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

Abstract

The invention relates to a method for preparing manganese oxide and nickel-cobalt oxide from nickel-cobalt-manganese ternary raw materials, which comprises the following steps: pulping the nickel-cobalt-manganese ternary raw materials, mixing with acid and a reducing agent, and carrying out reduction leaching; then carrying out solid-liquid separation to obtain a leaching solution; carrying out oxidation impurity removal on the obtained leaching solution to obtain a purified solution; pressurizing and oxidizing the obtained purified liquid to obtain a first precipitate and a first precipitate mother solution; the obtained first precipitate is used for preparing manganese oxide; the first precipitation mother liquor is used for preparing nickel-cobalt oxide. According to the method, extraction separation is not needed, the manganese oxide and the nickel-cobalt oxide can be directly obtained step by step through accurate control over reaction conditions, compared with a traditional method, the technological process is shorter, the product value is higher, and high-valued utilization of the nickel-cobalt-manganese ternary raw materials can be achieved.

Description

[0001] The present invention claims the priority of the prior application No. 2024110702502, whose application date is August 6, 2024. The name of the accepting agency of the prior application is China National Intellectual Property Administration, and the name of the invention of the prior application is “A method for preparing manganese oxide and nickel cobalt oxide from nickel-cobalt-manganese ternary raw materials”. Technical Field

[0002] The invention belongs to the technical field of hydrometallurgy, and relates to a method for utilizing a raw material containing nickel, cobalt and manganese, and in particular to a method for preparing manganese oxide and nickel-cobalt oxide from a ternary raw material of nickel, cobalt and manganese. Background Art

[0003] Since its introduction, lithium-ion batteries have been favored for their high energy density and excellent electrochemical activity, 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 new energy is also growing rapidly.

[0004] However, the life of lithium-ion batteries is generally 3-5 years. As lithium-ion batteries grow 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, they will not only cause serious damage to the environment, but also cause serious waste of resources.

[0005] Therefore, it is necessary to provide a method for preparing manganese oxide and nickel-cobalt oxide from nickel-cobalt-manganese ternary raw materials, which has a shorter process flow and higher product value than the traditional method. Summary of the invention

[0006] The object of the present invention is to provide a method for preparing manganese oxide and nickel cobalt oxide from nickel-cobalt-manganese ternary raw materials. The method does not require extraction and separation. Through precise control of reaction conditions, manganese oxide and nickel cobalt oxide can be directly obtained step by step. Compared with traditional methods, the process flow is shorter and the product value is higher, and high-value utilization of nickel-cobalt-manganese ternary raw materials can be achieved.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] The present invention provides a method for preparing manganese oxide and nickel-cobalt oxide from a nickel-cobalt-manganese ternary raw material, the method comprising the following steps:

[0009] After the nickel-cobalt-manganese ternary raw materials are pulped, they are mixed with acid and a reducing agent for reduction leaching; then the solid and liquid are separated to obtain a leachate;

[0010] The obtained leaching solution is oxidized and impurities are removed to obtain a purified solution;

[0011] The obtained purified liquid is subjected to pressure oxidation to obtain a first precipitate and a first precipitate mother liquid;

[0012] The obtained first precipitate is used to prepare manganese oxide;

[0013] The first precipitation mother liquor is used to prepare nickel-cobalt oxide.

[0014] The method provided by the present invention does not require extraction and separation. Through precise control of reaction conditions, manganese oxide and nickel-cobalt oxide can be directly obtained step by step. Compared with the traditional method, the process flow is shorter and the product value is higher, and high-value utilization of nickel-cobalt-manganese ternary raw materials can be achieved.

[0015] Preferably, the nickel-cobalt-manganese ternary raw material includes mixed hydroxide (MHP) and / or waste nickel-cobalt-manganese ternary positive electrode powder.

[0016] Preferably, during the slurrying, the solid-liquid ratio of the nickel-cobalt-manganese ternary raw material to the solvent is 1:(3-8), for example, it can be 1:3, 1:4, 1:5, 1:6 or 1:8, but is not limited to the listed values, and the remaining unlisted values ​​within the numerical range are also applicable. The unit of the solid-liquid ratio is g / mL.

[0017] Preferably, the amount of the acid used is 1.05-1.2 times the theoretical leaching requirements of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material, for example, it can be 1.05 times, 1.1 times, 1.15 times or 1.2 times, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0018] Preferably, the acid comprises any one of sulfuric acid, nitric acid or hydrochloric acid or a combination of at least two thereof, 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.

[0019] Preferably, the amount of the reducing agent used is 1.1-1.5 times the theoretical amount required to reduce nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material to divalent ions, for example, it 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 other values ​​not listed within the numerical range are also applicable.

[0020] Preferably, the reducing agent comprises sodium thiosulfate (Na 2 S 2 O 3 ), sodium metabisulfite (Na 2 S 2 O 5 ) or hydrogen peroxide (H 2 O 2), a typical but non-limiting combination includes a combination of sodium thiosulfate and sodium metabisulfite, or a combination of sodium thiosulfate, sodium metabisulfite and hydrogen peroxide.

[0021] Preferably, the reduction leaching temperature is 40-80°C, for example, 40°C, 50°C, 60°C, 70°C or 80°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0022] Preferably, the reduction leaching time is 4-12 h, for example, 4 h, 5 h, 6 h, 8 h, 10 h or 12 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0023] Preferably, the oxidation impurity removal comprises: mixing a first oxidant, an impurity remover and a leaching solution, adjusting the pH value to remove impurities, and separating the solid from the liquid to obtain a purified solution.

[0024] Preferably, the first oxidant comprises any one of sodium chlorate, hydrogen peroxide or oxygen, or a combination of at least two thereof. Typical but non-limiting combinations include 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.

[0025] Preferably, the impurity remover comprises sodium sulfide and / or sodium phosphate.

[0026] Preferably, the amount of the first oxidant is 2+ All oxidized to Fe 3+ actual usage.

[0027] For example, during the oxidation and impurity removal process, the residual Fe in the solution can be detected by titration. 2+ The concentration of Fe 2+ When , the addition of the first oxidant ends.

[0028] Preferably, the amount of the impurity remover is 2+ With Zn 2+ 1-1.2 times of the theoretical amount for complete precipitation, for example, 1 time, 1.05 times, 1.1 times, 1.15 times or 1.2 times, but not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0029] Preferably, the pH value during the impurity removal is 4.5-5, for example, 4.5, 4.8 or 5, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0030] Preferably, the impurity removal time 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 other unlisted values ​​within the numerical range are also applicable.

[0031] Preferably, the pressure oxidation comprises: mixing the second oxidant and the purification liquid to perform a pressure reaction.

[0032] Preferably, the second oxidant is potassium permanganate.

[0033] Preferably, the second oxidant and the Mn in the purification liquid 2+ The molar ratio is 2:3 or more.

[0034] Preferably, the temperature of the pressurized oxidation is 120-200°C, for example, 120°C, 140°C, 150°C, 160°C, 180°C or 200°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0035] The pressurized reaction of the present invention is carried out in a closed container, and the pressure of the pressurized reaction increases with the increase of temperature, which is usually the saturated vapor pressure corresponding to the temperature.

[0036] Preferably, the pressurized oxidation time is 4-12 hours, for example, 4 hours, 6 hours, 8 hours, 10 hours or 12 hours, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0037] Preferably, the first precipitate is washed and dried to obtain manganese dioxide.

[0038] Exemplarily, the washing refers to washing with deionized water until neutral.

[0039] Exemplarily, the drying refers to drying at 60-100°C, wherein the drying temperature is 60-100°C, for example, it can be 60°C, 70°C, 80°C, 90°C or 100°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0040] Preferably, the first precipitation mother liquor is adjusted to have Co 2+ and Ni 2+ The molar ratio of NiCo is then added to the precipitant for precipitation reaction, solid-liquid separation, and the obtained second precipitate is washed, dried and calcined to obtain NiCo 2 O 4 .

[0041] Preferably, the adjustment Co 2+ and Ni 2+ The molar ratio refers to adding cobalt salt and / or nickel salt to the first precipitation mother liquor to adjust the molar ratio.

[0042] Preferably, the cobalt salt comprises any one of cobalt sulfate, cobalt nitrate, cobalt acetate or cobalt chloride, or a combination of at least two thereof. 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.

[0043] Preferably, the nickel salt includes any one of nickel sulfate, nickel nitrate, nickel acetate or nickel chloride, or a combination of at least two of them. Typical but non-limiting combinations include a combination of nickel sulfate and nickel nitrate, a combination of nickel nitrate and nickel acetate, a combination of nickel acetate and nickel chloride, or a combination of nickel sulfate, nickel nitrate, nickel acetate and nickel chloride.

[0044] Preferably, the amount of the precipitant added is 1.2-1.5 times the theoretical amount required for 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 other values ​​not listed within the numerical range are also applicable.

[0045] Preferably, the precipitant comprises any one of sodium hydroxide, sodium carbonate, ammonium carbonate, oxalic acid or ammonium oxalate, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of sodium hydroxide and sodium carbonate, a combination of sodium carbonate and ammonium carbonate, a combination of oxalic acid and ammonium oxalate, or a combination of sodium hydroxide, sodium carbonate and ammonium carbonate.

[0046] Preferably, the calcination temperature is 300-400°C, for example, 300°C, 320°C, 350°C, 380°C or 400°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0047] Preferably, the calcination time is 2-4 h, for example, 2 h, 2.5 h, 3 h, 3.5 h or 4 h, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0048] As a preferred technical solution of the method provided by the present invention, the method comprises the following steps:

[0049] (1) After the nickel-cobalt-manganese ternary raw material is pulped, it is mixed with an acid and a reducing agent, and reduction leaching is performed at 40-80° C. for 4-12 hours; then the solid and liquid are separated to obtain a leachate;

[0050] The acid includes any one of sulfuric acid, nitric acid or hydrochloric acid or a combination of at least two of them, and the amount of the acid used is 1.05-1.2 times the theoretical leaching requirement of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material;

[0051] The reducing agent includes any one of sodium thiosulfate, sodium pyrosulfite or hydrogen peroxide or a combination of at least two thereof; the amount of the reducing agent used is 1.1-1.5 times the theoretical amount required to reduce nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material to divalent ions;

[0052] (2) mixing the first oxidant, the impurity remover and the leaching solution, adjusting the pH value to 4.5-5, removing impurities for 0.5-2h, and separating the solid and liquid to obtain a purified solution;

[0053] The first oxidant includes any one of sodium chlorate, hydrogen peroxide or oxygen or a combination of at least two thereof; the impurity remover includes sodium sulfide and / or sodium phosphate;

[0054] The amount of the first oxidant is to reduce the Fe 2+ All oxidized to Fe 3+ The actual amount of

[0055] The amount of the impurity remover is to reduce the Cu 2+ With Zn 2+ 1-1.2 times the theoretical amount for complete precipitation;

[0056] (3) mixing the second oxidant and the purified liquid, and reacting under pressure at 120-200° C. for 4-12 hours to obtain a first precipitate and a first precipitate mother liquor;

[0057] The second oxidant is potassium permanganate; the potassium permanganate and Mn in the purification solution 2+ The molar ratio is 2:3 or more;

[0058] (4) washing the obtained first precipitate and drying it at 60-100° C. to obtain manganese dioxide;

[0059] (5) Add cobalt salt and / or nickel salt to adjust the Co content of the first precipitation mother liquor. 2+ and Ni 2+ The molar ratio of is 2:1, and then a precipitant is added, and a precipitation reaction is carried out at 20-60°C for 4-12 hours, and the solid-liquid separation is performed. The obtained second precipitate is washed, dried at 60-100°C, and calcined at 300-400°C for 2-4 hours to obtain NiCo 2 O 4 ;

[0060] The precipitant is any one of sodium hydroxide, sodium carbonate, ammonium carbonate, oxalic acid or ammonium oxalate, or a combination of at least two thereof; the amount of the precipitant added is 1.2-1.5 times the theoretical amount required for the precipitation reaction;

[0061] Step (4) and step (5) are performed in no particular order.

[0062] Compared with the prior art, the present invention has the following beneficial effects:

[0063] The method provided by the present invention does not require extraction and separation. Through precise control of reaction conditions, manganese oxide and nickel-cobalt oxide can be directly obtained step by step. Compared with the traditional method, the process flow is shorter and the product value is higher, and high-value utilization of nickel-cobalt-manganese ternary raw materials can be achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] Figure 1 The present invention provides a process flow chart of a method for preparing manganese oxide and nickel-cobalt oxide from nickel-cobalt-manganese ternary raw materials. DETAILED DESCRIPTION

[0065] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0066] The main components of the nickel-cobalt-manganese ternary raw material processed in the specific embodiment of the present invention include: 22wt% Ni, 6.8wt% Co, 14wt% Mn, 0.9wt% Fe, 0.8wt% Al, 0.2wt% Cu and 0.1wt% Zn. The above description is only for the purpose of clearly explaining the technical solution and is not regarded as a further limitation of the present invention.

[0067] Example 1

[0068] This embodiment provides a Figure 1 The method for preparing manganese oxide and nickel-cobalt oxide from nickel-cobalt-manganese ternary raw materials shown in the figure comprises the following steps:

[0069] (1) After slurrying, the nickel-cobalt-manganese ternary raw materials are mixed with sulfuric acid and sodium thiosulfate, and reduction leaching is performed at 60° C. for 8 hours; then the solid and liquid are separated to obtain a leachate;

[0070] During the slurrying, 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;

[0071] The amount of sulfuric acid used is 1.15 times the theoretical amount of nickel, cobalt and manganese required for leaching in the nickel-cobalt-manganese ternary raw material;

[0072] The amount of sodium thiosulfate used is 1.3 times the theoretical amount required to reduce nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material to divalent ions;

[0073] (2) mixing the first oxidant, the impurity remover and the leaching solution, adjusting the pH value to 4.8 using sodium hydroxide, removing impurities for 1 hour, and separating the solid and the liquid to obtain a purified solution;

[0074] The first oxidant is sodium chlorate; the impurity remover is sodium sulfide;

[0075] The amount of the first oxidant is to reduce the Fe 2+ All oxidized to Fe 3+ The actual amount of

[0076] The amount of the impurity remover is to reduce the Cu 2+ With Zn 2+ 1.1 times the theoretical amount for complete precipitation;

[0077] (3) mixing the second oxidant and the purified liquid, and reacting under pressure at 160° C. for 8 h to obtain a first precipitate and a first precipitate mother liquor;

[0078] The second oxidant is potassium permanganate; the potassium permanganate and Mn in the purification solution 2+ The molar ratio is 2:3;

[0079] (4) washing the obtained first precipitate with deionized water until it becomes neutral, and drying it at 80° C. to obtain manganese dioxide;

[0080] (5) Using cobalt sulfate and nickel sulfate to adjust the Co in the first precipitation mother liquor 2+ and Ni 2+ The molar ratio of is 2:1, and then sodium hydroxide is added, and the precipitation reaction is carried out at 40°C for 8h, and the solid-liquid separation is performed. The obtained second precipitate is washed with deionized water until neutral, dried at 80°C and calcined at 350°C for 3h to obtain NiCo 2 O 4 ;

[0081] The amount of sodium hydroxide added is 1.3 times the theoretical amount required for the precipitation reaction;

[0082] Step (4) and step (5) are performed in no particular order.

[0083] Example 2

[0084] This embodiment provides a Figure 1 The method for preparing manganese oxide and nickel-cobalt oxide from nickel-cobalt-manganese ternary raw materials shown in the figure comprises the following steps:

[0085] (1) After the nickel-cobalt-manganese ternary raw materials are pulped, they are mixed with sulfuric acid and sodium metabisulfite and subjected to reduction leaching at 40° C. for 12 hours; then the solid and liquid are separated to obtain a leachate;

[0086] During the slurrying, 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;

[0087] The amount of sulfuric acid used is 1.2 times the theoretical amount of nickel, cobalt and manganese required for leaching in the nickel-cobalt-manganese ternary raw material;

[0088] The amount of sodium pyrosulfite used is 1.5 times the theoretical amount required to reduce nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material to divalent ions;

[0089] (2) mixing the first oxidant, the impurity remover and the leaching solution, adjusting the pH value to 4.5 using sodium hydroxide, removing impurities for 0.5 h, and performing solid-liquid separation to obtain a purified solution;

[0090] The first oxidant is hydrogen peroxide; the impurity remover is sodium phosphate;

[0091] The amount of the first oxidant is to reduce the Fe 2+ All oxidized to Fe 3+ The actual amount of

[0092] The amount of the impurity remover is to reduce the Cu 2+ With Zn 2+ 1 times the theoretical amount for complete precipitation;

[0093] (3) mixing the second oxidant and the purified liquid, and reacting under pressure at 120° C. for 12 hours to obtain a first precipitate and a first precipitate mother liquor;

[0094] The second oxidant is potassium permanganate; the potassium permanganate and Mn in the purification solution 2+ The molar ratio is 2:3;

[0095] (4) washing the obtained first precipitate with deionized water until it becomes neutral, and drying it at 60° C. to obtain manganese dioxide;

[0096] (5) Using cobalt sulfate and nickel sulfate to adjust the Co in the first precipitation mother liquor 2+ and Ni 2+ The molar ratio of is 2:1, and then sodium hydroxide is added, and the precipitation reaction is carried out at 20°C for 12 hours, and the solid-liquid separation is performed. The obtained second precipitate is washed with deionized water until neutral, dried at 60°C and calcined at 300°C for 4 hours to obtain NiCo 2 O 4 ;

[0097] The amount of sodium hydroxide added is 1.2 times the theoretical amount required for precipitation reaction;

[0098] Step (4) and step (5) are performed in no particular order.

[0099] Example 3

[0100] This embodiment provides a Figure 1 The method for preparing manganese oxide and nickel-cobalt oxide from nickel-cobalt-manganese ternary raw materials shown in the figure comprises the following steps:

[0101] (1) After slurrying, the nickel-cobalt-manganese ternary raw materials are mixed with hydrochloric acid and sodium thiosulfate, and reduction leaching is performed at 80° C. for 4 hours; then the solid and liquid are separated to obtain a leachate;

[0102] During the slurrying, 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;

[0103] The amount of hydrochloric acid used is 1.05 times the theoretical amount of nickel, cobalt and manganese required for leaching in the nickel-cobalt-manganese ternary raw material;

[0104] 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;

[0105] (2) mixing the first oxidant, the impurity remover and the leaching solution, adjusting the pH value to 5 using sodium hydroxide, removing impurities for 2 hours, and separating the solid and the liquid to obtain a purified solution;

[0106] The first oxidant is hydrogen peroxide; the impurity remover is sodium sulfide;

[0107] The amount of the first oxidant is to reduce the Fe 2+ All oxidized to Fe 3+ The actual amount of

[0108] The amount of the impurity remover is to reduce the Cu 2+ With Zn 2+ 1.2 times the theoretical amount for complete precipitation;

[0109] (3) mixing the second oxidant and the purified liquid, and reacting under pressure at 200° C. for 4 h to obtain a first precipitate and a first precipitate mother liquid;

[0110] The second oxidant is potassium permanganate; the potassium permanganate and Mn in the purification solution 2+ The molar ratio is 2:3;

[0111] (4) washing the obtained first precipitate with deionized water until it becomes neutral, and drying it at 100° C. to obtain manganese dioxide;

[0112] (5) Using cobalt sulfate and nickel sulfate to adjust the Co in the first precipitation mother liquor 2+ and Ni 2+ The molar ratio of is 2:1, and then sodium hydroxide is added, and the precipitation reaction is carried out at 60°C for 4 hours, and the solid-liquid separation is performed. The obtained second precipitate is washed with deionized water until neutral, dried at 100°C and calcined at 400°C for 2 hours to obtain NiCo 2 O 4 ;

[0113] The amount of sodium hydroxide added is 1.5 times the theoretical amount required for the precipitation reaction;

[0114] Step (4) and step (5) are performed in no particular order.

[0115] Example 4

[0116] This embodiment provides a method for preparing manganese oxide and nickel cobalt oxide from a nickel-cobalt-manganese ternary raw material. Except that the amount of sulfuric acid used in step (1) is 1 times the theoretical amount required for leaching nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material, the rest is the same as Example 1.

[0117] Example 5

[0118] This embodiment provides a method for preparing manganese oxide and nickel cobalt oxide from a nickel-cobalt-manganese ternary raw material, except that the amount of sulfuric acid used in step (1) is 1.3 times the theoretical amount of nickel, cobalt and manganese required for leaching in the nickel-cobalt-manganese ternary raw material, the rest is the same as Example 1.

[0119] Example 6

[0120] This embodiment provides a method for preparing manganese oxide and nickel cobalt oxide from a nickel-cobalt-manganese ternary raw material, except that the amount of sodium thiosulfate used in step (1) is 1 times the theoretical amount required for reducing nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material to divalent ions, the rest is the same as Example 1.

[0121] Example 7

[0122] This embodiment provides a method for preparing manganese oxide and nickel cobalt oxide from nickel cobalt manganese ternary raw materials, except that the amount of impurity remover used in step (2) is to reduce the amount of Cu in the leaching solution to 2+ With Zn 2+ Except for 1.3 times the theoretical amount for complete precipitation, the rest is the same as Example 1.

[0123] Example 8

[0124] This embodiment provides a method for preparing manganese oxide and nickel cobalt oxide from nickel-cobalt-manganese ternary raw materials, except that the amount of precipitant sodium hydroxide used in step (5) is 1.1 times the theoretical amount required for precipitation reaction, the rest is the same as Example 1.

[0125] Example 9

[0126] This embodiment provides a method for preparing manganese oxide and nickel cobalt oxide from nickel-cobalt-manganese ternary raw materials, except that the amount of precipitant sodium hydroxide used in step (5) is 1.6 times the theoretical amount required for precipitation reaction, and the rest is the same as Example 1.

[0127] Performance Characterization

[0128] In the method provided in the above embodiment, the recovery rates of Mn, Ni, and Co and the obtained manganese dioxide and NiCo 2 O4 The purity of the obtained products was determined and the results are shown in Table 1.

[0129] Among them, the recovery rates of Mn, Ni and Co are based on the contents of Mn, Ni and Co in the nickel-cobalt-manganese ternary raw materials.

[0130] Table 1

[0131]

[0132] In summary, the method provided by the present invention does not require extraction and separation. Through precise control of reaction conditions, manganese oxide and nickel-cobalt oxide can be directly obtained step by step. Compared with the traditional method, the process flow is shorter and the product value is higher, and high-value utilization of nickel-cobalt-manganese ternary raw materials can be achieved.

[0133] The above description is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention are within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing manganese oxide and nickel-cobalt oxide from nickel-cobalt-manganese ternary raw materials, characterized in that: The method comprises the following steps: After the nickel-cobalt-manganese ternary raw materials are pulped, they are mixed with acid and a reducing agent for reduction leaching; then the solid and liquid are separated to obtain a leachate; The obtained leaching solution is oxidized and impurities are removed to obtain a purified solution; The obtained purified liquid is subjected to pressure oxidation to obtain a first precipitate and a first precipitate mother liquid; The obtained first precipitate is used to prepare manganese oxide; The first precipitation mother liquor is used to prepare nickel-cobalt oxide.

2. The method according to claim 1, characterized in that The nickel-cobalt-manganese ternary raw material includes mixed hydroxide and / or waste nickel-cobalt-manganese ternary positive electrode powder.

3. The method according to claim 1 or 2, characterized in that: During the slurrying, 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; Preferably, the amount of the acid used is 1.05-1.2 times the theoretical amount of nickel, cobalt and manganese leaching required in the nickel-cobalt-manganese ternary raw material; Preferably, the amount of the reducing agent used is 1.1-1.5 times the theoretical amount required to reduce nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material to divalent ions.

4. The method according to any one of claims 1 to 3, characterized in that: The reduction leaching temperature is 40-80°C; Preferably, the reduction leaching time is 4-12 hours.

5. The method according to any one of claims 1 to 4, characterized in that: The oxidation impurity removal comprises: mixing a first oxidant, an impurity remover and a leaching solution, adjusting the pH value to remove impurities, and separating the solid from the liquid to obtain a purified solution; Preferably, the amount of the first oxidant is 2+ All oxidized to Fe 3+ The actual demand; Preferably, the amount of the impurity remover is 2+ With Zn 2+ 1-1.2 times the theoretical amount for complete precipitation; Preferably, the pH value during the impurity removal is 4.5-5; Preferably, the time for removing impurities is 0.5-2h.

6. The method according to any one of claims 1 to 5, characterized in that: The pressurized oxidation comprises: mixing a second oxidant and a purification liquid to perform a pressurized reaction; Preferably, the second oxidant and the Mn in the purification liquid 2+ The molar ratio is 2:3 or more; Preferably, the temperature of the pressurized oxidation is 120-200°C; Preferably, the pressurized oxidation time is 4-12 hours.

7. The method according to any one of claims 1 to 6, characterized in that: The first precipitate is washed and dried to obtain manganese dioxide.

8. The method according to any one of claims 1 to 7, characterized in that: The first precipitation mother liquor is adjusted to Co 2+ and Ni 2+ The molar ratio of , and then adding a precipitant to carry out precipitation reaction, solid-liquid separation, the obtained second precipitate is washed, dried and calcined to obtain NiCo2O4.

9. The method according to claim 8, characterized in that The amount of the precipitant added is 1.2-1.5 times the theoretical amount required for the precipitation reaction; Preferably, the calcination temperature is 300-400°C; Preferably, the calcination time is 2-4 hours.

10. The method according to claim 1, characterized in that The method comprises the following steps: (1) After the nickel-cobalt-manganese ternary raw material is pulped, it is mixed with an acid and a reducing agent, and reduction leaching is performed at 40-80° C. for 4-12 hours; then the solid and liquid are separated to obtain a leachate; The acid includes any one of sulfuric acid, nitric acid or hydrochloric acid or a combination of at least two thereof; The amount of the acid used is 1.05-1.2 times the theoretical amount of nickel, cobalt and manganese required for leaching in the nickel-cobalt-manganese ternary raw material; The reducing agent includes any one of sodium thiosulfate, sodium pyrosulfite or hydrogen peroxide, or a combination of at least two thereof; The amount of the reducing agent used is 1.1-1.5 times the theoretical amount required to reduce nickel, cobalt and manganese in the nickel-cobalt-manganese ternary raw material to divalent ions; (2) mixing the first oxidant, the impurity remover and the leaching solution, adjusting the pH value to 4.5-5, removing impurities for 0.5-2h, and separating the solid and liquid to obtain a purified solution; The first oxidant includes any one of sodium chlorate, hydrogen peroxide or oxygen or a combination of at least two thereof; the impurity remover includes sodium sulfide and / or sodium phosphate; The amount of the first oxidant is to reduce the Fe 2+ All oxidized to Fe 3+ The actual demand; The amount of the impurity remover is to reduce the Cu 2+ With Zn 2+ 1-1.2 times the theoretical amount for complete precipitation; (3) mixing the second oxidant and the purified liquid, and reacting under pressure at 120-200° C. for 4-12 hours to obtain a first precipitate and a first precipitate mother liquor; The second oxidant is potassium permanganate; the potassium permanganate and Mn in the purification solution 2+ The molar ratio is 2:3 or more; (4) washing the obtained first precipitate and drying it at 60-100° C. to obtain manganese dioxide; (5) Add cobalt salt and / or nickel salt to adjust the Co content of the first precipitation mother liquor. 2+ and Ni 2+ The molar ratio of is 2:1, and then a precipitant is added, and a precipitation reaction is carried out at 20-60°C for 4-12 hours, and the solid-liquid separation is performed. The obtained second precipitate is washed, dried at 60-100°C, and calcined at 300-400°C for 2-4 hours to obtain NiCo2O4; The precipitant is any one of sodium hydroxide, sodium carbonate, ammonium carbonate, oxalic acid or ammonium oxalate, or a combination of at least two thereof; The amount of the precipitant added is 1.2-1.5 times the theoretical amount required for the precipitation reaction; Step (4) and step (5) are performed in no particular order.

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