Method for recycling valuable metal in cobaltosic oxide waste by utilizing vulcanized tailings

Abstract

The invention discloses a method for recycling valuable metals in cobaltosic oxide waste by utilizing sulfurized tailings. The recycling method comprises the following steps: mixing the cobaltosic oxide waste material and the vulcanized tailings according to a mass ratio of 1: (0.5-3), and preparing into slurry; performing normal-pressure acid leaching treatment on the slurry to obtain a normal-pressure acid-leached material; the pH of the normal-pressure acid leaching material is adjusted back to 4.5-5.0, then filtering is conducted, and filter residues and nickel-cobalt filtrate are obtained; and the filter residues are subjected to high-pressure acid leaching treatment, and leaching liquid containing valuable metal and high-pressure acid leaching residues are obtained through filtering. The whole process is simple and easy to implement and convenient to operate, resource utilization of waste is achieved, the production cost is saved, and exploitation and consumption of natural resources are reduced.

Description

Technical Field

[0001] The invention belongs to the field of comprehensive waste recycling, and in particular relates to a method for recycling valuable metals in cobalt tetroxide waste by utilizing sulfide tailings. Background Art

[0002] Cobalt tetroxide (Co3O4) is an important battery raw material, mainly containing Co 2+ and Co 3+ Two valence states. 3+ It is not easy to leach, and the development of its recovery technology has attracted widespread attention. At present, the recovery technology of cobalt tetroxide mainly includes hydrometallurgy, pyrometallurgy and the combination of the two.

[0003] The traditional method of recycling cobalt trioxide waste is to carry out reduction roasting in a hydrogen atmosphere, but this method consumes a lot of energy and is highly dangerous. In contrast, the wet recovery process is favored for its lower pollution level, lower energy consumption and higher purity of the recovered product. However, the wet recovery process with the addition of a reducing agent under normal pressure cannot effectively recover cobalt trioxide, and it needs to be recovered by leaching with a pressurized reducing agent, but this will lead to problems such as increased equipment corrosion and increased depreciation costs.

[0004] Sulfide tailings are obtained by adding sodium sulfide precipitation to the raffinate liquid in the cobalt P507 extraction process, which contains valuable metals such as nickel, cobalt, and manganese. In order to recover these metal elements from this sulfide tailing, a high-pressure acid leaching method is usually used. This method requires oxygen to oxidize the sulfur in the sulfide into sulfate ions, thereby separating metals such as nickel, cobalt, and manganese. However, this method requires a large amount of oxygen and there is a certain risk during the operation. Summary of the invention

[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a method for recovering valuable metals in cobalt tetroxide waste by utilizing sulfide tailings, aiming to achieve effective comprehensive utilization of cobalt tetroxide waste and sulfide tailings, recover these materials at low cost, and produce high-value industrial products while protecting production equipment.

[0006] The purpose of the present invention is achieved through the following technical solutions: A method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings comprises the following steps: S1. Mixing cobalt trioxide waste and sulfide tailings in a mass ratio of 1:0.5-3 to prepare a slurry; S2, subjecting the slurry to normal pressure acid leaching treatment to obtain normal pressure acid leaching material; S3, adjusting the pH of the atmospheric pressure acid leaching material to 4.5-5.0 and filtering to obtain filter residue and nickel-cobalt filtrate; S4, subjecting the filter residue to high-pressure acid leaching treatment, filtering to obtain a leachate containing valuable metals and high-pressure acid leaching residue.

[0007] Preferably, the method further comprises recycling the high-pressure acid leaching residue to the normal-pressure acid leaching treatment process in step S1.

[0008] Preferably, in step S1, the main elements and corresponding mass percentage contents of the cobalt oxide 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.

[0009] Preferably, in step S1, the sulfide tailings are obtained by adding sodium sulfide precipitate to the raffinate liquid in the cobalt P507 extraction process, and 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.

[0010] Preferably, in step S1, the solid-liquid ratio of the slurry is 75-200 g / L.

[0011] Preferably, in step S2, sulfuric acid is used for atmospheric pressure acid leaching treatment, and 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, and the amount of sulfuric acid added is calculated based on the molar concentration of hydrogen ions.

[0012] Preferably, in step S2, the atmospheric pressure acid leaching treatment is carried out by acid leaching at 70-95° C. for 2-6 hours.

[0013] Preferably, in step S3, the pH of the atmospheric pressure acid soaking material is adjusted back to 4.5-5.0, and the mixture is filtered after reacting for 1-2 hours.

[0014] Preferably, in step S3, the pH value of the atmospheric pressure acid leaching material is adjusted to 4.5-5.0 by adding at least one of hydroxide waste and carbonate waste to adjust the pH value.

[0015] Preferably, the hydroxide waste is at least one of nickel hydroxide waste, cobalt hydroxide waste and manganese hydroxide waste.

[0016] Preferably, the carbonate waste is at least one of nickel carbonate waste, cobalt carbonate waste and manganese carbonate waste.

[0017] Preferably, in step S3, the filtration is pressure filtration.

[0018] Preferably, in step S4, sulfuric acid is used for high pressure acid leaching, and 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, and the amount of sulfuric acid added is calculated based on the molar concentration of hydrogen ions.

[0019] Preferably, in step S4, the high pressure acid leaching treatment is carried out by acid leaching at 155-195° C. for 6-18 hours.

[0020] Compared with the prior art, the beneficial effects of the present invention include: (1) The present invention mixes cobalt trioxide waste with sulfide tailings, and sequentially performs slurrying, atmospheric pressure acid leaching, pH adjustment / filter pressing, and high-pressure acid leaching to finally obtain a filtrate containing cobalt and nickel. The entire process is simple and easy to operate, and the resource utilization of waste is realized.

[0021] (2) This invention utilizes Co in cobalt tetroxide waste 3+ The oxidizability of sulfur and sulfur in the tailings 2- The reducibility of cobalt oxide promotes the occurrence of redox reactions under high pressure acidic conditions. Therefore, there is no need to add reducing agents such as sodium pyrosulfite and sodium thiosulfate when treating cobalt oxide waste; similarly, there is no need to add oxidizing agents such as oxygen, sodium persulfate or sodium chlorate when treating sulfide tailings. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The present invention is a schematic flow chart of a method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0024] The cobalt oxide waste described in the embodiment is provided by GEM Co., Ltd. The cobalt oxide waste refers to the waste generated during the production process due to unqualified chemical or physical indicators. The main elements and their corresponding mass percentage contents are: 72% Co, 0.012% Ni, 0.0001% Mn, 0.0252% Cu, 0.0002% Fe and 0.0334% Ca.

[0025] The sulfide tailings are provided by GEM Co., Ltd. The sulfide tailings are products obtained by reaction and precipitation of cobalt P507 raffinate and sodium sulfide. 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.

[0026] The nickel cobalt hydroxide waste is provided by GEM Co., Ltd. The nickel cobalt hydroxide waste is waste generated during the production process of NC precursor, a positive electrode material for lithium batteries, due to unqualified 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.

[0027] The calculation formulas for cobalt and nickel leaching rates are as follows:

[0028]

[0029] M1, M2, M3, and M4 are the masses (g) of cobalt oxide waste, sulfide tailings, nickel cobalt hydroxide waste and high-pressure acid leaching residue, respectively; C1, C2, C3, and C4 are the mass percentages (%) of cobalt in cobalt oxide waste, sulfide tailings, nickel cobalt hydroxide waste and high-pressure acid leaching residue, respectively; N1, N2, N3, and N4 are the mass percentages (%) of nickel in cobalt oxide waste, sulfide tailings, nickel cobalt hydroxide waste and high-pressure acid leaching residue, respectively.

[0030] Example 1 A method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings, comprising the following steps: 50 g of cobalt oxide waste and 95 g of sulfide tail material were mixed in a mass ratio of 1:1.9, and the solid-liquid ratio was 75 g / L for slurrying; 37 mL of sulfuric acid (the amount of sulfuric acid added was 1.1 times the total molar amount of nickel, cobalt, manganese, copper and iron in the cobalt oxide waste) was added to the above slurry for atmospheric pressure acid leaching, the atmospheric pressure acid leaching temperature was 70°C, and the atmospheric pressure acid leaching time was 6 h; after the atmospheric pressure acid leaching, 20 g of nickel hydroxide cobalt waste was added to adjust the pH to 4.5, and after the adjustment, the reaction was continued for 1 h and then filtered to obtain cobalt nickel filtrate and filter residue; (4) 33 mL of sulfuric acid (the amount of sulfuric acid added was 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, the high-pressure acid leaching temperature was 155°C, the high-pressure acid leaching time was 17 h, and after the high-pressure acid leaching, a leachate containing valuable metals and high-pressure acid leaching residue were obtained.

[0031] After testing, the wet weight of the high-pressure acid leaching slag is 16.1g, and the main components are: 23.53% Co, 11.15% Ni.

[0032] After calculation, the total leaching rate of cobalt is 90.16%, and the total leaching rate of nickel is 89.82%. This data is obtained when the high-pressure acid leaching residue is not recycled.

[0033] Example 2 A method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings, comprising the following steps: 50 g of cobalt oxide waste and 90 g of sulfide tail material were mixed in a mass ratio of 1:1.8, and the solid-liquid ratio was 140 g / L for slurrying; 40 mL of sulfuric acid (the amount of sulfuric acid added was 1.2 times the total molar amount of nickel, cobalt, manganese, copper and iron in the cobalt oxide waste) was added to the above slurry for atmospheric acid leaching, the atmospheric acid leaching temperature was 80°C, and the atmospheric acid leaching time was 4 h; after the atmospheric acid leaching, 23 g of nickel hydroxide cobalt waste was added to adjust the pH to 4.93, and after the adjustment, the reaction was continued for 1.5 h and then filtered to obtain a cobalt-nickel filtrate and a filter residue; (4) 38 mL of sulfuric acid (the amount of sulfuric acid added was 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, the high-pressure acid leaching temperature was 170°C, the high-pressure acid leaching time was 12 h, and after the high-pressure acid leaching, a leachate containing valuable metals and a high-pressure acid leaching residue were obtained.

[0034] After testing, the wet weight of the high-pressure acid leaching slag is 18.4g, and the main components are: 22.49% Co, 14.57% Ni.

[0035] After calculation, the total leaching rate of cobalt is 89.27%, and the total leaching rate of nickel is 87.71%. This data is obtained when the high-pressure acid leaching residue is not recycled.

[0036] Example 3 A method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings, comprising the following steps: 50 g of cobalt oxide waste and 110 g of sulfide tail material were mixed in a mass ratio of 1:2.2, and the solid-liquid ratio was 160 g / L for slurrying; 41 mL of sulfuric acid (the amount of sulfuric acid added was 1.25 times the total molar amount of nickel, cobalt, manganese, copper and iron in the cobalt oxide waste) was added to the above slurry for atmospheric acid leaching, the atmospheric acid leaching temperature was 90°C, and the atmospheric acid leaching time was 2 h; after the atmospheric acid leaching, 22.7 g of nickel hydroxide cobalt waste was added to adjust the pH to 4.68, and after the adjustment, the reaction was continued for 2 h and then filtered to obtain cobalt nickel filtrate and filter residue; (4) 35 mL of sulfuric acid (the amount of sulfuric acid added was 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, the high-pressure acid leaching temperature was 190°C, the high-pressure acid leaching time was 6 h, and after the high-pressure acid leaching, a leachate containing valuable metals and high-pressure acid leaching residue were obtained.

[0037] After testing, the wet weight of the high-pressure acid leaching slag is 13.6g, and the main components are: 30.66% Co, 11.85% Ni.

[0038] After calculation, the total leaching rate of cobalt is 91.65%, and the total leaching rate of nickel is 82.44%. This data is obtained when the high-pressure acid leaching residue is not recycled.

[0039] Example 4 A method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings, comprising the following steps: 50 g of cobalt oxide waste and 120 g of sulfide tail material were mixed in a mass ratio of 1:2.4, and the solid-liquid ratio was 170 g / L for slurrying to obtain a slurry; 43 mL of sulfuric acid (the amount of sulfuric acid added was 1.3 times the total molar amount of nickel, cobalt, manganese, copper and iron in the cobalt oxide waste) was added to the above slurry for atmospheric pressure acid leaching, the atmospheric pressure acid leaching temperature was 90°C, and the atmospheric pressure acid leaching time was 6 h; after the atmospheric pressure acid leaching, 30 g of nickel hydroxide cobalt waste was added to adjust the pH to 4.71, and after the adjustment, the reaction was continued for 2 h and then filtered to obtain a cobalt-nickel filtrate and a filter residue; (4) 45 mL of sulfuric acid (the amount of sulfuric acid added was 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, the high-pressure acid leaching temperature was 170°C, the high-pressure acid leaching time was 12 h, and after the high-pressure acid leaching, a leachate containing valuable metals and a high-pressure acid leaching residue were obtained.

[0040] After testing, the wet weight of the high-pressure acid leaching slag is 15.5g, and the main components are: 22.44% Co, 19.66% Ni.

[0041] After calculation, the total leaching rate of cobalt is 91.17%, and the total leaching rate of nickel is 87.46%. This data is obtained when the high-pressure acid leaching residue is not recycled.

[0042] Example 5 A method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings, comprising the following steps: 50 g of cobalt oxide waste and 100 g of sulfide tail material were mixed in a mass ratio of 1:2, and the solid-liquid ratio was 150 g / L for slurrying; 45 mL of sulfuric acid (the amount of sulfuric acid added was 1.36 times the total molar amount of nickel, cobalt, manganese, copper and iron in the cobalt oxide waste) was added to the above slurry for atmospheric pressure acid leaching, the atmospheric pressure acid leaching temperature was 90°C, and the atmospheric pressure acid leaching time was 6 h; after the atmospheric pressure acid leaching, 20.4 g of nickel hydroxide cobalt waste was added to adjust the pH to 4.6, and after the adjustment, the reaction was continued for 2 h and then filtered to obtain cobalt nickel filtrate and filter residue; (4) 45 mL of sulfuric acid (the amount of sulfuric acid added was 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, the high-pressure acid leaching temperature was 170°C, the high-pressure acid leaching time was 17 h, and after the high-pressure acid leaching, a leachate containing valuable metals and high-pressure acid leaching residue were obtained.

[0043] After testing, the wet weight of the high-pressure acid leaching slag is 11.3g, and the main components are: 11.44% Co, 32.78% Ni.

[0044] After calculation, the total leaching rate of cobalt is 95.65%, and the total leaching rate of nickel is 85.98%. This data is obtained when the high-pressure acid leaching residue is not recycled.

[0045] Example 6 A method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings, comprising the following steps: 50 g of cobalt oxide waste and 150 g of sulfide tail material were mixed in a mass ratio of 1:3, and the solid-liquid ratio was 200 g / L for slurrying; 45 mL of sulfuric acid (the amount of sulfuric acid added was 1.36 times the total molar amount of nickel, cobalt, manganese, copper and iron in the cobalt oxide waste) was added to the above slurry for atmospheric acid leaching, the atmospheric acid leaching temperature was 70°C, and the atmospheric acid leaching time was 6 h; after the atmospheric acid leaching, 23 g of nickel hydroxide cobalt waste was added to adjust the pH to 4.5, and after the adjustment, the reaction was continued for 1 h and then filtered to obtain cobalt nickel filtrate and filter residue; (4) 45 mL of sulfuric acid (the amount of sulfuric acid added was 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°C, the high-pressure acid leaching time was 17 h, and after the high-pressure acid leaching, a leachate containing valuable metals and high-pressure acid leaching residue were obtained.

[0046] After testing, the wet weight of the high-pressure acid leaching slag is 17g, and the main components are: 16.52% Co, 44.05% Ni.

[0047] After calculation, the total leaching rate of cobalt is 92.89%, and the total leaching rate of nickel is 79.72%. This data is obtained when the high-pressure acid leaching residue is not recycled.

[0048] The specific implementation of the present invention described above does not constitute a limitation on the protection scope of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings, characterized in that: The steps include: S1. Mixing cobalt trioxide waste and sulfide tailings in a mass ratio of 1:0.5-3 to prepare a slurry; S2, subjecting the slurry to normal pressure acid leaching treatment to obtain a normal pressure acid leaching material; S3, adjusting the pH of the atmospheric pressure acid leaching material to 4.5-5.0 and filtering to obtain filter residue and nickel-cobalt filtrate; S4, subjecting the filter residue to high-pressure acid leaching treatment, filtering 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 sulfide tailings according to claim 1, characterized in that: The method further includes recycling the high-pressure acid leaching residue to the normal-pressure acid leaching treatment process described in step S1.

3. The method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings according to claim 1 or 2, characterized in that: The solid-liquid ratio of the slurry in step S1 is 75-200 g / L.

4. The method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings according to claim 1, characterized in that: The atmospheric pressure acid leaching treatment in step S2 uses sulfuric acid, and 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, and the amount of sulfuric acid added is calculated according to the molar concentration of hydrogen ions.

5. The method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings according to claim 4, characterized in that: The normal pressure acid leaching treatment in step S2 is carried out by acid leaching at 70-95° C. for 2-6 hours.

6. The method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings according to claim 1 or 2, characterized in that: In step S3, the pH of the atmospheric pressure acid-leached material is adjusted back to 4.5-5.0, and the mixture is filtered after reacting for 1-2 hours.

7. The method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings according to claim 6, characterized in that: The method of adjusting the pH of the atmospheric pressure acid leaching material to 4.5-5.0 in step S3 is: adjusting the pH by adding at least one of hydroxide waste and carbonate waste.

8. The method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings according to claim 7, 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.

9. The method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings according to claim 1, characterized in that: The high pressure acid leaching treatment in step S4 uses sulfuric acid, and 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, and the amount of sulfuric acid added is calculated based on the molar concentration of hydrogen ions.

10. The method for recovering valuable metals from cobalt tetroxide waste using sulfide tailings according to claim 9, characterized in that: The high pressure acid leaching treatment in step S4 is carried out by acid leaching at 155-195° C. for 6-18 hours.

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