Method for preparing manganese oxide and nickel cobalt oxide from nickel-cobalt-manganese ternary raw material

Abstract

The present application relates to a method for preparing a manganese oxide and a nickel cobalt oxide from a nickel-cobalt-manganese ternary raw material. The method comprises the following steps: preparing the nickel-cobalt-manganese ternary raw material into a slurry and then mixing the slurry with an acid and a reducing agent for reductive leaching; then performing solid-liquid separation to obtain a leaching liquid; subjecting the obtained leaching liquid to oxidative impurity removal to obtain a purified liquid; subjecting the obtained purified liquid to pressure oxidation to obtain a first precipitate and a first precipitate mother liquor; using the obtained first precipitate to prepare a manganese oxide; and using the first precipitate mother liquor to prepare a nickel cobalt oxide. The method provided in the present application can directly obtain the manganese oxide and the nickel cobalt oxide in steps by precisely controlling reaction conditions, without requiring extraction and separation, and compared with conventional methods, the method has shorter process flow and higher product value and can realize the high-value utilization of the nickel-cobalt-manganese ternary raw material.

Description

Method for preparing manganese oxide and nickel-cobalt oxide from nickel-cobalt-manganese ternary raw material TECHNICAL FIELD

[0001] The application belongs to the technical field of hydrometallurgy, and relates to a utilization method of a nickel-cobalt-manganese-containing raw material, in particular to a method for preparing manganese oxide and nickel-cobalt oxide from a nickel-cobalt-manganese ternary raw material. BACKGROUND

[0002] Since the advent of lithium ion batteries, they have been favored due to their high energy density, excellent electrochemical activity and other advantages, and are widely used in energy storage fields such as power batteries. With the continuous development of new energy vehicles, the demand for lithium ion batteries as a representative of new energy is also growing rapidly.

[0003] However, the service life of lithium ion batteries is generally 3-5 years. While the demand for lithium ion batteries is growing rapidly, the number of waste lithium ion batteries will also increase year by year. Waste lithium ion batteries, especially ternary lithium ion batteries, contain a large amount of valuable metals such as nickel, cobalt, manganese and lithium. If they are not recycled and utilized, they will not only cause serious damage to the environment, but also cause serious waste of resources.

[0004] Therefore, it is necessary to provide a method for preparing manganese oxide and nickel-cobalt oxide from a nickel-cobalt-manganese ternary raw material, which has a shorter process flow and higher product value compared to traditional methods. SUMMARY

[0005] The application provides a method for preparing manganese oxide and nickel-cobalt oxide from a nickel-cobalt-manganese ternary raw material. The method does not require extraction separation, and by precisely controlling the reaction conditions, manganese oxide and nickel-cobalt oxide can be obtained directly in steps. Compared with traditional methods, the process flow is shorter, the product value is higher, and the high-value utilization of the nickel-cobalt-manganese ternary raw material can be realized.

[0006] The application provides a method for preparing manganese oxide and nickel-cobalt oxide from a nickel-cobalt-manganese ternary raw material, which comprises the following steps:

[0007] After the nickel-cobalt-manganese ternary raw material is slurried, it is mixed with acid and a reducing agent for reduction leaching; then solid-liquid separation is performed to obtain a leaching solution;

[0008] The obtained leaching solution is subjected to oxidation and impurity removal to obtain a purified solution;

[0009] The obtained purified solution is subjected to pressurized oxidation to obtain a first precipitate and a first precipitate mother liquor;

[0010] The obtained first precipitate is used to prepare manganese oxide;

[0011] The first precipitate mother liquor is used to prepare nickel-cobalt oxide.

[0012] The method provided by the application can directly obtain manganese oxides and nickel-cobalt-manganese ternary oxides through precise control of reaction conditions without extraction separation, has a shorter process flow than traditional methods, higher product value, and can realize high-value utilization of nickel-cobalt-manganese ternary raw materials.

[0013] In one embodiment, the nickel-cobalt-manganese ternary raw material comprises mixed hydroxides (MHP) and / or waste nickel-cobalt-manganese ternary positive electrode powder.

[0014] In one embodiment, the solid-liquid ratio of the nickel-cobalt-manganese ternary raw material to the solvent during the slurry preparation is 1: (3-8), for example, can be 1:3, 1:4, 1:5, 1:6 or 1:8, but is not limited to the listed values, and the remaining values in the value range are also applicable.

[0015] In one embodiment, the amount of the acid is 1.05-1.2 times the theoretical requirement for leaching of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material, for example, can be 1.05 times, 1.1 times, 1.15 times or 1.2 times, but is not limited to the listed values, and the remaining values in the value range are also applicable.

[0016] In one embodiment, the acid comprises any one or a combination of at least two of sulfuric acid, nitric acid or hydrochloric acid, and typical but non-limiting combinations include a combination of sulfuric acid and nitric acid, a combination of nitric acid and hydrochloric acid, a combination of sulfuric acid and hydrochloric acid, or a combination of sulfuric acid, nitric acid and hydrochloric acid.

[0017] In one embodiment, the amount of the reducing agent is 1.1-1.5 times the theoretical requirement for reducing nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material to divalent ions, for example, can be 1.1 times, 1.2 times, 1.3 times, 1.4 times or 1.5 times, but is not limited to the listed values, and the remaining values in the value range are also applicable.

[0018] In one embodiment, the reducing agent comprises any one or a combination of at least two of sodium thiosulfate (Na2S2O3), sodium metabisulfite (Na2S2O5) or hydrogen peroxide (H2O2), and typical but non-limiting combinations include a combination of sodium thiosulfate and sodium metabisulfite, or a combination of sodium thiosulfate, sodium metabisulfite and hydrogen peroxide.

[0019] In one embodiment, the temperature of the reduction leaching is 40-80°C, for example, can be 40°C, 50°C, 60°C, 70°C or 80°C, but is not limited to the listed values, and the remaining values in the value range are also applicable.

[0020] In one embodiment, the time for the reduction leaching is 4-12h, for example, it can be 4h, 5h, 6h, 8h, 10h or 12h, but is not limited to the listed values, and the remaining values in the range of values are also applicable.

[0021] In one embodiment, the oxidizing impurity removal includes mixing a first oxidizing agent, an impurity removal agent and the leaching solution, adjusting pH value for impurity removal, and solid-liquid separation to obtain a purified solution.

[0022] In one embodiment, the first oxidizing agent includes any one or a combination of at least two of sodium chlorate, hydrogen peroxide or oxygen, and a typical but non-limiting combination includes a combination of sodium chlorate and hydrogen peroxide, a combination of hydrogen peroxide and oxygen, a combination of sodium chlorate and oxygen, or a combination of sodium chlorate, hydrogen peroxide and oxygen.

[0023] In one embodiment, the impurity removal agent includes sodium sulfide and / or sodium phosphate.

[0024] In one embodiment, the amount of the first oxidizing agent is 1-1.2 times of the theoretical amount for completely oxidizing Fe 2+ to Fe 3+ .

[0025] Specifically, in the process of oxidizing impurity removal, the concentration of residual Fe 2+ in the solution can be detected by titration to determine the amount of the first oxidizing agent, and when Fe 2+ is not detected, it is the end point of adding the first oxidizing agent.

[0026] In one embodiment, the amount of the impurity removal agent is 1-1.2 times of the theoretical amount for completely precipitating Cu 2+ and Zn 2+ in the leaching solution, for example, it can be 1 times, 1.05 times, 1.1 times, 1.15 times or 1.2 times, but is not limited to the listed values, and the remaining values in the range of values are also applicable.

[0027] In one embodiment, the pH value during the impurity removal is 4.5-5, for example, it can be 4.5, 4.8 or 5, but is not limited to the listed values, and the remaining values in the range of values are also applicable.

[0028] In one embodiment, the time for the impurity removal is 0.5-2h, for example, it can be 0.5h, 0.8h, 1h, 1.2h, 1.5h or 2h, but is not limited to the listed values, and the remaining values in the range of values are also applicable.

[0029] In one embodiment, the pressure oxidation includes mixing a second oxidizing agent and the purified solution, and performing pressure reaction.

[0030] In one embodiment, the second oxidizing agent is potassium permanganate.

[0031] In one embodiment, the molar ratio of the second oxidizing agent to Mn 2+ in the purifying solution is above 2:3.

[0032] In one embodiment, the temperature of the pressurized oxidation is 120-200℃, such as 120℃, 140℃, 150℃, 160℃, 180℃ or 200℃, but not limited to the listed values, and the remaining values in the range are also applicable.

[0033] The pressurized reaction described herein is performed in a closed container, and the pressure of the pressurized reaction increases with the increase of temperature, and is generally the saturated vapor pressure corresponding to the temperature.

[0034] In one embodiment, the time of the pressurized oxidation is 4-12h, such as 4h, 6h, 8h, 10h or 12h, but not limited to the listed values, and the remaining values in the range are also applicable.

[0035] In one embodiment, the first precipitate is washed and dried to obtain manganese dioxide.

[0036] Specifically, the washing refers to washing to neutral with deionized water.

[0037] Specifically, the drying refers to drying at 60-100℃, wherein the temperature of the drying is 60-100℃, such as 60℃, 70℃, 80℃, 90℃ or 100℃, but not limited to the listed values, and the remaining values in the range are also applicable.

[0038] In one embodiment, the molar ratio of Co 2+ and Ni 2+ in the first precipitate mother liquor is adjusted, and then a precipitating agent is added for a precipitation reaction, followed by solid-liquid separation, and the obtained second precipitate is washed, dried and calcined to obtain NiCo2O4.

[0039] In one embodiment, the adjustment of the molar ratio of Co 2+ and Ni 2+ refers to adding a cobalt salt and / or a nickel salt in the first precipitate mother liquor to adjust the molar ratio.

[0040] In one embodiment, the cobalt salt includes any one or a combination of at least two of cobalt sulfate, cobalt nitrate, cobalt acetate or cobalt chloride, and typical but non-limiting combinations include a combination of cobalt sulfate and cobalt nitrate, a combination of cobalt nitrate and cobalt acetate, a combination of cobalt acetate and cobalt chloride, or a combination of cobalt sulfate, cobalt nitrate, cobalt acetate and cobalt chloride.

[0041] In one embodiment, the nickel salt comprises any one or a combination of at least two of nickel sulfate, nickel nitrate, nickel acetate or nickel chloride, typically but not limited to combinations including nickel sulfate and nickel nitrate, nickel nitrate and nickel acetate, nickel acetate and nickel chloride, or combinations of nickel sulfate, nickel nitrate, nickel acetate and nickel chloride.

[0042] In one embodiment, the amount of the precipitant added is 1.2-1.5 times the theoretical requirement of the precipitation reaction, for example, it can be 1.2 times, 1.3 times, 1.4 times or 1.5 times, but is not limited to the listed values, and the remaining values within the range are also applicable.

[0043] In one embodiment, the precipitant comprises any one or a combination of at least two of sodium hydroxide, sodium carbonate, ammonium carbonate, oxalic acid or ammonium oxalate, typically but not limited to combinations including sodium hydroxide and sodium carbonate, sodium carbonate and ammonium carbonate, oxalic acid and ammonium oxalate, or combinations of sodium hydroxide, sodium carbonate and ammonium carbonate.

[0044] In one embodiment, the temperature of the calcination is 300-400℃, for example, it can be 300℃, 320℃, 350℃, 380℃ or 400℃, but is not limited to the listed values, and the remaining values within the range are also applicable.

[0045] In one embodiment, the time of the calcination is 2-4h, for example, it can be 2h, 2.5h, 3h, 3.5h or 4h, but is not limited to the listed values, and the remaining values within the range are also applicable.

[0046] As an optional embodiment of the method provided in the present application, the method comprises the following steps:

[0047] (1) After the nickel-cobalt-manganese ternary raw material is slurried, it is mixed with an acid and a reducing agent, and reduction leaching is performed at 40-80℃ for 4-12h; then solid-liquid separation is performed to obtain a leaching solution;

[0048] The acid comprises any one or a combination of at least two of sulfuric acid, nitric acid or hydrochloric acid, and the amount of the acid is 1.05-1.2 times the theoretical requirement of leaching of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material;

[0049] The reducing agent comprises any one or a combination of at least two of sodium thiosulfate, sodium metabisulfite or hydrogen peroxide, and the amount of the reducing agent is 1.1-1.5 times the theoretical requirement of reducing nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material to divalent ions;

[0050] (2) A first oxidizing agent, a decontaminating agent and the leaching solution are mixed, the pH value is adjusted to 4.5-5, decontamination is performed for 0.5-2h, and solid-liquid separation is performed to obtain a purified solution;

[0051] The first oxidizing agent comprises any one or a combination of at least two of sodium chlorate, hydrogen peroxide or oxygen; and the impurity removing agent comprises sodium sulfide and / or sodium phosphate;

[0052] The amount of the first oxidizing agent is 1.2-1.5 times of the theoretical amount required for completely oxidizing Fe 2+ in the leaching solution; 3+ to Fe

[0053] The amount of the impurity removing agent is 1-1.2 times of the theoretical amount required for completely precipitating Cu 2+ and Zn 2+ in the leaching solution;

[0054] (3) mixing a second oxidizing agent with the purified solution and performing a pressurized reaction at 120-200°C for 4-12h to obtain a first precipitate and a first precipitate mother liquor;

[0055] The second oxidizing agent is potassium permanganate; and the molar ratio of the potassium permanganate to Mn 2+ in the purified solution is 2:3 or more;

[0056] (4) washing the first precipitate and drying at 60-100°C to obtain manganese dioxide;

[0057] (5) adding a cobalt salt and / or a nickel salt to adjust the molar ratio of Co 2+ and Ni 2+ in the first precipitate mother liquor to 2:1, then adding a precipitating agent and performing a precipitation reaction at 20-60°C for 4-12h, solid-liquid separation, washing the obtained second precipitate, drying at 60-100°C and calcining at 300-400°C for 2-4h to obtain NiCo2O4;

[0058] The precipitating agent is any one or a combination of at least two of sodium hydroxide, sodium carbonate, ammonium carbonate, oxalic acid or ammonium oxalate; and the amount of the precipitating agent added is 1.2-1.5 times of the theoretical amount required for the precipitation reaction;

[0059] Steps (4) and (5) are not in a specific order.

[0060] Compared with the prior art, the present application has the following beneficial effects:

[0061] The method provided by the present application does not need extraction separation, and through precise control of the reaction conditions, manganese oxides and nickel-cobalt oxides can be directly obtained in steps, the process flow is shorter than that of the traditional method, the product value is higher, and high-value utilization of nickel-cobalt-manganese ternary raw materials can be realized. BRIEF DESCRIPTION OF DRAWINGS

[0062] FIG. 1 is a process flow diagram of the method for preparing manganese oxides and nickel-cobalt oxides from nickel-cobalt-manganese ternary raw materials provided by the present application. DETAILED DESCRIPTION

[0063] The technical solutions of the present application are further illustrated by the detailed description below. Those skilled in the art should understand that the examples are only to help understand the present application and should not be regarded as specific limitations of the present application.

[0064] The main components of the nickel-cobalt-manganese ternary raw material processed in the detailed description of the present application include: 22wt% of Ni, 6.8wt% of Co, 14wt% of Mn, 0.9wt% of Fe, 0.8wt% of Al, 0.2wt% of Cu, and 0.1wt% of Zn. The above description is only for the purpose of clearly illustrating the technical solutions and should not be regarded as a further limitation of the present application.

[0065] Example 1

[0066] The present example provides a method for preparing manganese oxide and nickel-cobalt oxide from a nickel-cobalt-manganese ternary raw material as shown in Figure 1, the method comprising the following steps:

[0067] (1) After the nickel-cobalt-manganese ternary raw material is slurried, it is mixed with sulfuric acid and sodium thiosulfate, and reduction leaching is carried out at 60°C for 8h; then solid-liquid separation is carried out to obtain a leaching solution;

[0068] During the slurry preparation, the solid-liquid ratio of the nickel-cobalt-manganese ternary raw material to the solvent is 1:5, and the unit of the solid-liquid ratio is g / mL;

[0069] The amount of sulfuric acid used is 1.15 times the theoretical amount required for leaching of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material;

[0070] The amount of sodium thiosulfate used is 1.3 times the theoretical amount required for reducing nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material to divalent ions;

[0071] (2) Mix the first oxidizing agent, the impurity removal agent and the leaching solution, adjust the pH value to 4.8 using sodium hydroxide, carry out impurity removal for 1h, and then carry out solid-liquid separation to obtain a purified solution;

[0072] The first oxidizing agent is sodium chlorate; the impurity removal agent is sodium sulfide;

[0073] The amount of the first oxidizing agent used is 1.1 times the actual amount required for oxidizing Fe 2+ in the leaching solution to Fe 3+ ;

[0074] The amount of the impurity removal agent used is 1.1 times the theoretical amount required for completely precipitating Cu 2+ and Zn 2+ in the leaching solution;

[0075] (3) mixing the second oxidant with the purified solution, and performing pressurized reaction at 160℃ for 8h to obtain a first precipitate and a first precipitate mother liquor;

[0076] The second oxidant is potassium permanganate; the molar ratio of the potassium permanganate to Mn 2+ in the purified solution is 2:3;

[0077] (4) washing the first precipitate obtained by deionized water until neutral, and drying at 80℃ to obtain manganese dioxide;

[0078] (5) adjusting the molar ratio of Co 2+ and Ni 2+ in the first precipitate mother liquor to 2:1 by using cobalt sulfate and nickel sulfate, then adding sodium hydroxide, and performing precipitation reaction at 40℃ for 8h, and then solid-liquid separation, washing the second precipitate obtained by deionized water until neutral, drying at 80℃, and calcining at 350℃ for 3h to obtain NiCo2O4;

[0079] The adding amount of the sodium hydroxide is 1.3 times of the theoretical requirement of the precipitation reaction;

[0080] The step (4) and the step (5) are not in the order.

[0081] Embodiment 2

[0082] The embodiment provides a method for preparing manganese oxide and nickel cobalt oxide from a nickel cobalt manganese ternary raw material as shown in FIG. 1, and the method comprises the following steps:

[0083] (1) after the nickel cobalt manganese ternary raw material is slurried, the nickel cobalt manganese ternary raw material is mixed with sulfuric acid and sodium pyrosulfite, and reduction leaching is performed at 40℃ for 12h; and then solid-liquid separation is performed to obtain a leaching solution;

[0084] During the slurry preparation, the solid-liquid ratio of the nickel cobalt manganese ternary raw material to the solvent is 1:3, and the unit of the solid-liquid ratio is g / mL;

[0085] The amount of the sulfuric acid is 1.2 times of the theoretical requirement of leaching of nickel, cobalt and manganese in the nickel cobalt manganese ternary raw material;

[0086] The amount of the sodium pyrosulfite is 1.5 times of the theoretical requirement of reducing nickel, cobalt and manganese in the nickel cobalt manganese ternary raw material to divalent ions;

[0087] (2) mixing a first oxidant, a decontaminating agent and the leaching solution, adjusting the pH value to 4.5 by using sodium hydroxide, and performing decontamination for 0.5h, and then performing solid-liquid separation to obtain a purified solution;

[0088] The first oxidant is hydrogen peroxide; and the decontaminating agent is sodium phosphate;

[0089] The amount of the first oxidant is 1.2 times of the theoretical requirement of reducing Fe 2+All oxidized to Fe 3+ The actual amount used;

[0090] The amount of the impurity removal agent used is to remove Cu from the leachate. 2+ With Zn 2+ One times the theoretical dosage for complete precipitation;

[0091] (3) Mix the second oxidant and the purification liquid, and carry out a pressurized reaction at 120°C for 12 hours to obtain the first precipitate and the first precipitate mother liquor;

[0092] The second oxidant is potassium permanganate; the potassium permanganate reacts with Mn in the purification solution. 2+ The molar ratio is 2:3;

[0093] (4) Wash the first precipitate obtained by washing with deionized water until neutral, and dry it at 60°C to obtain manganese dioxide;

[0094] (5) Use cobalt sulfate and nickel sulfate to adjust the Co content in the first precipitate mother liquor. 2+ and Ni 2+ The molar ratio was 2:1, and then sodium hydroxide was added. The precipitation reaction was carried out at 20℃ for 12h. The solid and liquid were separated, and the second precipitate was washed with deionized water until neutral, dried at 60℃ and calcined at 300℃ for 4h to obtain NiCo2O4.

[0095] The amount of sodium hydroxide added is 1.2 times the theoretical amount required for the precipitation reaction;

[0096] Steps (4) and (5) are not in any particular order.

[0097] Example 3

[0098] This embodiment provides a method for preparing manganese oxide and nickel-cobalt oxide from a nickel-cobalt-manganese ternary raw material, as shown in Figure 1. The method includes the following steps:

[0099] (1) After the nickel-cobalt-manganese ternary raw materials are pulped, they are mixed with hydrochloric acid and sodium thiosulfate and leached at 80°C for 4 hours; then solid-liquid separation is performed to obtain the leachate.

[0100] During the pulping process, the solid-liquid ratio of the nickel-cobalt-manganese ternary raw material to the solvent is 1:8, and the unit of the solid-liquid ratio is g / mL.

[0101] The amount of hydrochloric acid used is 1.05 times the theoretical leaching amount of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material;

[0102] The amount of sodium thiosulfate used is 1.1 times the theoretical amount required to reduce nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material to divalent ions;

[0103] (2) mixing the first oxidizing agent, the impurity removing agent and the leaching solution, adjusting pH value to 5 by sodium hydroxide, removing impurities for 2 hours, solid-liquid separation, obtaining purified solution;

[0104] The first oxidizing agent is hydrogen peroxide, and the impurity removing agent is sodium sulfide.

[0105] The amount of the first oxidizing agent is 1.2 times of the theoretical amount of completely precipitating Fe 2+ in the leaching solution. 3+ The actual amount of use;

[0106] The amount of the impurity removing agent is 1.2 times of the theoretical amount of completely precipitating Cu 2+ and Zn 2+ in the leaching solution.

[0107] (3) mixing the second oxidizing agent and the purified solution, performing pressurized reaction at 200℃ for 4 hours, obtaining first precipitate and first precipitate mother liquor;

[0108] The second oxidizing agent is potassium permanganate, and the molar ratio of the potassium permanganate to Mn 2+ in the purified solution is 2:3.

[0109] (4) washing the obtained first precipitate with deionized water until neutral, drying at 100℃, obtaining manganese dioxide.

[0110] (5) adjusting the molar ratio of Co 2+ and Ni 2+ in the first precipitate mother liquor to 2:1 by using cobalt sulfate and nickel sulfate, then adding sodium hydroxide, performing precipitation reaction at 60℃ for 4 hours, solid-liquid separation, washing the obtained second precipitate with deionized water until neutral, drying at 100℃ and calcining at 400℃ for 2 hours, obtaining NiCo2O4.

[0111] The amount of the added sodium hydroxide is 1.5 times of the theoretical requirement of the precipitation reaction.

[0112] Steps (4) and (5) are not in a specific order.

[0113] Example 4

[0114] The embodiment provides a method for preparing manganese oxide and nickel-cobalt oxide from a nickel-cobalt-manganese ternary raw material, wherein, except that the amount of sulfuric acid in step (1) is 1 times of the theoretical requirement of leaching nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material, the rest is the same as in example 1.

[0115] Example 5

[0116] The embodiment provides a method for preparing manganese oxide and nickel cobalt oxide from a nickel cobalt manganese ternary raw material, wherein, except that the amount of sodium thiosulfate in step (1) is 1 times the theoretical requirement amount of nickel, cobalt and manganese in the nickel cobalt manganese ternary raw material, the rest is the same as in example 1.

[0117] Example 6

[0118] The embodiment provides a method for preparing manganese oxide and nickel cobalt oxide from a nickel cobalt manganese ternary raw material, wherein, except that the amount of sodium thiosulfate in step (1) is 1 times the theoretical requirement amount of nickel, cobalt and manganese in the nickel cobalt manganese ternary raw material, the rest is the same as in example 1.

[0119] Example 7

[0120] The embodiment provides a method for preparing manganese oxide and nickel cobalt oxide from a nickel cobalt manganese ternary raw material, wherein, except that the amount of sodium thiosulfate in step (1) is 1 times the theoretical requirement amount of nickel, cobalt and manganese in the nickel cobalt manganese ternary raw material, the rest is the same as in example 1. 2+ And Zn 2+ The rest is the same as in example 1.

[0121] Example 8

[0122] The embodiment provides a method for preparing manganese oxide and nickel cobalt oxide from a nickel cobalt manganese ternary raw material, wherein, except that the amount of sodium thiosulfate in step (1) is 1 times the theoretical requirement amount of nickel, cobalt and manganese in the nickel cobalt manganese ternary raw material, the rest is the same as in example 1.

[0123] Example 9

[0124] The embodiment provides a method for preparing manganese oxide and nickel cobalt oxide from a nickel cobalt manganese ternary raw material, wherein, except that the amount of sodium thiosulfate in step (1) is 1 times the theoretical requirement amount of nickel, cobalt and manganese in the nickel cobalt manganese ternary raw material, the rest is the same as in example 1.

[0125] Performance characterization

[0126] In the method provided in the above embodiment, the recovery rates of Mn, Ni and Co and the purity of the obtained manganese dioxide and NiCo2O4 are determined, and the obtained results are shown in Table 1.

[0127] Wherein, the recovery rates of Mn, Ni and Co are based on the content of Mn, Ni and Co in the nickel cobalt manganese ternary raw material.

[0128] Table 1

[0129] In summary, the method provided in the application does not need extraction separation, and through accurate control of the reaction conditions, manganese oxides and nickel-cobalt oxides can be directly obtained in steps, the process flow is shorter than that of the traditional method, the product value is higher, and high-value utilization of nickel-cobalt-manganese ternary raw materials can be realized.

[0130] The above merely describes a specific embodiment of the application, but the protection scope of the application is not limited thereto, and those skilled in the art should understand that any change or replacement within the technical scope disclosed in the application, which can be easily thought of by any person skilled in the art, falls within the protection scope and disclosure scope of the application.

Claims

1. A method for preparing manganese oxide and nickel-cobalt oxide from a nickel-cobalt-manganese ternary raw material, comprising the following steps: After the nickel-cobalt-manganese ternary raw material is slurried, the slurry is mixed with an acid and a reducing agent to perform a reduction leaching, and then solid-liquid separation is performed to obtain a leaching solution; The obtained leaching solution is subjected to oxidative impurity removal to obtain a purified solution; The obtained purified solution is subjected to pressurized oxidation to obtain a first precipitate and a first precipitate mother liquor; The obtained first precipitate is used to prepare manganese oxide; The first precipitate mother liquor is used to prepare nickel-cobalt oxide.

2. The method of claim 1, wherein, The nickel-cobalt-manganese ternary raw material comprises mixed hydroxides and / or waste nickel-cobalt-manganese ternary positive electrode powder.

3. The method of claim 1 or 2, wherein, During the slurry preparation, the solid-liquid ratio of the nickel-cobalt-manganese ternary raw material to the solvent is 1: (3-8), and the unit of the solid-liquid ratio is g / mL.

4. The method according to any one of claims 1 to 3, wherein, The amount of the acid is 1.05-1.2 times the theoretical amount required for leaching of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material; Optionally, the amount of the reducing agent is 1.1-1.5 times the theoretical amount required for reducing nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material to divalent ions.

5. The method according to any one of claims 1 to 4, wherein, The temperature of the reduction leaching is 40-80℃. Optionally, the time of the reduction leaching is 4-12h.

6. The method according to any one of claims 1 to 5, wherein, The oxidative impurity removal comprises mixing a first oxidizing agent, an impurity removal agent and the leaching solution, adjusting the pH value to perform impurity removal, and then performing solid-liquid separation to obtain the purified solution.

7. The method of claim 6, wherein, The amount of the first oxidizing agent is an amount that oxidizes Fe 2+ to Fe 3+ in the leach solution to the actual demand amount. Optionally, the amount of the impurity removal agent is 1-1.2 times the theoretical amount for complete precipitation of Cu 2+ with Zn 2+ 1-1.2 times the theoretical amount for complete precipitation Optionally, the pH value during the impurity removal is 4.5-5. Optionally, the time of the impurity removal is 0.5-2h.

8. The method of any one of claims 1-7, wherein, The pressurized oxidation comprises mixing a second oxidizing agent with the purified solution to perform pressurized reaction.

9. The method of claim 8, wherein, The second oxidant and Mn in the purification solution 2+ The molar ratio is 2:3 or higher; Optionally, the temperature of the pressurized oxidation is 120-200℃. Optionally, the time of the pressurized oxidation is 4-12h.

10. The method of any one of claims 1-9, wherein, The first precipitate is washed and dried to obtain manganese dioxide.

11. The method of any one of claims 1-10, wherein, The molar ratio of Co 2+ and Ni 2+ in the first precipitation mother liquor is adjusted, then a precipitant is added to perform a precipitation reaction, solid-liquid separation is performed, the obtained second precipitate is washed, dried and calcined to obtain NiCo2O4.

12. The method of claim 11, wherein, The amount of the precipitant added is 1.2-1.5 times the theoretical amount required for the precipitation reaction. Optionally, the temperature of the calcination is 300-400℃. Optionally, the time of the calcination is 2-4h.

13. The method of claim 1, wherein, The method comprises the following steps: (1) After the nickel-cobalt-manganese ternary raw material is slurried, the slurry is mixed with an acid and a reducing agent to perform reduction leaching at 40-80℃ for 4-12h, and then solid-liquid separation is performed to obtain a leaching solution; The acid comprises any one or a combination of at least two of sulfuric acid, nitric acid or hydrochloric acid; The amount of the acid is 1.05-1.2 times the theoretical amount required for leaching of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material; The reducing agent comprises any one or a combination of at least two of sodium thiosulfate, sodium metabisulfite or hydrogen peroxide; The amount of the reducing agent is 1.1-1.5 times the theoretical amount required for reducing nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material to divalent ions; (2) A first oxidizing agent, an impurity removal agent and the leaching solution are mixed, the pH value is adjusted to 4.5-5, impurity removal is performed for 0.5-2h, and then solid-liquid separation is performed to obtain a purified solution; The first oxidizing agent comprises any one or a combination of at least two of sodium chlorate, hydrogen peroxide or oxygen; and the impurity removal agent comprises sodium sulfide and / or sodium phosphate; The amount of the first oxidizing agent is an amount that oxidizes Fe 2+ to Fe 3+ in the leach solution to the actual demand amount. The amount of the impurity removal agent is 1-1.2 times the theoretical amount for complete precipitation of Cu 2+ with Zn 2+ 1-1.2 times the theoretical amount for complete precipitation. (3) A second oxidizing agent and the purified solution are mixed to perform pressurized reaction at 120-200℃ for 4-12h to obtain a first precipitate and a first precipitate mother liquor; The second oxidizing agent is potassium permanganate; the molar ratio of the potassium permanganate to Mn 2+ in the purification liquid is 2:3 or more. (4) washing the obtained first precipitate and drying at 60-100°C to obtain manganese dioxide; (5) adding cobalt salt and / or nickel salt to adjust the molar ratio of Co 2+ and Ni 2+ to 2:1, then adding precipitant, carrying out precipitation reaction at 20-60℃ for 4-12h, solid-liquid separation, washing the obtained second precipitate, drying at 60-100℃, and calcining at 300-400℃ for 2-4h to obtain NiCo2O4; The precipitant is any one or at least two combinations of sodium hydroxide, sodium carbonate, ammonium carbonate, oxalic acid or ammonium oxalate; The addition amount of the precipitant is 1.2-1.5 times of the theoretical requirement of the precipitation reaction; Steps (4) and (5) are not in a specific order.

Images