A method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings

Abstract

This invention discloses a method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings. The recovery method includes the following steps: mixing cobalt tetroxide waste and sulfidation tailings at a mass ratio of 1:0.5-3 to prepare a slurry; subjecting the slurry to atmospheric pressure acid leaching to obtain atmospheric pressure acid leaching material; adjusting the pH of the atmospheric pressure acid leaching material to 4.5-5.0 and then filtering to obtain filter residue and nickel-cobalt filtrate; subjecting the filter residue to high-pressure acid leaching to obtain a leachate containing valuable metals and high-pressure acid leaching residue. The entire process of this invention is simple, easy to implement, and convenient to operate. It not only achieves resource utilization of waste and saves production costs but also reduces the exploitation and consumption of natural resources.

Description

Technical Field

[0001] This invention belongs to the field of comprehensive waste recycling, and in particular relates to a method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings. Background Technology

[0002] Cobalt tetroxide (Co3O4) is an important battery material, mainly containing Co. 2+ and Co 3+ Two valence states. Due to Co 3+ Cobalt tetroxide is difficult to leach, making its recycling technology a focus of widespread attention. Currently, cobalt tetroxide recycling technologies mainly include hydrometallurgy, pyrometallurgy, and a combination of both.

[0003] Traditional methods for recovering cobalt tetroxide waste involve reduction roasting in a hydrogen atmosphere, but this method is energy-intensive and highly hazardous. In contrast, wet recycling processes are favored due to their lower pollution levels, lower energy consumption, and higher purity of the recovered products. However, wet recycling processes using reducing agents under normal pressure cannot effectively recover cobalt tetroxide; pressurized leaching with a reducing agent is required for recovery, which leads to increased equipment corrosion and depreciation costs.

[0004] Sulfide tailings are obtained by adding sodium sulfide to the raffinate from the cobalt P507 extraction process, and contain valuable metals such as nickel, cobalt, and manganese. To recover these metals from this tailings, a high-pressure acid leaching method is typically used. This method requires the introduction of oxygen to oxidize the sulfur in the sulfide to sulfate ions, thereby separating the nickel, cobalt, and manganese. However, this method requires a large amount of oxygen and involves certain safety hazards during operation. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings. The aim is to achieve effective and comprehensive utilization of cobalt tetroxide waste and sulfidation tailings, recover these materials at low cost, produce high-value industrial products, and protect production equipment.

[0006] The objective of this invention is achieved through the following technical solution:

[0007] A method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings includes the following steps:

[0008] S1. Mix cobalt tetroxide waste and sulfide tailings at a mass ratio of 1:0.5~3 and prepare a slurry;

[0009] S2. The slurry is subjected to atmospheric pressure acid leaching to obtain atmospheric pressure acid leaching material;

[0010] S3. After adjusting the pH of the acid leaching material to 4.5~5.0, filter it to obtain filter residue and nickel-cobalt filtrate;

[0011] S4. The filter residue is subjected to high-pressure acid leaching treatment to obtain a leachate containing valuable metals and high-pressure acid leaching residue.

[0012] Preferably, the process also includes reusing the high-pressure acid leaching residue in the atmospheric pressure acid leaching process of step S1.

[0013] Preferably, in step S1, the main elements and their corresponding mass percentage contents of the cobalt tetroxide waste are: 72% Co, 0.012% Ni, 0.0001% Mn, 0.0252% Cu, 0.0002% Fe, and 0.0334% Ca. Provided by GEM Co., Ltd.

[0014] Preferably, in step S1, the sulfidation tailings are obtained by adding sodium sulfide to the raffinate from the cobalt P507 extraction process to precipitate, and the main elements and their corresponding mass percentage contents are as follows: 1.561% Co, 15.37% Ni, 0.015% Mn, 0.373% Cu, 0.4457% Fe, 0.0334% Ca, 2.2% Cl and 14.91% S.

[0015] Preferably, in step S1, the solid-liquid ratio of the slurry is 75~200g / L.

[0016] Preferably, in step S2, sulfuric acid is used for the atmospheric pressure acid leaching treatment. The amount of sulfuric acid added is 1 to 2 times the total molar amount of nickel, cobalt, manganese, copper and iron in the cobalt tetroxide waste. The amount of sulfuric acid added is calculated based on the molar concentration of hydrogen ions.

[0017] Preferably, in step S2, the method of acid leaching under normal pressure is: acid leaching at 70~95℃ for 2~6 hours.

[0018] Preferably, in step S3, the pH of the acid leaching material under normal pressure is adjusted back to 4.5~5.0, and the reaction is carried out for 1~2 hours before filtration.

[0019] Preferably, in step S3, the pH of the atmospheric pressure acid leaching material is adjusted back to 4.5~5.0 by adding at least one of hydroxide waste and carbonate waste.

[0020] Preferably, the hydroxide waste is at least one of nickel hydroxide waste, cobalt hydroxide waste, and manganese hydroxide waste.

[0021] Preferably, the carbonate waste is at least one of nickel carbonate waste, cobalt carbonate waste, and manganese carbonate waste.

[0022] Preferably, in step S3, the filtration is pressure filtration.

[0023] Preferably, in step S4, sulfuric acid is used for high-pressure acid leaching. The amount of sulfuric acid added is 1 to 2 times the total molar amount of nickel, cobalt, manganese, copper and iron in the filter residue of step S3. The amount of sulfuric acid added is calculated based on the molar concentration of hydrogen ions.

[0024] Preferably, in step S4, the high-pressure acid leaching treatment is carried out by leaching at 155~195℃ for 6~18 hours.

[0025] Compared with the prior art, the beneficial effects of the present invention include:

[0026] (1) This invention mixes cobalt tetroxide waste with sulfidation tailings and sequentially performs slurrying, atmospheric pressure acid leaching, pH adjustment / pressure filtration, and high pressure acid leaching to finally obtain a cobalt-nickel-containing filtrate. The entire process is simple, easy to operate, and realizes the resource utilization of waste.

[0027] (2) This invention utilizes Co in cobalt tetroxide waste. 3+ Oxidizing properties and S in sulfurized tailings 2- Cobalt tetroxide's reducing properties promote redox reactions under high pressure and acidic conditions. Therefore, there is no need to add reducing agents such as sodium metabisulfite or sodium thiosulfate when treating cobalt tetroxide waste; similarly, there is no need to add oxidizing agents such as oxygen, sodium persulfate, or sodium chlorate when treating sulfidation tailings. Attached Figure Description

[0028] Figure 1 This is a schematic flowchart of the method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings, as described in this invention. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0030] The cobalt tetroxide waste described in this embodiment was provided by GEM Co., Ltd. Cobalt tetroxide waste refers to waste generated during the production process due to non-compliance with chemical or physical indicators. The main elements and their corresponding mass percentage contents are as follows: 72% Co, 0.012% Ni, 0.0001% Mn, 0.0252% Cu, 0.0002% Fe and 0.0334% Ca.

[0031] The sulfurized tailings were provided by GEM Co., Ltd. The sulfurized tailings are a product obtained by reacting cobalt P507 raffinate with sodium sulfide to form a precipitate. The main elements and their corresponding mass percentage contents are: 1.561% Co, 15.37% Ni, 0.015% Mn, 0.373% Cu, 0.4457% Fe, 0.0334% Ca, 2.2% Cl, and 14.91% S.

[0032] The nickel-cobalt hydroxide waste was provided by GEM Co., Ltd. This waste is generated during the production of NC precursors for lithium-ion battery cathode materials due to non-compliance with chemical or physical indicators. The main elements and their corresponding mass percentage contents are: 5.06% Co, 55.76% Ni, 0.5% Mn, and 19.39% H2O.

[0033] The formulas for calculating the leaching rates of cobalt and nickel are as follows:

[0034]

[0035]

[0036] M1, M2, M3, and M4 represent the mass (g) of cobalt tetroxide waste, sulfidation tailings, nickel-cobalt hydroxide waste, and high-pressure acid leaching residue, respectively; C1, C2, C3, and C4 represent the mass percentage (%) of cobalt in the cobalt tetroxide waste, sulfidation tailings, nickel-cobalt hydroxide waste, and high-pressure acid leaching residue, respectively; N1, N2, N3, and N4 represent the mass percentage (%) of nickel in the cobalt tetroxide waste, sulfidation tailings, nickel-cobalt hydroxide waste, and high-pressure acid leaching residue, respectively.

[0037] Example 1

[0038] A method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings includes the following steps:

[0039] 50g of cobalt tetroxide waste and 95g of sulfidation tailings were mixed at a mass ratio of 1:1.9 and slurryed at a solid-liquid ratio of 75g / L to obtain a slurry. 37mL of sulfuric acid (the amount of sulfuric acid added is 1.1 times the total molar amount of nickel, cobalt, manganese, copper and iron in the cobalt tetroxide waste) was added to the slurry for atmospheric pressure acid leaching treatment. The atmospheric pressure acid leaching temperature was 70℃ and the atmospheric pressure acid leaching time was 6h. After the atmospheric pressure acid leaching was completed, 20g of nickel cobalt hydroxide waste was added to adjust the pH to 4.5. After the adjustment was completed, the reaction was carried out again for 1h and then pressure filtered to obtain cobalt nickel filtrate and filter residue. (4) 33mL of sulfuric acid (the amount of sulfuric acid added is 1.05 times the total molar amount of nickel, cobalt, manganese, copper and iron in the filter residue) was added to the filter residue for high pressure acid leaching treatment. The high pressure acid leaching temperature was 155℃ and the high pressure acid leaching time was 17h. After the high pressure acid leaching was completed, leachate containing valence metals and high pressure acid leaching residue were obtained.

[0040] The wet weight of the high-pressure acid leaching residue was 16.1g, and its main components were 23.53% Co and 11.15% Ni.

[0041] Calculations show that the total leaching rate of cobalt is 90.16% and the total leaching rate of nickel is 89.82%. These figures are based on the assumption that the high-pressure acid leaching residue is not reused.

[0042] Example 2

[0043] A method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings includes the following steps:

[0044] 50g of cobalt tetroxide waste and 90g of sulfidation tailings were mixed at a mass ratio of 1:1.8 and slurryed at a solid-liquid ratio of 140g / L to obtain a slurry. 40mL of sulfuric acid (the amount of sulfuric acid added is 1.2 times the total molar amount of nickel, cobalt, manganese, copper and iron in the cobalt tetroxide waste) was added to the slurry for atmospheric pressure acid leaching treatment. The atmospheric pressure acid leaching temperature was 80℃ and the atmospheric pressure acid leaching time was 4h. After the atmospheric pressure acid leaching was completed, 23g of nickel cobalt hydroxide waste was added to adjust the pH to 4.93. After the adjustment was completed, the reaction was carried out again for 1.5h and then pressure filtered to obtain cobalt nickel filtrate and filter residue. (4) 38mL of sulfuric acid (the amount of sulfuric acid added is 1.15 times the total molar amount of nickel, cobalt, manganese, copper and iron in the filter residue) was added to the filter residue for high pressure acid leaching treatment. The high pressure acid leaching temperature was 170℃ and the high pressure acid leaching time was 12h. After the high pressure acid leaching was completed, leachate containing valuable metals and high pressure acid leaching residue were obtained.

[0045] The wet weight of the high-pressure acid leaching residue was 18.4g, and its main components were 22.49% Co and 14.57% Ni.

[0046] Calculations show that the total leaching rate of cobalt is 89.27%, and the total leaching rate of nickel is 87.71%. These figures are based on the assumption that the high-pressure acid leaching residue is not reused.

[0047] Example 3

[0048] A method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings includes the following steps:

[0049] 50g of cobalt tetroxide waste and 110g of sulfidation tailings were mixed at a mass ratio of 1:2.2 and slurryed at a solid-liquid ratio of 160g / L to obtain a slurry. 41mL of sulfuric acid (the amount of sulfuric acid added is 1.25 times the total molar amount of nickel, cobalt, manganese, copper and iron in the cobalt tetroxide waste) was added to the slurry for atmospheric pressure acid leaching treatment. The atmospheric pressure acid leaching temperature was 90℃ and the atmospheric pressure acid leaching time was 2h. After the atmospheric pressure acid leaching was completed, 22.7g of nickel cobalt hydroxide waste was added to adjust the pH to 4.68. After the adjustment was completed, the reaction was carried out for 2h and then pressure filtered to obtain cobalt nickel filtrate and filter residue. (4) 35mL of sulfuric acid (the amount of sulfuric acid added is 1.06 times the total molar amount of nickel, cobalt, manganese, copper and iron in the filter residue) was added to the filter residue for high pressure acid leaching treatment. The high pressure acid leaching temperature was 190℃ and the high pressure acid leaching time was 6h. After the high pressure acid leaching was completed, leachate containing valuable metals and high pressure acid leaching residue were obtained.

[0050] The wet weight of the high-pressure acid leaching residue was 13.6g, and its main components were 30.66% Co and 11.85% Ni.

[0051] Calculations show that the total leaching rate of cobalt is 91.65%, and the total leaching rate of nickel is 82.44%. These figures are based on the assumption that the high-pressure acid leaching residue is not reused.

[0052] Example 4

[0053] A method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings includes the following steps:

[0054] 50g of cobalt tetroxide waste and 120g of sulfidation tailings were mixed at a mass ratio of 1:2.4 and slurryed at a solid-liquid ratio of 170g / L to obtain a slurry. 43mL of sulfuric acid (the amount of sulfuric acid added is 1.3 times the total molar amount of nickel, cobalt, manganese, copper and iron in the cobalt tetroxide waste) was added to the slurry for atmospheric pressure acid leaching treatment. The atmospheric pressure acid leaching temperature was 90℃ and the atmospheric pressure acid leaching time was 6h. After the atmospheric pressure acid leaching was completed, 30g of nickel cobalt hydroxide waste was added to adjust the pH to 4.71. After the adjustment was completed, the reaction was carried out again for 2h and then pressure filtered to obtain cobalt nickel filtrate and filter residue. (4) 45mL of sulfuric acid (the amount of sulfuric acid added is 1.68 times the total molar amount of nickel, cobalt, manganese, copper and iron in the filter residue) was added to the filter residue for high pressure acid leaching treatment. The high pressure acid leaching temperature was 170℃ and the high pressure acid leaching time was 12h. After the high pressure acid leaching was completed, leachate containing valuable metals and high pressure acid leaching residue were obtained.

[0055] The wet weight of the high-pressure acid leaching residue was 15.5g, and its main components were 22.44% Co and 19.66% Ni.

[0056] Calculations show that the total leaching rate of cobalt is 91.17%, and the total leaching rate of nickel is 87.46%. These figures are based on the assumption that the high-pressure acid leaching residue is not reused.

[0057] Example 5

[0058] A method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings includes the following steps:

[0059] 50g of cobalt tetroxide waste and 100g of sulfidation tailings were mixed at a mass ratio of 1:2 and slurryed at a solid-liquid ratio of 150g / L to obtain slurry. 45mL of sulfuric acid (the amount of sulfuric acid added is 1.36 times the total molar amount of nickel, cobalt, manganese, copper and iron in the cobalt tetroxide waste) was added to the slurry for atmospheric pressure acid leaching treatment. The atmospheric pressure acid leaching temperature was 90℃ and the atmospheric pressure acid leaching time was 6h. After the atmospheric pressure acid leaching was completed, 20.4g of nickel cobalt hydroxide waste was added to adjust the pH to 4.6. After the adjustment was completed, the reaction was carried out again for 2h and then pressure filtered to obtain cobalt nickel filtrate and filter residue. (4) 45mL of sulfuric acid (the amount of sulfuric acid added is 1.8 times the total molar amount of nickel, cobalt, manganese, copper and iron in the filter residue) was added to the filter residue for high pressure acid leaching treatment. The high pressure acid leaching temperature was 170℃ and the high pressure acid leaching time was 17h. After the high pressure acid leaching was completed, leachate containing valence metals and high pressure acid leaching residue were obtained.

[0060] The wet weight of the high-pressure acid leaching residue was 11.3g, and its main components were 11.44% Co and 32.78% Ni.

[0061] Calculations show that the total leaching rate of cobalt is 95.65%, and the total leaching rate of nickel is 85.98%. These figures are based on the assumption that the high-pressure acid leaching residue is not reused.

[0062] Example 6

[0063] A method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings includes the following steps:

[0064] 50g of cobalt tetroxide waste and 150g of sulfidation tailings were mixed at a mass ratio of 1:3 and slurryed at a solid-liquid ratio of 200g / L to obtain a slurry. 45mL of sulfuric acid (the amount of sulfuric acid added is 1.36 times the total molar amount of nickel, cobalt, manganese, copper and iron in the cobalt tetroxide waste) was added to the slurry for atmospheric pressure acid leaching. The atmospheric pressure acid leaching temperature was 70℃ and the atmospheric pressure acid leaching time was 6h. After the atmospheric pressure acid leaching was completed, 23g of nickel cobalt hydroxide waste was added to adjust the pH to 4.5. After the adjustment was completed, the mixture was reacted again for 1h and then filtered to obtain cobalt nickel filtrate and filter residue. (4) 45mL of sulfuric acid (the amount of sulfuric acid added is 1.5 times the total molar amount of nickel, cobalt, manganese, copper and iron in the filter residue) was added to the filter residue for high pressure acid leaching. The high pressure acid leaching temperature was 155℃ and the high pressure acid leaching time was 17h. After the high pressure acid leaching was completed, leachate containing valuable metals and high pressure acid leaching residue were obtained.

[0065] The wet weight of the high-pressure acid leaching residue was 17g, and its main components were 16.52% Co and 44.05% Ni.

[0066] Calculations show that the total leaching rate of cobalt is 92.89%, and the total leaching rate of nickel is 79.72%. These figures are based on the assumption that the high-pressure acid leaching residue is not reused.

[0067] The specific embodiments of the present invention described above do not constitute a limitation on the scope of protection of the present invention. Any other corresponding changes and modifications made in accordance with the technical concept of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings, characterized in that, Includes the following steps: S1. Mix cobalt tetroxide waste and sulfide tailings at a mass ratio of 1:0.5~3 and prepare a slurry; The solid-liquid ratio of the slurry in step S1 is 75~200g / L; S2. The slurry is subjected to atmospheric pressure acid leaching to obtain atmospheric pressure acid leached material; The atmospheric pressure acid leaching treatment in step S2 uses sulfuric acid. The amount of sulfuric acid added is 1 to 2 times the total molar amount of nickel, cobalt, manganese, copper and iron in the cobalt tetroxide waste. The amount of sulfuric acid added is calculated based on the molar concentration of hydrogen ions. S3. After adjusting the pH of the acid leaching material to 4.5~5.0, filter it to obtain filter residue and nickel-cobalt filtrate; S4. The filter residue is subjected to high-pressure acid leaching treatment to obtain a leachate containing valuable metals and high-pressure acid leaching residue.

2. The method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings according to claim 1, characterized in that, It also includes reusing the high-pressure acid leaching residue in the atmospheric pressure acid leaching process described in step S1.

3. The method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings according to claim 1, characterized in that, The atmospheric pressure acid leaching treatment in step S2 is carried out by leaching at 70~95℃ for 2~6 hours.

4. The method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings according to claim 1 or 2, characterized in that, In step S3, the pH of the acid leaching material under normal pressure is adjusted back to 4.5~5.0, and the reaction is carried out for 1~2 hours before filtration.

5. The method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings according to claim 4, characterized in that, The method for adjusting the pH of the atmospheric pressure acid leaching material to 4.5~5.0 in step S3 is as follows: the pH is adjusted by adding at least one of hydroxide waste and carbonate waste.

6. The method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings according to claim 5, characterized in that, The hydroxide waste is at least one of nickel hydroxide waste, cobalt hydroxide waste, and manganese hydroxide waste; The carbonate waste is at least one of nickel carbonate waste, cobalt carbonate waste, and manganese carbonate waste.

7. The method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings according to claim 1, characterized in that, The high-pressure acid leaching treatment in step S4 uses sulfuric acid. The amount of sulfuric acid added is 1 to 2 times the total molar amount of nickel, cobalt, manganese, copper and iron in the filter residue in step S3. The amount of sulfuric acid added is calculated based on the molar concentration of hydrogen ions.

8. The method for recovering valuable metals from cobalt tetroxide waste using sulfidation tailings according to claim 7, characterized in that, The high-pressure acid leaching treatment in step S4 is performed by leaching at 155~195℃ for 6~18 hours.

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