Method for recycling valuable metal nickel, cobalt and manganese from waste battery black powder in one step

Abstract

The invention relates to a method for recovering valuable metal nickel, cobalt and manganese from waste battery black powder in one step, which comprises the following steps of: removing Cu and Mn powder from a waste battery black powder leaching solution by a chemical method, removing Zn by a replacement method, and removing Fe and Al by an oxidation method to obtain a solution without Cu, Zn, Fe and Al; the pH value of the solution after Cu, Zn, Fe and Al are removed is adjusted to 3.0-3.5 through dilute sulphuric acid, battery black powder extraction pre-liquid is obtained, and the battery black powder extraction pre-liquid is subjected to DY-319 full extraction, so that the Ni-Co-Mn composite solution is obtained. The method is simple in process and short in flow, and new impurity elements are not introduced. And 2, by adopting the method disclosed by the invention, the extraction separation effect is good, the recycled Ni-Co-Mn composite solution can be directly used for producing the ternary positive electrode material, and the recycling of valuable metals in the waste battery black powder is realized. Meanwhile, less wastewater and waste residues are produced, and environmental pollution is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of resource recovery of waste battery materials, and in particular to a method for recovering valuable metals nickel, cobalt and manganese from black powder of waste batteries in one step. Background Art

[0002] In recent years, as new energy vehicles have entered a period of rapid development, as power batteries for new energy, ternary batteries such as nickel, cobalt and manganese have the advantages of high efficiency, large capacity, long life and high safety performance, and are one of the key materials supported by the country to develop lithium-ion batteries. The continuous growth of battery production capacity will inevitably lead to the problem of recycling of waste batteries. In order to save resources, reduce environmental pollution and reduce production costs, it is particularly important to recover the valuable metal elements nickel, cobalt and manganese from the black powder of waste batteries.

[0003] At present, the extraction process of valuable metals nickel, cobalt and manganese in battery black powder is lengthy. It requires at least three extraction processes of P204, P507 and C272 to extract the valuable metals nickel, cobalt and manganese separately. The recovery rate of valuable metals nickel, cobalt and manganese is low, the cost is high, and the volume of waste slag and wastewater produced is large. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a method for recovering valuable metals nickel, cobalt and manganese from waste battery black powder in one step, which has a short process flow and good extraction and separation effect.

[0005] In order to solve the above problems, the present invention discloses a method for recovering valuable metals nickel, cobalt and manganese from waste battery black powder in one step, characterized in that: the method refers to subjecting the waste battery black powder leachate to chemical method to remove Cu, Mn powder replacement method to remove Zn and oxidation method to remove Fe and Al, so as to obtain a solution after removing Cu, Zn, Fe and Al; the solution after removing Cu, Zn, Fe and Al is adjusted to pH 3.0-3.5 with dilute sulfuric acid to obtain a battery black powder extraction pre-liquid; the battery black powder extraction pre-liquid is fully extracted with DY-319 to obtain a Ni-Co-Mn composite solution.

[0006] The components of the waste battery black powder leaching solution are: Ni 40-80 g / L, Na 0.4-0.6 g / L, Si 0.1-0.5 g / L, Ca 0.1-5 g / L, Al 0.02-0.1 g / L, Co 5-15 g / L, Mn 15-25 g / L, Zn 0.004-0.1 g / L, Mg 0.7-5 g / L, Cu 0.008-0.1 g / L, Fe 1.5-3 g / L, F - 0.1~0.5g / L, Cl - 0.2~0.5g / L, Li 0.1~0.3g / L, pH=5.0~5.5.

[0007] The chemical method for removing Cu is to add sodium thiosulfate to the waste battery black powder leachate, react at 40-60° C. for 1.5-2.0 hours to obtain a Cu-removed liquid; the molar ratio of the sodium thiosulfate to the copper ions in the waste battery black powder leachate is 1-1.5:1-2.

[0008] The Mn powder replacement method for removing Zn refers to adding Mn powder to the Cu-removed liquid and reacting at 30° C. for 75 minutes to obtain a Cu-removed and Zn-removed liquid with Cu≤0.002 g / L and Zn≤0.002 g / L; the amount of Mn powder used is 2.0 to 3.0 times the theoretical amount of Zn.

[0009] The oxidation method for removing Fe and Al refers to adding hydrogen peroxide with a mass concentration of 30% to the liquid after Cu and Zn are removed, heating to 60°C, adjusting the pH to 5 with sodium carbonate, and reacting for 2 hours to obtain a solution after Cu, Zn, Fe, and Al are removed with Fe≤0.005g / L and Al≤0.001g / L; the volume ratio of the liquid after Cu and Zn are removed to hydrogen peroxide is 15:1.

[0010] The DY-319 full extraction is carried out as follows: ⑴ DY-319 extractant and diluent white oil were mixed in a volume ratio of 1:3 to obtain [H + ] In the pre-soap organic phase of 0.8~0.85g / L, liquid alkali with a mass concentration of 30~35% is added to the pre-soap organic phase to carry out sodium soap reaction at room temperature to obtain [H + ] is 0.45~0.48g / L of sodium soap organic phase; ⑵ The sodium soap organic phase is countercurrently extracted with the battery black powder extraction pre-liquid, and the extraction ratio is controlled at 7~7.5:1; [H + ] is 1~2g / L dilute sulfuric acid to wash the sodium, and then use [H + ] 4~5g / L dilute sulfuric acid was used to strip the DY-319 loaded organic phase, and the pH value of the stripping endpoint was controlled to be 4.5~5.0 to obtain a stripping solution rich in Ni, Co, and Mn valuable metal elements, namely, a Ni-Co-Mn composite solution; the organic phase after stripping was treated with [H + ] is regenerated with 5~6g / L hydrochloric acid.

[0011] Compared with the prior art, the present invention has the following advantages: 1. The present invention utilizes post-soap organic DY-319 and a full extraction process of valuable metals nickel, cobalt and manganese to achieve the recovery and utilization of valuable metal elements nickel, cobalt and manganese in waste battery black powder and the efficient selective separation of a multi-component solution system. Not only is the process simple and the flow short, but no new impurity elements are introduced, thereby greatly reducing the cost.

[0012] 2. The method of the present invention has good extraction and separation effects. The recovered Ni-Co-Mn composite solution can be directly used in the production of ternary positive electrode materials, realizing the recycling of valuable metals in the black powder of waste batteries. At the same time, less waste water and waste residue are produced, reducing environmental pollution. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The specific implementation modes of the present invention will be further described in detail below in conjunction with the accompanying drawings.

[0014] Figure 1 It is a flow chart of the present invention. DETAILED DESCRIPTION

[0015] like Figure 1 As shown, a method for recovering valuable metals nickel, cobalt and manganese from waste battery black powder in one step, the method is to remove Cu from waste battery black powder leaching solution by chemical method, remove Zn by Mn powder replacement method and remove Fe and Al by oxidation method, so as to obtain a solution after removing Cu, Zn, Fe and Al; the solution after removing Cu, Zn, Fe and Al is adjusted to pH 3.0-3.5 by dilute sulfuric acid to obtain a battery black powder extraction pre-liquid, and the battery black powder extraction pre-liquid is fully extracted by DY-319 to obtain a Ni-Co-Mn composite solution. The specific process is as follows: First, add sodium thiosulfate to the waste battery black powder leachate, and the molar ratio of sodium thiosulfate to copper ions in the waste battery black powder leachate is 1~1.5:1~2. React at 40~60℃ for 1.5~2.0h to obtain the solution after Cu removal. Among them: the components of the waste battery black powder leachate: Ni 40~80g / L, Na 0.4~0.6g / L, Si 0.1~0.5g / L, Ca 0.1~5g / L, Al 0.02~0.1g / L, Co 5~15g / L, Mn 15~25g / L, Zn0.004~0.1g / L, Mg 0.7~5g / L, Cu 0.008~0.1g / L, Fe 1.5~3g / L, F - 0.1~0.5g / L, Cl - 0.2~0.5g / L, Li 0.1~0.3g / L, pH=5.0~5.5.

[0016] Then, add Mn powder to the Cu-removed liquid, the amount of Mn powder is 2.0~3.0 times the theoretical amount of Zn. React at 30℃ for 75min to obtain the Cu-removed and Zn-removed liquid with Cu≤0.002g / L and Zn≤0.002g / L.

[0017] Secondly, add 30% hydrogen peroxide to the solution after Cu and Zn removal, and the volume ratio (L / L) of the solution after Cu and Zn removal to hydrogen peroxide is 15:1. Raise the temperature to 60°C, adjust the pH to 5 with sodium carbonate, and react for 2h to obtain a solution after Cu, Zn, Fe, and Al removal with Fe≤0.005g / L and Al≤0.001g / L.

[0018] Finally, after removing Cu, Zn, Fe and Al, the solution is adjusted to pH 3.0-3.5 with dilute sulfuric acid to obtain the battery black powder extraction pre-liquid, which is fully extracted with DY-319 according to the following method: ⑴ DY-319 extractant and diluent white oil were mixed in a volume ratio of 1:3 (L / L) to obtain [H + ] In the pre-soap organic phase of 0.8~0.85g / L, liquid alkali with a mass concentration of 30~35% is added to the pre-soap organic phase to carry out sodium soap reaction at room temperature to obtain [H + ] is 0.45~0.48g / L of sodium soap organic phase; ⑵ The sodium soap organic phase is countercurrently extracted with the battery black powder extraction pre-liquid, and the extraction ratio (O / A) is controlled at 7~7.5:1; [H + ] is 1~2g / L dilute sulfuric acid to wash the sodium, and then use [H + ] 4~5g / L dilute sulfuric acid was used to strip the DY-319 loaded organic phase, and the pH value of the stripping endpoint was controlled to be 4.5~5.0 to obtain a stripping solution rich in Ni, Co, and Mn valuable metal elements, namely, a Ni-Co-Mn composite solution; the organic phase after stripping was treated with [H + ] is regenerated with 5~6g / L hydrochloric acid.

[0019] The present invention adopts a one-step extraction method to recover Ni-Co-Mn valuable metal elements for the production of ternary positive electrode materials. - , Cl - 、Na + , Si impurity elements remain in the raffinate and are removed.

[0020] Example 1 Black powder leachate composition: Ni 41.22g / L, Na 0.48g / L, Si 0.11g / L, Ca 0.13g / L, Al0.029g / L, Co 7.54g / L, Mn 17.06g / L, Zn0.0042g / L, Mg 0.78g / L, Cu 0.008g / L, Fe 1.54g / L, F - 0.1g / L, Cl - 0.25g / L, Li 0.3g / L, pH=5.0.

[0021] (1) The chemical Cu removal reagent uses sodium thiosulfate. The process technical conditions for removing Cu with sodium thiosulfate are: temperature 50°C, the molar ratio of sodium thiosulfate to copper ions in the black powder leachate is 1:1.5, and the reaction time is 1.5h.

[0022] (2) Mn powder replacement method was used to remove Zn. The amount of Mn powder was 2.5 times the theoretical amount of Zn. The reaction temperature was 30°C and the reaction time was 75 min. After impurities were removed, Cu ≤ 0.002 g / L and Zn ≤ 0.002 g / L.

[0023] (3) Technical conditions for oxidation removal of Fe and Al: Hydrogen peroxide mass percentage concentration: 30% Reaction temperature: 60℃ Reaction end point pH: 5 Reaction time: 2h The solution composition after chemical removal of Cu, Zn, Fe and Al is: Ni 43.26g / L, Na 2.37g / L, Si 0.072g / L, Al 0.001g / L, Ca 0.16g / L, Co 7.76g / L, Mn 17.52g / L, Zn 0.002g / L, Mg 0.81g / L, Cu 0.0005g / L, Fe 0.002g / L, F － 0.049g / L, Cl － 0.013g / L, Li 0.3g / L, pH=5.0.

[0024] Battery black powder extraction pre-liquid composition: Ni 43.26g / L, Na 2.37g / L, Si 0.072g / L, Al 0.001g / L, Ca 0.16g / L, Co7.76g / L, Mn 17.52g / L, Zn 0.002g / L, Mg 0.81g / L, Cu0.0005g / L, Fe0.002g / L, F － 0.049g / L, Cl － 0.013g / L, Li 0.3g / L, pH=3.0-3.5.

[0025] (4) DY-319 full extraction Ni-Co-Mn process technical conditions Organic phase composition: 25% DY-319 + 75% solvent oil (volume ratio) Saponification rate: 40~45% Impurity removal ratio O / A: 7~7.5:1 After the DY-319 full extraction of Ni-Co-Mn, the components of the stripped Ni-Co-Mn composite solution are as follows: Ni 86.23 g / L, Na 0.016 g / L, Si 0.0047 g / L, Al 0.001 g / L, Ca 0.008 g / L, Co 13.06 g / L, Mn 10.12 g / L, Zn 0.002 g / L, Mg 0.0041 g / L, Cu < 0.001 g / L, Fe 0.001 g / L, F － 0.01g / L, Cl － 0.05g / L, Li<0.001g / L, P 0.001g / L, pH=4.5~5.0, can be directly used in the production of ternary positive electrode materials.

[0026] Example 2 Black powder leachate composition: Ni 50.22g / L, Na 0.5g / L, Si 0.3g / L, Ca 0.3g / L, Al0.08g / L, Co12g / L, Mn 20g / L, Zn 0.009g / L, Mg 1g / L, Cu0.009g / L, Fe 2g / L, F - 0.5g / L, Cl - 0.5g / L, Li0.1g / L, pH=5.0.

[0027] (1) The chemical Cu removal reagent uses sodium thiosulfate. The process technical conditions for removing Cu with sodium thiosulfate are: temperature 50°C, the molar ratio of sodium thiosulfate to copper ions in the black powder leachate is 1.5:2, and the reaction time is 1.5h.

[0028] (2) Mn powder replacement method was used to remove Zn. The amount of Mn powder was twice the amount of Zn. The reaction temperature was 30°C and the reaction time was 75 min. After impurities were removed, Cu was less than 0.002 g / L and Zn was less than 0.002 g / L.

[0029] (3) Technical conditions for oxidation removal of Fe and Al Hydrogen peroxide mass percentage concentration: 30% Reaction temperature: 60℃ Reaction end point pH: 5 Reaction time: 2h The solution composition after chemical removal of Cu, Zn, Fe and Al is: Ni 52.26g / L, Na 4g / L, Si0.3g / L, Al0.001g / L, Ca 0.3g / L, Co 12.68g / L, Mn 22g / L, Zn 0.002g / L, Mg 1g / L, Cu 0.0008g / L, Fe0.002g / L, F － 0.5g / L, Cl－ 0.5g / L, Li 0.1g / L, pH=5.0.

[0030] Battery black powder extraction pre-liquid composition: Ni 52.26g / L, Na 4g / L, Si 0.3g / L, Al 0.001g / L, Ca0.3g / L, Co 12.68g / L, Mn 22g / L, Zn 0.002g / L, Mg1g / L, Cu 0.0008g / L, Fe 0.002g / L, F － 0.5g / L, Cl － 0.5g / L, Li 0.1g / L, pH=3.0-3.5.

[0031] (4) DY-319 full extraction Ni-Co-Mn process technical conditions Organic phase composition: 25% DY-319 + 75% solvent oil (volume ratio) Saponification rate: 40~45% Impurity removal ratio O / A: 7~7.5:1 After the DY-319 full extraction of Ni-Co-Mn, the components of the stripped Ni-Co-Mn composite solution are: Ni 90g / L, Na 0.016g / L, Si 0.005g / L, Al 0.001g / L, Ca 0.009g / L, Co 20g / L, Mn 15g / L, Zn 0.002g / L, Mg 0.0041g / L, Cu <0.001g / L, Fe <0.001g / L, F － 0.02g / L, Cl － 0.04g / L, Li<0.001g / L, P 0.001g / L, pH=4.5-5.0, can be directly used in the production of ternary positive electrode materials.

Claims

1. A method for recovering valuable metals nickel, cobalt and manganese from waste battery black powder in one step, characterized in that: The method is that waste battery black powder leachate is subjected to chemical method to remove Cu, Mn powder replacement method to remove Zn and oxidation method to remove Fe and Al, so as to obtain a solution after removing Cu, Zn, Fe and Al; the solution after removing Cu, Zn, Fe and Al is adjusted to pH 3.0-3.5 by using dilute sulfuric acid to obtain a battery black powder material extraction pre-liquid; the battery black powder material extraction pre-liquid is fully extracted with DY-319 to obtain a Ni-Co-Mn composite solution.

2. A method for recovering valuable metals nickel, cobalt and manganese from waste battery black powder in one step as claimed in claim 1, characterized in that: The components of the waste battery black powder leaching solution are: Ni 40-80 g / L, Na 0.4-0.6 g / L, Si 0.1-0.5 g / L, Ca 0.1-5 g / L, Al 0.02-0.1 g / L, Co 5-15 g / L, Mn 15-25 g / L, Zn 0.004-0.1 g / L, Mg 0.7-5 g / L, Cu 0.008-0.1 g / L, Fe 1.5-3 g / L, F - 0.1~0.5g / L, Cl - 0.2~0.5g / L, Li 0.1~0.3g / L, pH=5.0~5.

5.

3. A method for recovering valuable metals nickel, cobalt and manganese from waste battery black powder in one step as claimed in claim 1, characterized in that: The chemical method for removing Cu is to add sodium thiosulfate to the waste battery black powder leachate, react at 40-60° C. for 1.5-2.0 hours to obtain a Cu-removed liquid; the molar ratio of the sodium thiosulfate to the copper ions in the waste battery black powder leachate is 1-1.5:1-2.

4. A method for recovering valuable metals nickel, cobalt and manganese from waste battery black powder in one step as claimed in claim 1, characterized in that: The Mn powder replacement method for removing Zn refers to adding Mn powder to the Cu-removed liquid and reacting at 30° C. for 75 minutes to obtain a Cu-removed and Zn-removed liquid with Cu≤0.002 g / L and Zn≤0.002 g / L; the amount of Mn powder used is 2.0 to 3.0 times the theoretical amount of Zn.

5. A method for recovering valuable metals nickel, cobalt and manganese from waste battery black powder in one step as claimed in claim 1, characterized in that: The oxidation method for removing Fe and Al refers to adding hydrogen peroxide with a mass concentration of 30% to the liquid after Cu and Zn are removed, heating to 60°C, adjusting the pH to 5 with sodium carbonate, and reacting for 2 hours to obtain a solution after Cu, Zn, Fe, and Al are removed with Fe≤0.005g / L and Al≤0.001g / L; the volume ratio of the liquid after Cu and Zn are removed to hydrogen peroxide is 15:

1.

6. A method for recovering valuable metals nickel, cobalt and manganese from waste battery black powder in one step as claimed in claim 1, characterized in that: The DY-319 full extraction is carried out as follows: ⑴ DY-319 extractant and diluent white oil were mixed in a volume ratio of 1:3 to obtain [H + ] In the pre-soap organic phase of 0.8~0.85g / L, liquid alkali with a mass concentration of 30~35% is added to the pre-soap organic phase to carry out sodium soap reaction at room temperature to obtain [H + ] is 0.45~0.48g / L of sodium soap organic phase; ⑵ The sodium soap organic phase is countercurrently extracted with the battery black powder extraction pre-liquid, and the extraction ratio is controlled at 7~7.5:1; [H + ] is 1~2g / L dilute sulfuric acid to wash the sodium, and then use [H + ] 4~5g / L dilute sulfuric acid was used to strip the DY-319 loaded organic phase, and the pH value of the stripping endpoint was controlled to be 4.5~5.0 to obtain a stripping solution rich in Ni, Co, and Mn valuable metal elements, namely, a Ni-Co-Mn composite solution; the organic phase after stripping was treated with [H + ] is regenerated with 5~6g / L hydrochloric acid.

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