Method for combined dressing and smelting of high-calcium-magnesium-copper-cobalt ore

Abstract

The invention provides a combined beneficiation and smelting method for high-calcium-magnesium-copper-cobalt ore. The method comprises the steps that first flotation is conducted on the high-calcium-magnesium-copper-cobalt ore, and copper-cobalt sulfide roughing concentrate and copper-cobalt sulfide roughing tailings are obtained; a reducing agent is added into the copper-cobalt sulfide roughing concentrate for roasting, and after roasting slag is obtained, normal-pressure leaching is conducted, and normal-pressure leaching liquid and normal-pressure leaching slag are obtained; a vulcanizing agent is added into the copper-cobalt sulfide roughing tailings for vulcanization, then a second collecting agent is added for second flotation, and copper-cobalt oxide roughing concentrate and copper-cobalt oxide roughing tailings are obtained; performing magnetic separation on the copper cobalt oxide roughing tailings to obtain cobalt oxide magnetic separation concentrate; and finally, the normal-pressure leaching residues, the copper cobalt oxide roughing concentrate and the cobalt oxide magnetic separation concentrate are mixed for oxygen pressure leaching, and oxygen pressure leaching liquid and oxygen pressure leaching residues are obtained. According to the method, efficient leaching of copper and cobalt in the high-calcium-magnesium-copper-cobalt ore is carried out by adopting a sulfur-oxygen flotation enrichment-normal-pressure oxygen-pressure combined leaching process, the process is simple, the cost is low, and the copper and cobalt recovery rate is high.

Description

Technical Field

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

[0002] High calcium magnesium copper-cobalt ore refers to an ore with an oxidation rate of 10-90%, and the CaO and MgO contents in the gangue minerals are close to or exceed 10%. It is characterized by a high oxidation rate of the ore and a large calcium and magnesium content, including sandstone-type ore. Sandstone-type high calcium magnesium copper-cobalt ore mainly contains the following components: chalcocite, bornite, covellite, etc. in the form of copper sulfide ore, malachite, chrysocolla, cuprite, etc. in the form of copper oxide ore, sulfide copper-cobalt ore, etc. in the form of cobalt sulfide ore, cobalt-containing dolomite, cobalt clinospermite, etc. in the form of cobalt oxide ore, and the gangue minerals are mainly siltstone, quartz and dolomite. The copper in high calcium magnesium copper-cobalt ore is mainly copper sulfide, and the cobalt is mainly 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 contents 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 a high calcium-magnesium sulfur-oxygen mixed copper-cobalt ore, which obtains sulfide concentrate and oxidized coarse concentrate through a step-by-step flotation process, and separates most of the calcium-magnesium gangue minerals at the same time. The obtained oxidized copper-cobalt coarse concentrate enters the next wet copper smelting process, which can reduce the amount of ore to be processed and the acid consumption of wet leaching, thereby achieving the purpose of saving resources and reducing costs. However, it only processes the oxidized copper-cobalt coarse concentrate obtained by flotation, and the comprehensive recovery rate of copper is only 85.12%, and the comprehensive recovery rate of cobalt is only 73.93%, which is a low recovery rate of copper and cobalt. Chinese application CN 114950712 A discloses a combined treatment process for comprehensive recovery of copper and cobalt, wherein cobalt-copper ore and single cobalt ore are subjected to flotation and magnetic separation to produce sulfide copper concentrate, oxidized copper concentrate, flotation cobalt concentrate, and magnetic separation cobalt concentrate respectively, and the sulfide copper concentrate enters wet leaching after roasting, and the oxidized copper concentrate, flotation cobalt concentrate, and magnetic separation cobalt concentrate directly enter wet leaching. However, the wet leaching slag of the copper sulfide concentrate is not further recovered, and the wet leaching adopts normal pressure leaching. Due to the presence of sulfur, the leaching rates of Cu and Co are still low.

[0004] At present, there are three main process routes for processing high-calcium-magnesium copper-cobalt ores, namely pyrometallurgy, acid leaching, and flotation. The pyrometallurgical treatment process is mainly matte smelting-copper matte blowing process, which has problems such as large investment, high smelting cost, high environmental pressure, and high copper content in slag. When using acid leaching to treat high-calcium-magnesium copper-cobalt ores, there are disadvantages of high acid consumption and high production cost. At the same time, it will also cause a large amount of difficult-to-leach copper-cobalt sulfide ores in the ore to be discarded in the tailings, which is not conducive to the comprehensive recovery of copper and cobalt. The flotation method mainly has the mineral processing process of "copper-cobalt mixed flotation", but there are problems such as low recovery rate of oxidized copper-cobalt ore and high calcium and magnesium content in the concentrate. High calcium and magnesium concentrate will reduce the quality of the concentrate and increase the difficulty of subsequent smelting. Summary of the invention

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

[0006] In order to achieve the above-mentioned object, according to one aspect of the present invention, a method for combined beneficiation of high-calcium-magnesium copper-cobalt ore is provided, comprising the following steps: step S1, adding water to the high-calcium-magnesium copper-cobalt ore to obtain slurry, adding a first collector to the slurry, performing a first flotation, and obtaining 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, performing roasting, and obtaining roasting slag and flue gas; step S3, adding water and sulfuric acid to the roasting slag, performing normal pressure leaching, and obtaining after solid-liquid separation. Atmospheric pressure leaching liquid and atmospheric pressure leaching residue; step S4, adding a sulfiding agent to the copper-cobalt sulfide roughing tailings for sulfidation, and then adding a second collector for second flotation to obtain copper-cobalt oxide roughing concentrate and copper-cobalt oxide roughing tailings; step S5, magnetically separating the copper-cobalt oxide roughing tailings to obtain cobalt oxide magnetic separation concentrate and cobalt oxide magnetic separation tailings; step S6, mixing the atmospheric pressure leaching residue, the copper-cobalt oxide roughing concentrate and the cobalt oxide magnetic separation concentrate, adding water and sulfuric acid, performing oxygen pressure leaching, and obtaining oxygen pressure leaching liquid and oxygen pressure leaching residue after solid-liquid separation.

[0007] Furthermore, in step S1, the solid content of the slurry is 20-40%; preferably, step S1 also includes the following steps: grinding the high-calcium magnesium copper-cobalt ore to obtain a grinding material, and then adding water to the grinding material to obtain a slurry; in the grinding material, the weight proportion of particles ≤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 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; preferably, the 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 includes CaO, Ca(OH) 2 and CaCO 3 One or more of the above are used to adjust the pH of the slurry to 7-10. The first foaming agent includes pine oil and / or 2# oil, and the addition amount is 20-50g / t.

[0009] Furthermore, 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 roughing concentrate to the reducing agent is 1:(0.2-0.5); and / or the roasting temperature is 400-600°C and the time is 2-4h; preferably, step S2 also 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-ore ratio of 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 atmospheric pressure leaching is 25-90°C, the time is 60-240 min, and the pH of the leaching end point liquid is 0.8-2.5.

[0011] Further, in step S4, the sulfiding agent includes Na 2 S and / or NaHS, the addition amount is 1000-3000g / t; and / or the second collector includes one or more of ethyl xanthate, butyl xanthate, amyl xanthate, potassium amyl xanthate and sodium amyl xanthate, the addition amount is 500-2000g / t; and / or the sulfidation time is 30-80 min; and / or the stirring time of the second flotation is 2-6min, and the flotation time is 2-10min; preferably, the sulfiding agent is added to the sulfide copper-cobalt roughing tailings for sulfidation, and then the second collector, the second frother and the inhibitor are added in sequence for the second flotation; wherein the second frother includes pine oil and / or 2# oil, the addition amount is 20-50g / t, and the inhibitor includes sodium hexametaphosphate and / or carboxymethyl cellulose, the addition amount is 40-200g / t.

[0012] Furthermore, in step S5, the background magnetic field strength of the magnetic separation is 0.3-2.0 T; preferably, the magnetic separation includes magnetic roughing separation, magnetic concentrating separation and magnetic scanning separation performed in sequence.

[0013] Further, in step S6, the acid-ore ratio of 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 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 liquid is 1.2-2.0.

[0014] Furthermore, in step S6, the atmospheric pressure leaching residue is first subjected to a third flotation to obtain enriched copper-cobalt sulfide leaching residue; then the enriched copper-cobalt sulfide leaching residue, the copper-cobalt oxide rougher concentrate and the cobalt oxide magnetic concentrate are mixed, water and sulfuric acid are added, and oxygen pressure leaching is performed.

[0015] Furthermore, in terms of 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.%.

[0016] The technical scheme of the present invention is applied, and a process of flotation enrichment followed by oxygen and then oxygen-pressure combined leaching is adopted to efficiently leach copper and cobalt from high-calcium-magnesium copper-cobalt ore. First, roughly selected copper-cobalt sulfide concentrate, copper-cobalt oxide concentrate, and magnetically separated cobalt concentrate are obtained through flotation and magnetic separation processes, and then the copper-cobalt sulfide concentrate is roasted and leached at normal pressure to obtain a copper-cobalt leaching solution and a leaching residue containing unleached copper-cobalt sulfide, and finally the leaching residue, copper-cobalt oxide concentrate, and magnetically separated cobalt concentrate are subjected to oxygen pressure leaching 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. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0018] Figure 1 The process flow chart of the combined beneficiation of high-calcium-magnesium-cobalt ore according to Example 1 of the present invention is shown;

[0019] Figure 2 A process flow chart of the combined beneficiation of high-calcium-magnesium-cobalt ore according to Example 2 of the present invention is shown. DETAILED DESCRIPTION

[0020] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0021] Terminology explanation:

[0022] The amount of reagent added is 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 acid used in the leaching process (in kg) to the weight of the material to be leached (in t).

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

[0025] As described in the background technology of the present invention, the prior art has the problems of high process cost and low copper and cobalt recovery rate when processing high calcium magnesium copper-cobalt ore. In order to solve the above problems, in a typical embodiment of the present invention, a method for combined beneficiation of high calcium magnesium copper-cobalt ore is provided, comprising the following steps: step S1, adding water to the high calcium magnesium copper-cobalt ore to obtain slurry, adding a first collector to the slurry, performing a first flotation, and obtaining a copper-cobalt sulfide roughing concentrate and a copper-cobalt sulfide roughing tailings; step S2, adding a reducing agent to the copper-cobalt sulfide roughing concentrate, roasting, and obtaining roasting slag and flue gas; step S3, adding water and sulfuric acid to the roasting slag, performing normal pressure leaching, and after solid-liquid separation, The method comprises the following steps: obtaining a normal pressure leaching solution and a normal pressure leaching residue; step S4, adding a sulfiding agent to the copper-cobalt sulfide roughing tailings for sulfidation, and then adding a second collector for second flotation to obtain a copper-cobalt oxide roughing concentrate and a copper-cobalt oxide roughing tailings; step S5, magnetically separating the copper-cobalt oxide roughing tailings to obtain a cobalt oxide magnetic separation concentrate and a cobalt oxide magnetic separation tailings; and step S6, mixing the normal pressure leaching residue, the copper-cobalt oxide roughing concentrate and the cobalt oxide magnetic separation concentrate, adding water and sulfuric acid, performing oxygen pressure leaching, and obtaining an oxygen pressure leaching solution and an oxygen pressure leaching residue after solid-liquid separation.

[0026] The prior art usually adopts a combined beneficiation process of multiple flotation when processing high-calcium magnesium copper-cobalt ores. Multiple flotation processes will cause a large loss of metal elements and reduce the metal recovery rate. The present invention is aimed at high-calcium magnesium copper-cobalt ores, adopts a process of first sulfur and then oxygen flotation enrichment-normal pressure oxygen pressure combined leaching, and performs efficient leaching of copper and cobalt. Only the roughing of sulfide copper-cobalt concentrate, oxide copper-cobalt concentrate, and cobalt concentrate is performed, the beneficiation process is simple, and the metal loss is less.

[0027] Specifically, water is first added to the high-calcium-magnesium copper-cobalt ore to prepare a slurry, and then a first collector is added to perform a first flotation. The collector can chemically adsorb to the surface of copper sulfide and cobalt sulfide minerals to make them hydrophobic, thereby adsorbing the copper-cobalt sulfide ore on the bubbles for rough selection and floating to obtain a copper-cobalt sulfide roughing concentrate and a copper-cobalt sulfide roughing tailings, which are then treated separately.

[0028] Subsequently, a reducing agent is added to the copper-cobalt sulfide rougher concentrate for sulfidation roasting. During this process, the reducing agent converts the metal sulfides in the copper-cobalt sulfide rougher concentrate into soluble salts, which are more easily dissolved in the acidic leaching solution, thereby improving the leaching efficiency of the metal, and reducing the generated sulfur dioxide to sulfates (such as copper sulfate and cobalt sulfate), thereby reducing the escape of sulfur dioxide and playing a role in sulfur fixation. Water and sulfuric acid are added to the obtained roasting slag for atmospheric pressure leaching. Based on the principle of acidic leaching, the soluble copper and cobalt obtained in the roasting slag are dissolved into the solution through chemical reaction, and the copper and cobalt in the copper-cobalt sulfide rougher concentrate are preliminarily recovered. After solid-liquid separation, atmospheric pressure leaching solution and atmospheric pressure leaching slag are obtained. Since the amount of atmospheric pressure leaching slag is small, 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 copper-cobalt sulfide rougher concentrate, it cannot be recovered in the atmospheric pressure leaching process, and directly sending it to the tailings pond will cause copper and cobalt losses. Therefore, the present invention further performs oxygen pressure leaching treatment on it to perform secondary recovery and improve the copper and cobalt recovery rate.

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

[0030] The rough copper-cobalt oxide tailings still contain a small amount of cobalt, but they are wrapped by limonite, making direct leaching difficult. Therefore, the rough copper-cobalt oxide tailings are subjected to magnetic separation. Based on the magnetic difference between limonite and cobalt, the 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 cobalt oxide magnetic separation concentrate and cobalt oxide magnetic separation tailings. Finally, the obtained cobalt oxide magnetic separation concentrate is also subjected to oxygen pressure leaching to achieve a higher comprehensive recovery rate of copper and cobalt.

[0031] Compared with normal pressure leaching, the invention mixes normal pressure leaching residue, copper-cobalt oxide rougher concentrate and cobalt oxide magnetic concentrate, adds them into an autoclave together with water and sulfuric acid, and introduces oxygen for oxygen pressure leaching. In this process, oxygen can be used as a strong oxidant to replace sulfuric acid, thereby reducing the amount of sulfuric acid used; high pressure can increase the solubility of oxygen, directly oxidize metal sulfides to generate sulfates, and further reduce sulfuric acid consumption; oxygen pressure conditions can more effectively dissolve metals and reduce metal residues in the leaching residue, thereby significantly increasing the leaching rate of copper and cobalt while reducing sulfuric acid consumption, and greatly reducing the loss of metals in high-calcium-magnesium copper-cobalt ores.

[0032] In summary, the present invention adopts a process of first sulfur and then oxygen flotation enrichment-normal pressure oxygen pressure combined leaching to efficiently leach copper and cobalt in high calcium magnesium copper-cobalt ore. First, rough copper-cobalt sulfide concentrate, copper-cobalt oxide concentrate, and magnetic cobalt concentrate are obtained by flotation and magnetic separation processes, and then the copper-cobalt sulfide concentrate is roasted and leached at normal pressure to obtain a copper-cobalt leaching solution and a leaching residue containing unleached copper-cobalt sulfide. Finally, the leaching residue, copper-cobalt oxide concentrate, and magnetic 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, the cost is low, the copper-cobalt recovery rate is high, 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 slurry is 20-40%; while reducing the amount of liquid processed in the subsequent leaching process, thereby reducing energy consumption and wastewater treatment costs, the fluidity and stability of the slurry can be improved, which is beneficial to the uniform distribution and capture effect of the flotation reagent, and further improves the recovery efficiency of copper and cobalt. Preferably, step S1 also includes the following steps: grinding the high-calcium magnesium copper-cobalt ore to obtain a grinding ore, and then adding water to the grinding ore to obtain a slurry; in the grinding ore, the weight proportion of particles ≤0.074 mm is 65-85%.

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

[0035] In order to significantly improve the recovery efficiency of copper and cobalt in the raw material high-calcium magnesium copper-cobalt ore while reducing the cost of reagent use 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 ethiocarbamate (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, the adjusting agent, the first collecting agent and the first frother are added to the ore pulp in sequence to perform the first flotation; wherein the adjusting agent includes CaO, Ca(OH) 2 and CaCO 3 One or more of the above are used to adjust the pH of the slurry to 7-10. The first foaming agent includes pine oil and / or 2# oil, and the addition amount is 20-50g / t.

[0036] In the first collector of the above type, its specific chemical structure can form a stable hydrophobic film with the surface of copper-cobalt sulfide minerals, significantly enhancing the hydrophobicity of the minerals, thereby more effectively separating copper-cobalt minerals from gangue during flotation. 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 low energy consumption, and the flotation time within the above range can further improve the recovery rate while maintaining high processing efficiency. By optimizing the stirring time and flotation time, it is more conducive to effectively reducing energy consumption while allowing the minerals to fully contact and selectively separate.

[0037] The above-mentioned adjusting agent 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-mentioned frother 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 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 hours. 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, which can not only improve the solubility of the metal, but also have a sulfur-fixing effect, which can reduce the emission of sulfur dioxide during the roasting process, and is beneficial to environmental protection and subsequent acid recycling.

[0039] Limiting the weight ratio of the copper-cobalt sulfide rougher concentrate to the reducing agent within the above range is more conducive to promoting the full contact and reaction between the reducing agent and the metal sulfide, reducing the incomplete conversion caused by insufficient reducing agent, or the additional cost and possible increase in slag caused 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 proper decomposition of sulfides, increasing the leaching rate of metals, and 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 comprises 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. The sulfur dioxide generated during the roasting of the copper-cobalt sulfide rougher concentrate is further recycled to produce acid, and then recycled to the atmospheric pressure leaching and oxygen pressure leaching processes, which can further reduce environmental pollution, save resources and production costs.

[0041] The present invention also significantly improves the economic and environmental performance of the raw material high-calcium magnesium copper-cobalt ore treatment by optimizing the leaching parameters, while improving the metal recovery rate. In a preferred embodiment, in step S3, the acid-ore ratio of 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 atmospheric pressure leaching is 25-90°C, the time is 60-240 min, and the pH of the leaching end point liquid is 0.8-2.5.

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

[0043] The leaching temperature and time are set within the above range, which is more conducive to promoting the full dissolution of copper and cobalt minerals, improving the metal recovery rate, reducing energy waste and equipment loss caused by high temperature, and taking into account the balance between reaction rate and energy consumption. Within the above pH range of the leaching end point solution, 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 sulfiding agent includes Na 2S and / or NaHS, added in an amount of 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, added in an amount of 500-2000 g / t; and / or the sulfidation 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 sulfide copper-cobalt roughing tailings for sulfidation, and then a second collector, a second frother and an inhibitor are added in sequence for second flotation; wherein the second frother includes pine oil and / or 2# oil, added in an amount of 20-50 g / t, and the inhibitor includes sodium hexametaphosphate and / or carboxymethyl cellulose, added in an amount of 40-200 g / t.

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

[0046] The addition of the second frother can promote the formation of bubbles, increase the chance of minerals and bubbles attaching, and improve the flotation efficiency. The use of the inhibitor is conducive to controlling the flotation of harmful gangue and reducing the loss of copper and cobalt during the flotation process, thereby further improving the recovery rate of copper and cobalt.

[0047] In order to more fully and specifically recover the trace cobalt enclosed in limonite in the copper-cobalt oxide roughing tailings, effectively remove non-magnetic gangue, improve the cobalt recovery rate and reduce the subsequent processing cost, in a preferred embodiment, in step S5, the background magnetic field intensity of the magnetic separation is 0.3~2.0T; preferably, the magnetic separation includes magnetic roughing, magnetic concentration and magnetic scanning separation performed in sequence, and the 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 of subsequent processing.

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

[0049] In a preferred embodiment, in step S6, the acid-ore ratio of 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 oxygen pressure leaching is 160-220°C, the time is 0.8-2h, the oxygen partial pressure is 0.3-0.8Mpa, and the pH of the leaching end point liquid is 1.2-2.0. Accurate control of the acid-ore ratio and the liquid-solid ratio can promote full contact between the acid solution and the ore, accelerate the dissolution of copper and cobalt metals, and reduce excessive acid consumption, reduce costs and reduce environmental pollution.

[0050] The temperature, time and oxygen partial pressure of oxygen pressure leaching are within the above ranges, which 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 difficult-to-leach metal sulfides and oxides, and promotes the dissolution of metal ions, especially the leaching effect of residual copper cobalt sulfide and copper cobalt oxide ores in the previous treatment. Controlling the pH of the leaching end point liquid to an acidic environment is conducive to the stable existence of copper and cobalt metal ions, improving the leaching rate of the metal and the subsequent separation and purification efficiency. The above oxygen pressure leaching conditions can improve the solubility and leaching rate of metals in complex high-calcium magnesium copper-cobalt ores on the one hand, and on the other hand, it is conducive to reducing unnecessary side reactions and waste of resources, while improving the recovery rate of copper and cobalt, and can take into account both cost and environmental protection.

[0051] Flotation of atmospheric leaching residue can further reduce the amount of residue that needs oxygen pressure leaching. In a preferred embodiment, in step S6, the atmospheric leaching residue is first subjected to a third flotation to obtain enriched copper-cobalt sulfide leaching residue; then the enriched copper-cobalt sulfide leaching residue, copper-cobalt oxide roughing concentrate and cobalt oxide magnetic separation concentrate are mixed, water and sulfuric acid are added, and oxygen pressure leaching is performed. The enrichment treatment of atmospheric leaching residue by the third flotation can effectively remove non-metallic minerals and low-value components therein, reduce the amount of invalid ore during oxygen pressure leaching, save the use of acid and oxygen, and reduce costs. In the mixed oxygen pressure leaching process of the enriched copper-cobalt sulfide leaching residue, copper-cobalt oxide roughing concentrate and cobalt oxide magnetic separation concentrate, the synergistic effect of copper-cobalt minerals in different forms can be utilized to improve the leaching efficiency and recovery rate of the metal, especially for the residual copper-cobalt sulfide minerals, oxygen pressure leaching under high temperature, high pressure and strong oxidizing environment can achieve more thorough metal dissolution, significantly improving the recovery efficiency of copper-cobalt sulfide.

[0052] More preferably, the third flotation comprises: first adding water to adjust the solid content of the slurry to 25-35%, then adding a supplementary adjusting agent to adjust the pH of the slurry to 7-9, and then sequentially adding a supplementary collector and a supplementary frother to perform the third flotation. Further preferably, the supplementary adjusting agent comprises CaO, Ca(OH) 2 and CaCO 3 one or more of the following: the supplementary collector includes one or more of ethyl xanthate, butyl xanthate, amyl xanthate and ethionamide, and the addition amount is 40-60 g / t; the supplementary frother includes pine oil and / or 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 of the flotation process, reducing metal losses, and improving the purity of the concentrate. 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 costs can be reduced.

[0054] In a preferred embodiment, in terms of weight percentage, in the high calcium magnesium copper-cobalt ore, the Cu content is 0.5-5wt.%, the Co content is 0.1-1wt.%, the MgO content is 8-15wt.%, the CaO content is 9-16wt.%, and the S content is 0.2-0.6wt.%. Ore within this composition range, due to the high proportion 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 is generally mainly sulfide, 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 and then oxygen" flotation and "normal pressure-oxygen pressure" combined leaching of the present invention. For ores with high CaO and MgO contents, the present invention effectively removes these acid-consuming gangues through processes such as flotation and leaching, thereby reducing the consumption of collectors and the acid consumption in the subsequent acid leaching process, saving costs, and achieving comprehensive recovery of copper and cobalt resources, with a higher comprehensive metal recovery rate.

[0055] Typically but not limitatively, in step S1, the amount of the first collector added is 50 g / t, 100 g / t, 150 g / t, 200 g / t, 250 g / t, 300 g / t or a range consisting of any two of them.

[0056] Typically but not limiting, 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 consisting of any two of them.

[0057] Typically but not limiting, in step S2, the calcination temperature is 400°C, 450°C, 500°C, 550°C, 600°C or a range consisting of any two of them, and the calcination time is 2h, 2.5h, 3h, 3.5h, 4h or a range consisting of any two of them.

[0058] Typically but not limiting, in step S4, the amount of the vulcanizing agent added is 1000 g / t, 1500 g / t, 2000 g / t, 2500 g / t, 3000 g / t or a range consisting of any two of them.

[0059] Typically but not limiting, in step S4, the amount of the second collector added is 500 g / t, 1000 g / t, 1500 g / t, 2000 g / t or a range consisting of any two of them.

[0060] Typically but not limiting, in step S4, the vulcanization time is 30 min, 40 min, 50 min, 60 min, 70 min, 80 min or a range consisting of any two of them.

[0061] Typically but not limiting, in step S5, the background magnetic field strength of the magnetic separation is 0.3 T, 0.5 T, 1.0 T, 1.5 T, 2.0 T or a range consisting of any two of them.

[0062] Typically but not limitatively, in step S6, the temperature of the oxygen pressure leaching is 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C or a range consisting of any two of them, the time is 0.8 h, 1.0 h, 1.2 h, 1.5 h, 1.8 h, 2 h or a range consisting of any two of them, 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 consisting of any two of them.

[0063] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0064] Example 1

[0065] See the process flow chart Figure 1 .

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

[0067] Step S1, grinding the high calcium magnesium copper-cobalt ore to obtain a grinding ore material (the weight proportion of the particle size ≤ 0.074 mm is 75%), then adding water to the grinding ore material to obtain a pulp (solid content is 30%), and sequentially adding a regulator (CaO, adjusting the pH of the pulp to 8), a first collector (amyl xanthate, added in an amount of 100 g / t) and a first frother (pine oil, added in an amount of 30 g / t) to the pulp, performing a first flotation (stirring time is 2 min, flotation time is 3 min), and obtaining a copper-cobalt sulfide roughing concentrate and a copper-cobalt sulfide roughing tailings;

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

[0069] Step S3, adding water and sulfuric acid to the roasted slag, performing atmospheric pressure leaching (acid-ore ratio of 280 kg / t, liquid-solid ratio of 4:1, stirring speed of 500 r / min, temperature of 80° C., time of 120 min, pH of the leaching end point liquid of 0.8), and obtaining atmospheric pressure leaching solution and atmospheric pressure leaching slag after solid-liquid separation;

[0070] Step S4, adding a sulfiding agent (NaHS, added in an amount of 2000 g / t) to the copper-cobalt sulfide rougher tailings, performing sulfidation (time of 60 min), then sequentially adding a second collector (amyl potassium xanthate, added in an amount of 1500 g / t), a second frother (pine oil, added in an amount of 30 g / t) and an inhibitor (sodium hexametaphosphate, added in an amount of 80 g / t), performing a second flotation (stirring time of 2 min, flotation time of 3 min), and obtaining a copper-cobalt oxide rougher concentrate and a copper-cobalt oxide rougher tailings;

[0071] Step S5, subjecting the copper-cobalt oxide roughing tailings to magnetic roughing (background magnetic field strength of 1.3 T), magnetic concentration (background magnetic field strength of 1.0 T) and magnetic sweeping (background magnetic field strength of 0.8 T) in sequence to obtain cobalt oxide magnetic separation concentrate and cobalt oxide magnetic separation tailings;

[0072] Step S6, subjecting the atmospheric pressure leaching residue to a third flotation, including sequentially adding water (adjusting the solid content of the slurry to 30%), supplementing the adjusting agent (CaO, adjusting the pH of the slurry to 8), supplementing the collecting agent (amyl xanthate, added in an amount of 50 g / t) and supplementing the frother (pine oil, added in an amount of 20 g / t), and subjecting the third flotation (stirring time of 2 min, flotation time of 3 min), to obtain enriched copper cobalt sulfide leaching residue; and mixing the enriched copper cobalt sulfide leaching residue, the copper cobalt oxide rougher concentrate and the cobalt oxide magnetic separation concentrate, adding water and sulfuric acid, and subjecting the mixture to oxygen pressure leaching (acid-ore ratio of 200 kg / t, liquid-solid ratio of 8:1, stirring speed of 800 r / min, temperature of 200°C, time of 1 h, oxygen partial pressure of 0.4 MPa, pH of the leaching end point liquid of 1.4), and obtaining oxygen pressure leaching solution and oxygen pressure leaching residue after solid-liquid separation.

[0073] Example 2

[0074] See the process flow chart Figure 2 .

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

[0076] Step S1, grinding the high calcium magnesium copper-cobalt ore to obtain a grinding ore material (the weight proportion of the particle size ≤ 0.074 mm is 75%), then adding water to the grinding ore material to obtain a pulp (solid content is 30%), and sequentially adding a regulator (CaO, adjusting the pH of the pulp to 8), a first collector (amyl xanthate, added in an amount of 100 g / t) and a first frother (pine oil, added in an amount of 30 g / t) to the pulp, performing a first flotation (stirring time is 2 min, flotation time is 3 min), and obtaining a copper-cobalt sulfide roughing concentrate and a copper-cobalt sulfide roughing tailings;

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

[0078] Step S3, adding water and sulfuric acid to the roasted slag, performing atmospheric pressure leaching (acid-ore ratio of 280 kg / t, liquid-solid ratio of 4:1, stirring speed of 500 r / min, temperature of 80° C., time of 120 min, pH of the leaching end point liquid of 0.8), and obtaining atmospheric pressure leaching solution and atmospheric pressure leaching slag after solid-liquid separation;

[0079] Step S4, adding a sulfiding agent (NaHS, added in an amount of 2000 g / t) to the copper-cobalt sulfide rougher tailings, performing sulfidation (time of 60 min), then sequentially adding a second collector (amyl potassium xanthate, added in an amount of 1500 g / t), a second frother (pine oil, added in an amount of 30 g / t) and an inhibitor (sodium hexametaphosphate, added in an amount of 80 g / t), performing a second flotation (stirring time of 2 min, flotation time of 3 min), and obtaining a copper-cobalt oxide rougher concentrate and a copper-cobalt oxide rougher tailings;

[0080] Step S5, subjecting the copper-cobalt oxide roughing tailings to magnetic roughing (background magnetic field strength of 1.3 T), magnetic concentration (background magnetic field strength of 1.0 T) and magnetic sweeping (background magnetic field strength of 0.8 T) in sequence to obtain cobalt oxide magnetic separation concentrate and cobalt oxide magnetic separation tailings;

[0081] Step S6, mixing the atmospheric pressure leaching residue, the copper and cobalt oxide rougher concentrate and the cobalt oxide magnetic separation concentrate, adding water and sulfuric acid, and performing oxygen pressure leaching (acid-ore ratio of 200 kg / t, liquid-solid ratio of 8:1, stirring speed of 800 r / min, temperature of 200°C, time of 1 h, oxygen partial pressure of 0.4 MPa, pH of the leaching end point liquid of 1.4), and obtaining oxygen pressure leaching solution and oxygen pressure leaching residue after solid-liquid separation.

[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 a grinding material (the weight proportion of the particle size ≤ 0.074 mm is 65%), and then water is added to the grinding material to obtain a slurry (solid content is 40%), and a regulator (Ca(OH) 2 , adjusting the pH value of the slurry to 7), the first collector (ethyl xanthate, added in an amount of 50 g / t) and the first frother (pine oil, added in an amount of 20 g / t), and performing the first flotation (stirring time of 5 min, flotation time of 10 min) to obtain copper-cobalt sulfide roughing concentrate and copper-cobalt sulfide roughing tailings.

[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 a grinding material (the weight proportion of the particle size ≤ 0.074 mm is 85%), and then water is added to the grinding material to obtain a slurry (solid content is 20%), and the adjusting agent (CaCO 3 , adjusting the pH value of the slurry to 10), the first collector (butyl xanthate, added in an amount of 300 g / t) and the first frother (2# oil, added in an amount of 50 g / t), and performing the first flotation (stirring time of 1 min, flotation time of 2 min) to obtain copper-cobalt sulfide roughing concentrate and copper-cobalt sulfide roughing tailings.

[0086] Example 5

[0087] The difference from Example 1 is that in step S2, a reducing agent (sodium sulfate, a weight ratio of the copper-cobalt sulfide rougher concentrate to the reducing agent is 1: 0.2) is added to the copper-cobalt sulfide rougher concentrate, and roasting is carried out (temperature is 400° C., time is 4 hours) to obtain roasting slag and flue gas; water is added to the flue gas to produce acid to obtain sulfuric acid, and the sulfuric acid is returned to normal 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, a weight ratio of the copper-cobalt sulfide rougher concentrate to the reducing agent is 1: 0.5) is added to the copper-cobalt sulfide rougher concentrate, and roasting is carried out (temperature is 600° C., time is 2 h) to obtain roasting slag and flue gas; water is added to the flue gas to produce acid to obtain sulfuric acid, and the sulfuric acid is returned to normal 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 to carry out 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, pH value of leaching end point liquid is 2.5), and atmospheric pressure leaching solution and atmospheric pressure leaching slag are obtained after solid-liquid separation.

[0092] Example 8

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

[0094] Example 9

[0095] The difference from Example 1 is that in step S4, a sulfiding agent (Na 2 S, added in an amount of 1000g / t), sulfidation (time of 80min), and then the second collector (amyl xanthate, added in an amount of 500g / t), the second frother (pine oil, added in an amount of 20g / t) and the inhibitor (sodium hexametaphosphate, added in an amount of 40g / t) were added in sequence, and the second flotation (stirring time of 6min, flotation time of 10min) was carried out to obtain 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, added in an amount of 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, added in an amount of 2000 g / t), a second frother (2# oil, added in an amount of 50 g / t) and an inhibitor (carboxymethyl cellulose, added in an amount of 200 g / t) are added in sequence, and a second flotation is performed (stirring time is 2 min, flotation time is 2 min), to obtain a copper-cobalt oxide rougher concentrate and a copper-cobalt oxide rougher tailings.

[0098] Embodiment 11

[0099] The difference from Example 1 is that in step S5, the copper-cobalt oxide roughing tailings are sequentially subjected to magnetic roughing (background magnetic field strength is 1.2 T), magnetic concentration (background magnetic field strength is 0.9 T) and magnetic scanning (background magnetic field strength 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 roughing tailings are sequentially subjected to magnetic roughing (background magnetic field strength is 1.5 T), magnetic concentration (background magnetic field strength is 1.1 T) and magnetic scanning (background magnetic field strength 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 leaching residue is subjected to a third flotation, including sequentially adding water (adjusting the solid content of the pulp to 25%) and a supplementary adjusting agent (Ca(OH) 2 , adjusting the pH value of the slurry to 7), supplementing the collector (ethyl xanthate, the addition amount is 40g / t) and the supplementing frother (pine oil, the addition amount is 10g / t), and performing the third flotation (stirring time is 5min, flotation time is 10min) to obtain enriched copper cobalt sulfide leaching residue; the enriched copper cobalt sulfide leaching residue, the copper cobalt oxide rougher concentrate and the cobalt oxide magnetic separation concentrate are mixed, and water and sulfuric acid are added to perform oxygen pressure leaching (acid-ore ratio is 180kg / t, liquid-solid ratio is 10:1, stirring speed is 600r / min, temperature is 160℃, time is 2h, oxygen partial pressure is 0.8Mpa, pH value of the leaching end point liquid is 2.0), and oxygen pressure leaching solution and oxygen pressure leaching residue are obtained after solid-liquid separation.

[0104] Embodiment 14

[0105] The difference from Example 1 is that in step S6, the atmospheric leaching residue is subjected to a third flotation, including sequentially adding water (adjusting the solid content of the slurry to 35%) and a supplementary adjusting agent (CaCO 3 , adjusting the pH value of the slurry to 9), supplementing the collector (butyl xanthate, the addition amount is 60g / t) and the supplementary frother (2# oil, the addition amount is 30g / t), and performing the third flotation (stirring time is 1min, flotation time is 2min) to obtain enriched copper cobalt sulfide leaching residue; the enriched copper cobalt sulfide leaching residue, the copper cobalt oxide rougher concentrate and the cobalt oxide magnetic separation concentrate are mixed, and water and sulfuric acid are added to perform oxygen pressure leaching (acid-ore ratio is 220kg / t, liquid-solid ratio is 6:1, stirring speed is 800r / min, temperature is 220℃, time is 0.8h, oxygen partial pressure is 0.3Mpa, pH value of the leaching end point liquid is 1.2), and oxygen pressure leaching solution and oxygen pressure leaching residue are obtained after solid-liquid separation.

[0106] Embodiment 15

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

[0108] Example 16

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

[0110] Comparative Example 1

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

[0112] Comparative Example 2

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

[0114] Results test:

[0115] The metal contents in the above 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: Atomic absorption spectrometry (other chemical analysis methods such as inductively coupled plasma mass spectrometry, X-ray fluorescence spectrometry, etc.) is used to determine the cobalt content in high calcium magnesium copper cobalt ore, oxygen pressure leaching slag, and cobalt oxide magnetic separation tailings. Comprehensive recovery rate of cobalt = (cobalt content in high calcium magnesium copper cobalt ore - cobalt content in oxygen pressure leaching slag - cobalt content in cobalt oxide magnetic separation tailings) ÷ cobalt content in high calcium magnesium copper cobalt ore.

[0117] Comprehensive recovery rate of copper: Atomic absorption spectrometry (other chemical analysis methods such as inductively coupled plasma mass spectrometry, X-ray fluorescence spectrometry, etc.) is used to determine the copper content in high calcium magnesium copper cobalt ore, oxygen pressure leaching slag, and cobalt oxide magnetic separation tailings. Comprehensive recovery rate of copper = (copper content in high calcium magnesium copper cobalt ore - copper content in oxygen pressure leaching slag - copper content in cobalt oxide magnetic separation tailings) ÷ copper content in high calcium magnesium copper cobalt ore.

[0118] Table 1

[0119]

[0120] As can be seen from the above, compared with the comparative example, each embodiment of the present invention adopts a process of first sulfur and then oxygen flotation enrichment-normal pressure oxygen pressure combined leaching to efficiently leach copper and cobalt in high calcium magnesium copper-cobalt ore. First, the roughly selected copper-cobalt sulfide concentrate, copper-cobalt oxide concentrate, and magnetic cobalt concentrate are obtained by flotation and magnetic separation processes, and then the copper-cobalt sulfide concentrate is roasted and leached at normal pressure to obtain a copper-cobalt leaching solution and a leaching residue containing unleached copper-cobalt sulfide. Finally, the leaching residue, copper-cobalt oxide concentrate, and magnetic cobalt concentrate are subjected to oxygen pressure leaching 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 overall effect is better.

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

Claims

1. A method for the combined beneficiation of high calcium magnesium copper-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, mixing the atmospheric pressure leaching residue, the copper cobalt oxide rougher concentrate and the cobalt oxide magnetic separation concentrate, adding water and sulfuric acid, performing oxygen pressure leaching, and obtaining oxygen pressure leaching solution and oxygen pressure leaching residue after solid-liquid separation.

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 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 2-4h; 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 the step S5, The background magnetic field strength of the magnetic separation is 0.3-2.0T; and / or The magnetic separation includes magnetic roughing separation, magnetic concentrating separation and magnetic sweeping separation performed sequentially.

8. 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.

9. The method for combined beneficiation of high calcium magnesium copper-cobalt ore according to claim 1 or 2, characterized in that: In step S6, First, the atmospheric pressure leaching residue is subjected to a third flotation to obtain enriched copper-cobalt sulfide leaching residue; then the enriched copper-cobalt sulfide leaching residue, the copper-cobalt oxide rougher concentrate and the cobalt oxide magnetic concentrate are mixed, water and sulfuric acid are added, and the oxygen pressure leaching is performed.

10. 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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