Waste power battery ternary leachate one-step impurity removal treatment method

Abstract

The invention provides a waste power battery ternary leachate one-step impurity removal treatment method, which comprises the following steps: introducing a part of an aluminum source, controlling the Al / F molar ratio in a solution system to be greater than or equal to 4, adding an alkali source to adjust the pH value, and carrying out precipitation treatment, so that one-step precipitation impurity removal of Fe, Al and F can be realized, Ca, Mg and other elements are not introduced, in the liquid subjected to one-step impurity removal, the F content is lower than 100mg / L, the Fe content is lower than 10mg / L, the Al content is lower than 10mg / L, and the impurity removal rate is lower than 10mg / L; the method has the advantages of simple operation, simple equipment, low energy consumption, no pollution and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of recycling of waste power batteries, and specifically belongs to a method for one-step impurity removal treatment of ternary leaching solution of waste power batteries. Background Art

[0002] As the "heart" of new energy vehicles, the usage amount of power batteries is increasing day by day. Therefore, many countries are working on the low-cost and high-efficiency recycling of waste power batteries, hoping to maximize profits.

[0003] Currently, the power batteries used in new energy vehicles are mainly divided into two categories: ternary material lithium-ion batteries and lithium iron phosphate lithium-ion batteries. Among them, the ternary material lithium-ion batteries have higher energy density. The waste ternary material ion batteries contain various valuable metals such as Ni, Co, Mn, Cu, and Al. The heavy metals and electrolytes contained in them will cause great damage to the natural environment, and the various valuable metals and non-metallic materials contained in them have great recycling value and space.

[0004] The black powder after the disassembly and crushing of waste power batteries is usually subjected to reduction leaching with sulfuric acid and a reducing agent. The leaching solution (hereinafter referred to as ternary leaching solution) adjusts the pH by introducing a calcium source to achieve the purpose of removing iron and aluminum. The material solution after removing iron and aluminum enters P204 and P508 extraction for further purification and crystallization. The organic material solution of this full extraction process needs to be saponified by adding liquid alkali, and the alkali consumption is relatively high. Before extraction, the method for removing impurities from the ternary leaching solution is crucial. By semi-extraction and fine impurity removal, the alkali consumption in the extraction section can be reduced.

[0005] Although the method of adjusting the pH by adding a calcium source to remove iron and aluminum from the ternary leaching solution can reduce the iron and aluminum to below 1 ppm, the large introduction of calcium will form calcium slag to block the pipeline during the subsequent extraction and purification stage due to sulfuric acid back-extraction, and industrial lime will also introduce impurity magnesium.

[0006] Therefore, removing iron, aluminum, and fluoride ions from the ternary leaching solution by a one-step sedimentation method to avoid the introduction of calcium and magnesium impurities has important application prospects. Summary of the Invention

[0007] In view of the problems existing in the prior art, that is, for the impurity removal treatment of the ternary leaching solution of waste power batteries before extraction, Ca and Mg impurities are often introduced. The present invention provides a method for one-step impurity removal treatment of the ternary leaching solution of waste power batteries. By introducing a partial aluminum source and controlling the Al / F molar ratio in the solution system ≥ 4, and then adding an alkali source to adjust the pH for precipitation treatment, the one-step precipitation and impurity removal of Fe, Al, and F can be achieved without introducing other elements such as Ca and Mg, and it has the advantages of simple operation, simple equipment, low energy consumption, and no pollution.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] The object of the present invention is to provide a method for one-step impurity removal treatment of ternary leaching solution of waste power batteries. The method for one-step impurity removal treatment of ternary leaching solution of waste power batteries includes the following steps:

[0010] Prepare the ternary leaching solution of waste power batteries and perform a heating treatment. First, add an aluminum source until it is completely dissolved, control the Al / F molar ratio in the solution system to be ≥4, and then add an alkali source for precipitation treatment. After solid-liquid separation, a post-liquid after one-step impurity removal is obtained.

[0011] In the method for one-step impurity removal treatment of ternary leaching solution of waste power batteries of the present invention, by introducing a partial aluminum source, controlling the Al / F molar ratio in the solution system to be ≥4, and then adding an alkali source to adjust the pH for precipitation treatment, one-step precipitation impurity removal of Fe, Al, and F can be achieved without introducing other elements such as Ca and Mg, and it has the advantages of simple operation, simple equipment, low energy consumption, and no pollution.

[0012] Through experimental research, if the Al / F molar ratio after adding the aluminum source is <4, the precipitation generated by subsequent addition of the alkali source is less, the adsorption effect on F ions is weakened, and the impurity removal effect is affected.

[0013] As a preferred technical solution of the present invention, the source of the ternary leaching solution of waste power batteries includes: the black powder obtained by disassembling, crushing, and screening waste power batteries, and the ternary leaching solution obtained by leaching with sulfuric acid and hydrogen peroxide. It should be noted that after the black powder is leached with sulfuric acid and hydrogen peroxide, not only can Ni, Co, and Mn be leached in the form of low-valence ions, but also divalent iron can be oxidized to trivalent iron in the environment of hydrogen peroxide.

[0014] As a preferred technical solution of the present invention, in the ternary leaching solution of waste power batteries, the F content is 3-5 g / L, the Fe content is 0.7-0.9 g / L, and the Al content is 10-12 g / L.

[0015] It should be noted that, as is well known to those skilled in the art, the ternary leaching solution of waste power batteries of the present invention contains relatively high concentrations of nickel, cobalt, and manganese. However, the present invention focuses on the impurity removal treatment before the extraction operation and pays more attention to the contents of impurity elements such as F, Fe, and Al. Therefore, the present invention does not limit the specific concentrations of nickel, cobalt, and manganese.

[0016] As a preferred technical solution of the present invention, the target temperature of the heating treatment is 60-80 °C, such as 60 °C, 61 °C, 63 °C, 65 °C, 67 °C, 70 °C, 72 °C, 75 °C, 78 °C, or 80 °C, etc.

[0017] As a preferred technical solution of the present invention, the aluminum source includes aluminum sulfate octadecahydrate.

[0018] As a preferred technical solution of the present invention, an aluminum source is added until completely dissolved, and the Al / F molar ratio in the solution system is controlled to be 4-10. For example, the Al / F molar ratio is 4, the Al / F molar ratio is 4.5, the Al / F molar ratio is 5, the Al / F molar ratio is 5.5, the Al / F molar ratio is 6, the Al / F molar ratio is 6.5, the Al / F molar ratio is 7, the Al / F molar ratio is 7.5, the Al / F molar ratio is 8, the Al / F molar ratio is 8.5, the Al / F molar ratio is 9, or the Al / F molar ratio is 10, etc.

[0019] As a preferred technical solution of the present invention, the alkali source includes any one or a combination of at least two of sodium carbonate, sodium bicarbonate, sodium hydroxide, nickel hydroxide, or MHP.

[0020] It should be noted that, as is well known to those skilled in the art, MHP refers to nickel cobalt hydroxide, such as a nickel intermediate prepared from laterite nickel ore by high-pressure acid leaching technology. MHP is alkaline and has low contents of F, Fe, and Al impurities, and can fully be used as an alkali source for the present invention.

[0021] As a preferred technical solution of the present invention, an alkali source is added to adjust the pH of the reaction system to 4.5-5. For example, the pH of the reaction system is 4.5, the pH of the reaction system is 4.6, the pH of the reaction system is 4.7, the pH of the reaction system is 4.8, the pH of the reaction system is 4.9, or the pH of the reaction system is 5, etc.

[0022] As a preferred technical solution of the present invention, the time for the precipitation treatment is 2-5 h. For example, it is 2 h, 2.2 h, 2.5 h, 2.8 h, 3 h, 3.2 h, 3.5 h, 3.8 h, 4 h, 4.2 h, 4.5 h, 4.8 h, or 5 h, etc.

[0023] As a preferred technical solution of the present invention, in the liquid after one-step impurity removal, the F content is lower than 100 mg / L, the Fe content is lower than 10 mg / L, and the Al content is lower than 10 mg / L.

[0024] Compared with the prior art solutions, the present invention has at least the following beneficial effects:

[0025] (1) For the method for one-step impurity removal treatment of the ternary leaching solution of waste power batteries of the present invention, by introducing a partial aluminum source, controlling the Al / F molar ratio in the solution system ≥4, and then adding an alkali source to adjust the pH for precipitation treatment, the purpose of simultaneous precipitation of iron, aluminum, and fluorine is achieved, and the problems in the prior art such as the introduction of calcium and magnesium impurities due to impurity removal in the ternary leaching solution and the high fluorine concentration are solved.

[0026] (2) The one-step impurity removal treatment method for the ternary leaching solution of waste power batteries according to the present invention realizes the purpose of low-cost impurity removal from the ternary leaching solution and no introduction of new impurities through the one-step precipitation method by introducing an aluminum source, and has important application prospects.

[0027] (3) The one-step impurity removal treatment method for the ternary leaching solution of waste power batteries according to the present invention has the advantages of simple operation, simple equipment, low energy consumption, and no pollution. Specific embodiments

[0028] To facilitate the understanding of the present invention, the following examples are listed. Those skilled in the art should understand that the examples are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0029] The present invention provides a one-step impurity removal treatment method for the ternary leaching solution of waste power batteries. The one-step impurity removal treatment method for the ternary leaching solution of waste power batteries includes the following steps:

[0030] Step S1: Prepare the ternary leaching solution of waste power batteries. The source of the ternary leaching solution of waste power batteries includes: the black powder obtained by disassembling, crushing, and screening waste power batteries, and the ternary leaching solution obtained by leaching with sulfuric acid and hydrogen peroxide. In the ternary leaching solution of waste power batteries, the F content is 3-5 g / L, the Fe content is 0.7-0.9 g / L, the Al content is 10-12 g / L. Heat it to 60-80 °C, and add aluminum sulfate octadecahydrate according to the molar ratio of Al / F ≥ 4, and stir well until completely dissolved;

[0031] Step S2: Add an alkali source to the material solution obtained in Step S1, adjust the pH of the reaction system to 4.5-5, and stir for 2-5 h at 60-80 °C for precipitation treatment. After solid-liquid separation, obtain the solution after one-step impurity removal. In the solution after one-step impurity removal, the F content is less than 100 mg / L, the Fe content is less than 10 mg / L, and the Al content is less than 10 mg / L.

[0032] The source of the ternary leaching solution of waste power batteries in the specific embodiments of the present invention is all: the black powder obtained by disassembling, crushing, and screening waste power batteries, and the ternary leaching solution obtained by leaching with sulfuric acid and hydrogen peroxide; after the black powder is leached with sulfuric acid and hydrogen peroxide, not only can Ni, Co, and Mn be leached in the form of low-valent ions, but also divalent iron can be oxidized to trivalent iron in the environment of hydrogen peroxide.

[0033] Example 1

[0034] This example provides a one-step impurity removal treatment method for the ternary leaching solution of waste power batteries. The one-step impurity removal treatment method for the ternary leaching solution of waste power batteries includes the following steps:

[0035] Step S1: Measure 4 L of the ternary leaching solution of waste power batteries, with an F content of 4.1 g / L, an Fe content of 829.1 mg / L, and an Al content of 11.64 g / L. Pour it into a glass reactor, heat it up to 60 °C, and add aluminum sulfate octadecahydrate in proportion according to the molar ratio of Al / F = 4. Stir well until completely dissolved;

[0036] Step S2: Add sodium carbonate as an alkali source to the material solution obtained in Step S1, adjust the pH of the reaction system to 4.5, and stir at 60 °C for 2 h for precipitation treatment. After filtration, obtain the liquid after primary impurity removal; Through test analysis, in the liquid after primary impurity removal, the F content is 75.03 mg / L, the Fe content is 0.1 mg / L, and the Al content is 9.6 mg / L.

[0037] Example 2

[0038] This example provides a method for primary impurity removal treatment of the ternary leaching solution of waste power batteries. The method for primary impurity removal treatment of the ternary leaching solution of waste power batteries includes the following steps:

[0039] Step S1: Measure 4 L of the ternary leaching solution of waste power batteries, with an F content of 4.1 g / L, an Fe content of 829.1 mg / L, and an Al content of 11.64 g / L. Pour it into a glass reactor, heat it up to 80 °C, and add aluminum sulfate octadecahydrate in proportion according to the molar ratio of Al / F = 5. Stir well until completely dissolved;

[0040] Step S2: Add sodium carbonate as an alkali source to the material solution obtained in Step S1, adjust the pH of the reaction system to 5, and stir at 80 °C for 2 h for precipitation treatment. After filtration, obtain the liquid after primary impurity removal; Through test analysis, in the liquid after primary impurity removal, the F content is 24.70 mg / L, the Fe content is 0.1 mg / L, and the Al content is 4.2 mg / L.

[0041] Example 3

[0042] This example provides a method for primary impurity removal treatment of the ternary leaching solution of waste power batteries. The method for primary impurity removal treatment of the ternary leaching solution of waste power batteries includes the following steps:

[0043] Step S1: Measure 4 L of the ternary leaching solution of waste power batteries, with an F content of 4.1 g / L, an Fe content of 829.1 mg / L, and an Al content of 11.64 g / L. Pour it into a glass reactor, heat it up to 60 °C, and add aluminum sulfate octadecahydrate in proportion according to the molar ratio of Al / F = 5. Stir well until completely dissolved;

[0044] Step S2: adding sodium carbonate as an alkali source to the feed solution obtained in step S1, adjusting the pH of the reaction system to 5, stirring at 60° C. for 2 hours for precipitation treatment, and filtering to obtain a one-step impurity-removed liquid; after testing and analysis, the one-step impurity-removed liquid has an F content of 65.30 mg / L, an Fe content of 0.1 mg / L, and an Al content of 6.3 mg / L.

[0045] Example 4

[0046] This embodiment provides a one-step impurity removal treatment method for a ternary leachate of a waste power battery, and the one-step impurity removal treatment method for a ternary leachate of a waste power battery comprises the following steps:

[0047] Step S1: 4 L of ternary leachate from waste power batteries, with a F content of 4.1 g / L, a Fe content of 829.1 mg / L, and an Al content of 11.64 g / L, is measured and poured into a glass reactor, heated to 60° C., and aluminum sulfate 18hydrate is added at a molar ratio of Al / F=7, and stirred thoroughly until completely dissolved;

[0048] Step S2: adding sodium carbonate as an alkali source to the feed solution obtained in step S1, adjusting the pH of the reaction system to 4.5, stirring at 60° C. for 2 h for precipitation treatment, and filtering to obtain a one-step impurity-removed liquid; after testing and analysis, the one-step impurity-removed liquid has a F content of 20.37 mg / L, a Fe content of 0.1 mg / L, and an Al content of 9.82 mg / L; compared with the one-step impurity-removed liquid of Example 1, the F content corresponding to this example is significantly reduced.

[0049] Example 5

[0050] This embodiment provides a one-step impurity removal treatment method for a ternary leachate of a waste power battery, and the one-step impurity removal treatment method for a ternary leachate of a waste power battery comprises the following steps:

[0051] Step S1: 4L of ternary leachate from waste power batteries, with a F content of 4.1g / L, a Fe content of 829.1mg / L, and an Al content of 11.64g / L, is measured and poured into a glass reactor, heated to 60°C, and aluminum sulfate 18hydrate is added at a ratio of Al / F molar ratio = 10, and stirred thoroughly until completely dissolved;

[0052] Step S2: adding sodium carbonate as an alkali source to the feed solution obtained in step S1, adjusting the pH of the reaction system to 4.5, stirring at 60° C. for 2 h for precipitation treatment, and filtering to obtain a one-step impurity-removed liquid; after testing and analysis, the one-step impurity-removed liquid has an F content of 15.44 mg / L, an Fe content of 0.1 mg / L, and an Al content of 9.61 mg / L; compared with the one-step impurity-removed liquid of Example 1, the F content corresponding to this example is significantly reduced.

[0053] Example 6

[0054] This example provides a method for one-step impurity removal treatment of ternary leaching solution from waste power batteries. The method for one-step impurity removal treatment of ternary leaching solution from waste power batteries includes the following steps:

[0055] Step S1: Measure 4 L of ternary leaching solution from waste power batteries, with an F content of 4.1 g / L, an Fe content of 829.1 mg / L, and an Al content of 11.64 g / L. Pour it into a glass reaction kettle, heat it up to 60 °C, and add aluminum sulfate octadecahydrate in accordance with the molar ratio of Al / F = 11, and stir thoroughly until completely dissolved;

[0056] Step S2: Add sodium carbonate as an alkali source to the material solution obtained in Step S1, adjust the pH of the reaction system to 4.5, stir at 60 °C for 2 h for precipitation treatment, and filter to obtain the solution after one-step impurity removal. After test analysis, in the solution after one-step impurity removal, the F content is 14.96 mg / L, the Fe content is 0.5 mg / L, and the Al content is 11.7 mg / L; compared with the solution after one-step impurity removal in Example 1, the F content in this example is significantly reduced, but the Al content is significantly increased, which is not conducive to subsequent impurity removal and will increase the use cost of chemical reagents.

[0057] Example 7

[0058] This example provides a method for one-step impurity removal treatment of ternary leaching solution from waste power batteries. The method for one-step impurity removal treatment of ternary leaching solution from waste power batteries includes the following steps:

[0059] Step S1: Measure 4 L of ternary leaching solution from waste power batteries, with an F content of 4.1 g / L, an Fe content of 829.1 mg / L, and an Al content of 11.64 g / L. Pour it into a glass reaction kettle, heat it up to 60 °C, and add aluminum sulfate octadecahydrate in accordance with the molar ratio of Al / F = 4, and stir thoroughly until completely dissolved;

[0060] Step S2: Add sodium carbonate as an alkali source to the material solution obtained in Step S1, adjust the pH of the reaction system to 4, stir at 60 °C for 2 h for precipitation treatment, and filter to obtain the solution after one-step impurity removal. After test analysis, in the solution after one-step impurity removal, the F content is 103.4 mg / L, the Fe content is 7.11 mg / L, and the Al content is 12.13 mg / L; compared with the solution after one-step impurity removal in Example 1, the F content, Fe content, and Al content in this example are all increased, and the F and Al contents exceed the standard.

[0061] Example 8

[0062] This embodiment provides a method for one-step impurity removal treatment of ternary leaching solution from waste power batteries. The method for one-step impurity removal treatment of ternary leaching solution from waste power batteries includes the following steps:

[0063] Step S1: Measure 4 L of ternary leaching solution from waste power batteries, with an F content of 4.1 g / L, an Fe content of 829.1 mg / L, and an Al content of 11.64 g / L. Pour it into a glass reaction kettle, heat it up to 60 °C, and supplement aluminum sulfate octadecahydrate according to the molar ratio of Al / F = 4. Stir thoroughly until completely dissolved;

[0064] Step S2: Add sodium carbonate as an alkali source to the material liquid obtained in Step S1, adjust the pH of the reaction system to 5.5, stir at 60 °C for 2 h for precipitation treatment, and filter to obtain the liquid after one-step impurity removal. After testing and analysis, in the liquid after one-step impurity removal, the F content is 25.15 mg / L, the Fe content is 0.1 mg / L, and the Al content is 8.83 mg / L. Compared with the liquid after one-step impurity removal in Example 1, the F content and Al content in this embodiment are significantly reduced, indicating that adding an alkali source to adjust the pH of the reaction system to a higher value is beneficial for impurity removal, but it will cause more loss of main elements such as Ni, Co, and Mn, which is not conducive to the subsequent extraction process.

[0065] Comparative Example 1

[0066] This embodiment provides a method for treating ternary leaching solution from waste power batteries. The treatment method includes the following steps:

[0067] Step S1: Measure 4 L of ternary leaching solution from waste power batteries, with an F content of 4.1 g / L, an Fe content of 829.1 mg / L, and an Al content of 11.64 g / L. Pour it into a glass reaction kettle, heat it up to 60 °C, and supplement aluminum sulfate octadecahydrate according to the molar ratio of Al / F = 3. Stir thoroughly until completely dissolved;

[0068] Step S2: Add sodium carbonate as an alkali source to the material liquid obtained in Step S1, adjust the pH of the reaction system to 4.5, stir at 60 °C for 2 h for precipitation treatment, and filter to obtain the liquid after one-step impurity removal. After testing and analysis, in the liquid after one-step impurity removal, the F content is 144.97 mg / L, the Fe content is 2.55 mg / L, and the Al content is 11.21 mg / L. Compared with the liquid after one-step impurity removal in Example 1, the F content, Fe content, and Al content in this comparative example are all significantly increased and far exceed the standard of "F content less than 100 mg / L, Fe content less than 10 mg / L, and Al content less than 10 mg / L".

[0069] In summary, for the method for one-step impurity removal treatment of the ternary leaching solution of waste power batteries according to the present invention, by introducing a partial aluminum source, controlling the Al / F molar ratio in the solution system to be ≥4, and then adding an alkali source to adjust the pH for precipitation treatment, the purpose of simultaneous precipitation of iron, aluminum, and fluorine is achieved, and the problems in the prior art such as the introduction of calcium and magnesium impurities due to impurity removal in the ternary leaching solution and a relatively high fluorine concentration are solved; by introducing an aluminum source for one-step precipitation method, the present invention achieves the purpose of low-cost impurity removal from the ternary leaching solution without introducing new impurities, has important application prospects, and has the advantages of simple operation, simple equipment, low energy consumption, and no pollution.

[0070] The present invention uses the above embodiments to illustrate the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A method for one-step impurity removal treatment of ternary leaching solution of waste power batteries, characterized in that, The one-step impurity removal treatment method for the ternary leaching solution of waste power batteries comprises the following steps: Prepare the ternary leaching solution of waste power batteries and perform a temperature-raising treatment. First, add an aluminum source until it is completely dissolved, control the Al / F molar ratio in the solution system to be ≥4, and then add an alkali source for precipitation treatment. After solid-liquid separation, a post-liquid after one-step impurity removal is obtained.

2. The one-step impurity removal treatment method for ternary leaching solution of waste power batteries according to claim 1, wherein The source of the ternary leaching solution of waste power batteries includes: the black powder obtained by disassembling, crushing, and screening waste power batteries, and the ternary leaching solution obtained by leaching with sulfuric acid and hydrogen peroxide.

3. The method for one-step impurity removal treatment of the ternary leaching solution of waste power batteries according to claim 1, wherein, In the ternary leaching solution of waste power batteries, the F content is 3-5 g / L, the Fe content is 0.7-0.9 g / L, and the Al content is 10-12 g / L.

4. The one-step impurity removal treatment method for ternary leaching solution of waste power batteries according to claim 1, wherein, The target temperature of the temperature-raising treatment is 60-80 °C.

5. The one-step impurity removal treatment method for ternary leaching solution of waste power batteries according to claim 1, characterized in that, The aluminum source includes aluminum sulfate octadecahydrate.

6. The method for one-step impurity removal treatment of the ternary leaching solution of waste power batteries according to claim 1, wherein Add the aluminum source until it is completely dissolved, and control the Al / F molar ratio in the solution system to be 4-10.

7. The one-step impurity removal treatment method for ternary leaching solution of waste power batteries according to claim 1, characterized in that, The alkali source includes any one or a combination of at least two of sodium carbonate, sodium bicarbonate, sodium hydroxide, nickel hydroxide, or MHP.

8. The method for one-step impurity removal treatment of ternary leaching solution of waste power batteries according to claim 1, wherein, Add the alkali source and adjust the pH of the reaction system to 4.5-5.

9. The method for one-step impurity removal treatment of the ternary leaching solution of waste power batteries according to claim 1, wherein, The time for the precipitation treatment is 2-5 h.

10. The method for one-step impurity removal treatment of ternary leaching solution of waste power batteries according to claim 1, characterized in that, In the post-liquid after one-step impurity removal, the F content is less than 100 mg / L, the Fe content is less than 10 mg / L, and the Al content is less than 10 mg / L.