (background magnetic field intensity is 1.5 T), magnetic cleaning separation (background magnetic field intensity is 1.1 T), and magnetic scavenging separation (background magnetic field intensity is 0.85 T) to obtain cobalt oxide magnetic separation concentrate and cobalt oxide magnetic separation tailings.

[0102] Example 13

[0103] The difference from Example 1 is that in step S6, the atmospheric pressure leaching residue is subjected to third flotation, including successively adding water (adjusting the solid content of the pulp to 25%), adding supplementary regulators (Ca(OH)2, adjusting the pH of the pulp to 7), adding supplementary collectors (ethyl xanthate, addition amount is 40 g / t), and adding supplementary frothers (pine oil, addition amount is 10 g / t), and performing third flotation (stirring time is 5 min, flotation time is 10 min) to obtain an enriched copper-cobalt sulfide leaching residue; mixing the enriched copper-cobalt sulfide leaching residue, the rough concentrate of copper-cobalt oxide, and the magnetic concentrate of cobalt oxide, adding water and sulfuric acid, and performing oxygen pressure leaching (acid-to-ore ratio is 180 kg / t, liquid-to-solid ratio is 10:1, stirring speed is 600 r / min, temperature is 160 °C, time is 2 h, oxygen partial pressure is 0.8 Mpa, pH of the leaching end-point liquor is 2.0), and after solid-liquid separation, an oxygen pressure leaching solution and an oxygen pressure leaching residue are obtained.

[0104] Example 14

[0105] The difference from Example 1 is that in step S6, the atmospheric pressure leaching residue is subjected to third flotation, including successively adding water (adjusting the solid content of the pulp to 35%), adding supplementary regulators (CaCO3, adjusting the pH of the pulp to 9), adding supplementary collectors (butyl xanthate, addition amount is 60 g / t), and adding supplementary frothers (No. 2 oil, addition amount is 30 g / t), and performing third flotation (stirring time is 1 min, flotation time is 2 min) to obtain an enriched copper-cobalt sulfide leaching residue; mixing the enriched copper-cobalt sulfide leaching residue, the rough concentrate of copper-cobalt oxide, and the magnetic concentrate of cobalt oxide, adding water and sulfuric acid, and performing oxygen pressure leaching (acid-to-ore ratio is 220 kg / t, liquid-to-solid ratio is 6:1, stirring speed is 800 r / min, temperature is 220 °C, time is 0.8 h, oxygen partial pressure is 0.3 Mpa, pH of the leaching end-point liquor is 1.2), and after solid-liquid separation, an oxygen pressure leaching solution and an oxygen pressure leaching residue are obtained.

[0106] Example 15

[0107] The difference from Example 1 is that by weight percentage, in the high-calcium-magnesium copper-cobalt ore, the Cu content is 0.5 wt.%, the Co content is 0.1 wt.%, the MgO content is 15 wt.%, the CaO content is 9 wt.%, and the S content is 0.2 wt.%.

[0108] Example 16

[0109] The difference from Example 1 is that by weight percentage, in the high-calcium-magnesium copper-cobalt ore, the Cu content is 5 wt.%, the Co content is 1 wt.%, the MgO content is 8 wt.%, the CaO content is 16 wt.%, and the S content is 0.6 wt.%.

[0110] Comparative Example 1

[0111] The difference from Example 2 is that in step S6, the atmospheric pressure leaching residue, the rough concentrate of copper oxide cobalt ore, and the magnetic separation concentrate of cobalt oxide are mixed, water and sulfuric acid are added, and atmospheric pressure leaching is carried out (the acid-to-ore ratio is 800 kg / t, the liquid-to-solid ratio is 4:1, the stirring speed is 500 r / min, the temperature is 80 °C, and the time is 2 h). After solid-liquid separation, the leaching solution and the leaching residue are obtained.

[0112] Comparative Example 2

[0113] The difference from Example 1 is that the high-calcium magnesium copper cobalt ore is processed according to the method of Example 1 of Chinese Application CN 114950712 A.

[0114] Result test:

[0115] The metal contents in the above-mentioned examples and comparative examples were measured respectively, and the comprehensive recovery rates of cobalt and copper were calculated. The results are shown in Table 1.

[0116] Comprehensive recovery rate of cobalt: The cobalt contents in the high-calcium magnesium copper cobalt ore, the oxygen pressure leaching residue, and the magnetic separation tailings of cobalt oxide were measured by atomic absorption spectrometry (other chemical analysis methods such as inductively coupled plasma mass spectrometry, X-ray fluorescence spectrometry, etc. can also be used). The comprehensive recovery rate of cobalt = (cobalt content in the high-calcium magnesium copper cobalt ore - cobalt content in the oxygen pressure leaching residue - cobalt content in the magnetic separation tailings of cobalt oxide) ÷ cobalt content in the high-calcium magnesium copper cobalt ore.

[0117] Comprehensive recovery rate of copper: The copper contents in the high-calcium magnesium copper cobalt ore, the oxygen pressure leaching residue, and the magnetic separation tailings of cobalt oxide were measured by atomic absorption spectrometry (other chemical analysis methods such as inductively coupled plasma mass spectrometry, X-ray fluorescence spectrometry, etc. can also be used). The comprehensive recovery rate of copper = (copper content in the high-calcium magnesium copper cobalt ore - copper content in the oxygen pressure leaching residue - copper content in the magnetic separation tailings of cobalt oxide) ÷ copper content in the high-calcium magnesium copper cobalt ore.

[0118] Table 1

[0119]

[0120] As can be seen from the above, compared with the comparative examples, each embodiment of the present invention adopts the process of sulfur-first and oxygen-second flotation enrichment - combined atmospheric pressure and oxygen pressure leaching to efficiently leach copper and cobalt from the high-calcium magnesium copper cobalt ore. First, the rough sulfide copper cobalt concentrate, copper oxide cobalt concentrate, and magnetic separation cobalt concentrate are obtained through flotation and magnetic separation processes. Then, the sulfide copper cobalt concentrate is roasted and leached under atmospheric pressure to obtain a copper cobalt leaching solution and a leaching residue containing un-leached sulfide copper cobalt. Finally, the leaching residue, copper oxide cobalt concentrate, and magnetic separation cobalt concentrate are leached under oxygen pressure to obtain a copper cobalt leaching solution with a high metal recovery rate. The process of the present invention is simple, the cost is low, and the copper cobalt recovery rate is high.

[0121] In addition, it can be seen that when each process parameter is within the preferred range of the present invention, the comprehensive effect is better.

[0122] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for the combined beneficiation of high-calcium-magnesium-cobalt ore, characterized in that: The following steps are involved: Step S1, adding water to the high-calcium-magnesium copper-cobalt ore to obtain a pulp, adding a first collector to the pulp, and performing a first flotation to obtain a copper-cobalt sulfide rougher concentrate and a copper-cobalt sulfide rougher tailings; Step S2, adding a reducing agent to the copper-cobalt sulfide rougher concentrate, and roasting to obtain roasting slag and flue gas; Step S3, adding water and sulfuric acid to the roasted slag to carry out atmospheric pressure leaching, and obtaining atmospheric pressure leaching liquid and atmospheric pressure leaching slag after solid-liquid separation; Step S4, adding a sulfiding agent to the copper-cobalt sulfide rougher tailings for sulfidation, and then adding a second collector for second flotation to obtain a copper-cobalt oxide rougher concentrate and a copper-cobalt oxide rougher tailings; Step S5, magnetically separating the copper-cobalt oxide rougher tailings to obtain cobalt oxide magnetic separation concentrate and cobalt oxide magnetic separation tailings; Step S6, firstly subjecting the atmospheric pressure leaching residue to a third flotation to obtain enriched copper-cobalt sulfide leaching residue; then mixing the enriched copper-cobalt sulfide leaching residue, the copper-cobalt oxide rougher concentrate and the cobalt oxide magnetic concentrate, adding water and sulfuric acid, and subjecting to oxygen pressure leaching, and obtaining oxygen pressure leaching solution and oxygen pressure leaching residue after solid-liquid separation; The reducing agent includes one or more of sodium carbonate, sodium sulfate and sodium chloride, and the weight ratio of the copper-cobalt sulfide rougher concentrate to the reducing agent is 1:(0.2-0.5); The magnetic separation includes magnetic roughing, magnetic concentrating and magnetic scanning which are performed sequentially. The background magnetic field strength of the magnetic roughing is 1.2-1.5T, the background magnetic field strength of the magnetic concentrating is 0.9-1.1T, and the background magnetic field strength of the magnetic scanning is 0.75-0.85T.

2. The method for combined beneficiation of high calcium magnesium copper-cobalt ore according to claim 1, characterized in that: In the step S1, The solid content of the slurry is 20-40%; and / or The step S1 also includes the following steps: grinding the high calcium magnesium copper cobalt ore to obtain grinding material, and then adding water to the grinding material to obtain the slurry; in the grinding material, the weight proportion of particles with a particle size of ≤0.074 mm is 65-85%.

3. The method for combined beneficiation of high calcium magnesium copper-cobalt ore according to claim 1 or 2, characterized in that: In the step S1, The first collector comprises one or more of ethyl xanthate, butyl xanthate, amyl xanthate and ethionamide, and the addition amount is 50-300 g / t; and / or the stirring time of the first flotation is 1-5 min, and the flotation time is 2-10 min; and / or An adjusting agent, the first collecting agent and the first frother are sequentially added to the slurry to perform the first flotation; wherein the adjusting agent comprises one or more of CaO, Ca(OH)2 and CaCO3 to adjust the pH of the slurry to 7-10, and the first frother comprises pine oil and / or 2# oil, and the addition amount is 20-50 g / t.

4. The method for combined beneficiation of high calcium magnesium copper-cobalt ore according to claim 1 or 2, characterized in that: In the step S2, The calcination temperature is 400-600°C and the calcination time is 2-4 hours; and / or The step S2 further includes the following steps: adding water to the flue gas to produce sulfuric acid, and returning the sulfuric acid to the normal pressure leaching and / or the oxygen pressure leaching.

5. The method for combined beneficiation of high calcium magnesium copper-cobalt ore according to claim 1 or 2, characterized in that: In the step S3, The acid-ore ratio of the atmospheric pressure leaching is 180-280 kg / t, the liquid-solid ratio is (3-5):1, and the stirring speed is 300-600 r / min; and / or The temperature of the atmospheric pressure leaching is 25-90° C., the time is 60-240 min, and the pH of the leaching end point solution is 0.8-2.

5.

6. The method for combined beneficiation of high calcium magnesium copper-cobalt ore according to claim 1 or 2, characterized in that: In the step S4, The sulfiding agent includes Na2S and / or NaHS, and the addition amount is 1000-3000 g / t; and / or the second collector includes one or more of ethyl xanthate, butyl xanthate, amyl xanthate, potassium amyl xanthate and sodium amyl xanthate, and the addition amount is 500-2000 g / t; and / or the sulfiding time is 30-80 min; and / or the stirring time of the second flotation is 2-6 min, and the flotation time is 2-10 min; and / or The sulfiding agent is added to the copper-cobalt sulfide roughing tailings for sulfidation, and then the second collector, the second frother and the depressant are sequentially added for the second flotation; wherein the second frother comprises pine oil and / or 2# oil, and the addition amount is 20-50 g / t, and the depressant comprises sodium hexametaphosphate and / or carboxymethyl cellulose, and the addition amount is 40-200 g / t.

7. The method for combined beneficiation of high calcium magnesium copper-cobalt ore according to claim 1 or 2, characterized in that: In step S6, The acid-ore ratio of the oxygen pressure leaching is 180-220 kg / t, the liquid-solid ratio is (6-10):1, and the stirring speed is 600-800 r / min; and / or The temperature of the oxygen pressure leaching is 160-220° C., the time is 0.8-2 h, the oxygen partial pressure is 0.3-0.8 MPa, and the pH of the leaching end point solution is 1.2-2.

0.

8. The method for combined beneficiation of high calcium magnesium copper-cobalt ore according to claim 1 or 2, characterized in that: Calculated by weight percentage, the high-calcium magnesium copper-cobalt ore has a Cu content of 0.5-5wt.%, a Co content of 0.1-1wt.%, a MgO content of 8-15wt.%, a CaO content of 9-16wt.%, and a S content of 0.2-0.6wt.%.

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