A method for separating nickel, cobalt and manganese in a high chloride concentration system

Abstract

A method for selectively separating Ni, Co and Mn metal ions in leaching solution by using adsorbent M2EHAG-PAEA in high chloride ion concentration system, comprising the following steps: step one, preparation of leaching solution containing Ni, Co and Mn metal ions: dissolving the substance containing Ni, Co and Mn metal ions with water, wherein the Cl ion concentration in the solution is 0.1 mol / L or more; step two, selectively separating metal ions Ni, Co and Mn by using adsorbent M2EHAG-PAEA: mixing adsorbent M2EHAG-PAEA with the leaching solution containing Ni, Co and Mn metal ions prepared in step one, shaking and centrifuging. The adsorbent M2EHAG-PAEA used in the method is a high molecular material, and has the advantages of simple preparation method, simple operation condition, good selectivity, fast adsorption rate and reusability.

Description

TECHNICAL FIELD

[0001] The application relates to a method for separating nickel, cobalt and manganese metals in a high-chloride-ion-concentration system and belongs to the technical field of solid-phase adsorption. BACKGROUND

[0002] Nickel (Ni) and cobalt (Co) are widely used rare metal resources. With the rapid development of new energy vehicles, the demand for ternary power lithium batteries increases year by year, and the demand for Ni and Co metal resources in the field of new energy vehicles is increasing. Ni and Co are one of the main metal materials for preparing ternary power lithium batteries, and Ni and Co metals can effectively improve the performance of lithium batteries. At present, the ternary power lithium batteries in the field of new energy vehicles have begun to retire, and a large number of waste ternary lithium batteries will be generated. Randomly stacking waste ternary lithium batteries not only pollutes the environment, but also wastes resources. Therefore, recycling waste ternary power batteries has good social value and economic value. The separation of Ni, Co and Mn metals has always been a problem in the recycling process, so separating Ni, Co and Mn in waste ternary power lithium batteries is a key problem to be solved.

[0003] In traditional industries, waste ternary power lithium batteries are mainly treated by hydrochloric acid leaching to form a leaching solution containing Li, Ni, Co and Mn metal ions. The chemical precipitation method and the solvent extraction method are mainly used in industry to separate Ni, Co and Mn. The chemical precipitation method can separate metal Ni, Co and Mn ions in the form of solid precipitate, and then recover the required metal. The chemical precipitation method mainly uses oxalate, carbonate and alkali solution, and has the advantages of low cost and low energy consumption. However, the purity of the separated metal is low, and it is difficult to completely separate it from other metals. The solvent extraction method can effectively separate metal Mn ions by using extractants. The extractants mainly used in industry are 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507) and di(2-ethylhexyl) phosphate (P204). The solvent extraction method has the advantages of low energy consumption, good separation effect and simple operation conditions. However, the extractant is expensive and the process is complex, which increases the processing cost of the recycling industry. In actual production process, Ni, Co and Mn metal ions generally exist in a solution system containing high chloride ion concentration. Therefore, in order to meet the needs of higher technology and environment, it is necessary to provide a method for separating Ni, Co and Mn metal ions in the leaching solution of waste ternary power lithium batteries in a high-chloride-ion-concentration system, which is an urgent problem to be solved by those skilled in the art. SUMMARY

[0004] The purpose of the present application is to provide a method for separating Ni, Co and Mn metal ions in the leaching solution of waste ternary power lithium batteries.

[0005] To achieve the above object, the present application adopts the following technical solutions:

[0006] A method for separating Ni, Co and Mn metal ions in leaching solution by using adsorbent M2EHAG-PAEA, comprising the following steps:

[0007] Step one, preparation of leaching solution containing Ni, Co and Mn metal ions: dissolving the substance containing Ni, Co and Mn metal ions in water, wherein the Cl ion concentration in the solution is 0.1 mol / L or more;

[0008] Step two, selective separation of metal ions Ni, Co and Mn by using adsorbent M2EHAG-PAEA: mixing adsorbent M2EHAG-PAEA with the leaching solution containing Ni, Co and Mn metal ions prepared in step one, shaking and centrifuging.

[0009] In one embodiment, the substance containing Ni, Co and Mn metal ions is a waste ternary power lithium battery.

[0010] In one embodiment, the leaching solution is an inorganic acid leaching solution of the waste ternary power lithium battery, for example, a hydrochloric acid leaching solution.

[0011] In one embodiment, the preparation process of step one is to add the mixture containing nickel dichloride, cobalt dichloride and manganese dichloride in the waste ternary power lithium battery into the aqueous solution, stir and dissolve, so that the concentration of Ni, Co and Mn ions in the solution is 10-50 mg / L, for example, 20-40 mg / L, such as 30 mg / L.

[0012] In one embodiment, the pH of the leaching solution in step one is adjusted to 3-5, for example, 4, by using hydrochloric acid and ammonia water.

[0013] In one embodiment, the leaching solution is a high Cl ion concentration system, that is, the Cl ion concentration in step one is 0.5-6 mol / L, for example, 2-4 mol / L.

[0014] In one embodiment, the adsorbent M2EHAG-PAEA is described in the document Highly Selective Adsorption of 99 TcO4 - / ReO4 - by a Novel Polyamide-Functionalized PolyacrylamidePolymerMaterial, therefore the document is incorporated herein by reference in its entirety;

[0015] wherein the adsorbent M2EHAG-PAEA is the p-(Amide)-PAM described in Highly Selective Adsorption of 99 TcO4 - / ReO4 - p-(Amide)-PAM described in Highly Selective Adsorption of

[0016] In one embodiment, the shaking of step two is performed on a shaker.

[0017] In one embodiment, the method further comprises step three, which is desorption of the metal ions Ni, Co, Mn adsorbed on the adsorbent M2EHAG-PAEA in step two using a desorbent; the desorbent is an inorganic acid, such as hydrochloric acid.

[0018] In one embodiment, the concentration of the desorbent is 0.05-0.5 mol / L, such as 0.1-0.3 mol / L.

[0019] Advantages

[0020] The present application uses M2EHAG-PAEA to adsorb metal ions Ni, Co, Mn in the leaching solution containing metal ions Ni, Co, Mn, and can selectively separate Ni, Co, Mn. In the existing field of new energy vehicles, the ternary power lithium battery containing metal ions Ni, Co, Mn has begun to be retired, and the method of the present application can meet the development of higher technology and the needs of the environment. The adsorbent M2EHAG-PAEA used is a high molecular material, the preparation method is simple, and has the advantages of simple adsorption operation condition, good selectivity, fast adsorption rate and reusability. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 The flow chart for the preparation of M2EHAG-PAEA.

[0022] Figure 2 The infrared spectra of PAAM, N-PAAM, and M2EHAG-PAEA.

[0023] Figure 3 The X-ray photoelectron spectrograms of N-PAAM and M2EHAG-PAEA. DETAILED DESCRIPTION

[0024] The technical solutions of the present application will be further described in detail below in combination with specific embodiments. It should be understood that the following embodiments are only illustratively described and explained, and should not be interpreted as limiting the scope of protection of the present application. Any technology achieved based on the above description of the present application is covered within the scope intended to be protected by the present application.

[0025] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0026] Unless otherwise specified, the metal ion concentration in this application is obtained by ICP-OES test.

[0027] The calculation method of adsorption rate in the following examples is The calculation method of desorption rate is E represents the adsorption rate of the adsorbent to the metal ion (%), D represents the desorption rate of the desorbent to the metal ion on the adsorbent (%), C0 and C e respectively represent the initial concentration and the equilibrium concentration of the metal ion (mg / L), C d represents the equilibrium concentration of the metal ion after the desorbent is used on the adsorbent.

[0028] Example 1

[0029] Synthesis of N-PAAM: Polyacrylamide (4.5 g, cationic, molecular weight 1800) was poured into a 100 mL round-bottom flask, 30 mL of ethylenediamine was added and stirred at 500 rpm with a magnetic stirrer in a 100 ℃ oil bath for 3 days. After the reaction was completed, solid-liquid separation was carried out through a funnel, and the separated solid was washed with ethanol for 4 times, and finally placed in a vacuum drying oven for drying for 2 days, with a drying temperature of 70 ℃.

[0030] Synthesis of M2EHAG-PAEA: N-PAAM (3 g) synthesized in the above step was poured into a 100 mL round-bottom flask, 50 mL of N,N-dimethylformamide was added as the solvent for the reaction, and M2EHAG (N-[N,N-(2-ethylhexyl) aminocarbonylmethyl] glycine) (7.32 g) was dissolved in N,N-dimethylformamide solution, added dropwise into the flask and stirred at a speed of 500 rpm with a magnetic stirrer in an oil bath for 15 hours, with a reaction temperature of 100 ℃. After the reaction was completed, the solid was separated out through a funnel, washed with ethanol for 3 times, and finally placed in a vacuum drying oven for drying for 1 day, with a drying temperature of 80 ℃. The specific synthesis route of M2EHAG-PAEA is shown in Figure 1 .

[0031] Characterization of M2EHAG-PAEA synthesis: as Figure 2As shown in the FT-IR diagram, the anti-symmetry and symmetry stretching vibration frequencies of -NH2 on polyacrylamide (PAAM) are 3345 cm -1 and 3183 cm -1 , respectively. The peaks of the synthesized N-PAAM and M2EHAG-PAEA at this wave number are greatly weakened, indicating that most of the -NH2 on the polyacrylamide is involved in the reaction. In addition, the stretching vibration frequency of C=O is 1650 cm -1 , and the peak area of C=O on M2EHAG-PAEA is larger than that of N-PAAM, indicating that there is more C=O on M2EHAG-PAEA, that is, N-PAAM has chemically reacted with M2EHAG. As shown in the N1s XPS diagram, Figure 3 the binding energies of -NH and C-N peaks on N-PAAM are 400.5 eV and 399.0 eV, respectively, and the binding energies of -NH and C-N peaks on M2EHAG-PAEA are 400.8 eV and 399.2 eV, respectively. Compared with N-PAAM, the peak area of -NH on M2EHAG-PAEA is larger, indicating that the amount of -NH increases, and the binding energies of -NH and C-N increase, indicating that the chemical reaction increases the charge density. In summary, it is known that M2EHAG has chemically reacted with N-PAAM, and the target adsorbent M2EHAG-PAEA has been prepared.

[0032] Preparation of hydrochloric acid leaching solution of waste ternary power lithium battery: taking nickel dichloride, cobalt dichloride and manganese dichloride as raw materials, dissolving with ultrapure water, adjusting pH value with hydrochloric acid and concentrated ammonia water, adjusting Cl ion concentration with ammonium chloride, so that the pH value is 4.0, the Cl ion concentration is 2 mol / L, and the Mn, Ni and Co ion concentrations are all 30 mg / L, 30 mL.

[0033] Preparation of desorption acid solution: prepared by diluting concentrated hydrochloric acid with water, 0.1 mol / L, 500 mL.

[0034] Take M2EHAG-PAEA (60 mg) and add it to a 15 mL centrifuge tube, then use a pipette to take 2 mL of leaching solution and add it to the centrifuge tube, shake it on a shaker at 250 rpm for 1 minute, and then put the centrifuge tube into a centrifuge at 3000 rpm for 3 minutes.

[0035] After adsorbing metal ions, M2EHAG-PAEA is added to 2 mL of hydrochloric acid, shaken on a shaker at 250 rpm for 10 minutes, and then put the centrifuge tube into a centrifuge at 3000 rpm for 3 minutes.

[0036] According to tests and calculations, M2EHAG-PAEA has an adsorption rate of 58% for Ni ions, 28% for Co ions, and 2% for Mn ions. The desorption rate of hydrochloric acid for Ni, Co, and Mn ions is 100%.

[0037] Example 2

[0038] Synthesis of N-PAAM: Polyacrylamide (5g, cationic, molecular weight 1800) was poured into a 100mL round-bottom flask, 30mL of ethylenediamine was added, and the mixture was stirred with a magnetic stirrer at 400rpm for 3 days in an oil bath at 105℃. After the reaction was completed, solid-liquid separation was performed using a funnel. The obtained solid was then washed four times with ethanol and finally dried in a vacuum drying oven at 80℃ for 1 day.

[0039] Synthesis of M2EHAG-PAEA: 3g of N-PAAM was poured into a 100mL round-bottom flask, and 50mL of N,N-dimethylformamide was added as the reaction solvent. 9.15g of M2EHAG (N-[N,N-(2-ethylhexyl)aminocarbonylmethyl]glycine) was dissolved in the N,N-dimethylformamide solution and added dropwise to the flask. The mixture was stirred with a magnetic stirrer at 500rpm for 12 hours in an oil bath at 105℃. After the reaction was complete, the solid was separated through a funnel, washed three times with ethanol, and finally dried in a vacuum drying oven for 2 days at 70℃.

[0040] Characterization of M2EHAG-PAEA synthesis: such as Figure 2 As shown in the FT-IR image, the antisymmetric and symmetric stretching vibration frequencies of -NH2 on polyacrylamide (PAAM) are 3345 cm⁻¹. -1 and 3183cm -1 The peaks of the synthesized N-PAAM and M2EHAG-PAEA were significantly weakened at this wavenumber, indicating that most of the -NH2 groups on the polyacrylamide participated in the reaction. Furthermore, the stretching vibration frequency of C=O was 1650 cm⁻¹. -1 The peak area of ​​C=O on M2EHAG-PAEA is larger than that on N-PAAM, indicating that there is more C=O on M2EHAG-PAEA, meaning that N-PAAM and M2EHAG have undergone a chemical reaction. Figure 3As shown in the XPS plot of N1s, the binding energies of the -NH and CN peaks on N-PAAM are 400.5 eV and 399.0 eV, respectively, while those on M2EHAG-PAEA are 400.8 eV and 399.2 eV, respectively. Compared to N-PAAM, the peak area of ​​-NH on M2EHAG-PAEA is larger, indicating an increase in the number of -NH peaks. Furthermore, the increased binding energy between -NH and CN indicates a chemical reaction that increases the charge density. In conclusion, this demonstrates that a chemical reaction occurred between M2EHAG and N-PAAM, resulting in the preparation of the target adsorbent M2EHAG-PAEA.

[0041] Preparation of hydrochloric acid leachate stock solution for waste ternary lithium-ion batteries: Nickel dichloride, cobalt dichloride and manganese dichloride are used as raw materials, dissolved in ultrapure water, and the pH value is adjusted with hydrochloric acid and concentrated ammonia. The Cl ion concentration is adjusted with ammonium chloride to make the pH value 4.0, the Cl ion concentration 4 mol / L, and the Mn, Ni and Co ion concentrations 30 mg / L, 30 mL.

[0042] Preparation of desorption acid solution: prepared by diluting concentrated hydrochloric acid with water, 0.1 mol / L, 500 mL.

[0043] Add 60 mg of M2EHAG-PAEA to a 15 mL centrifuge tube, then add 2 mL of the extract stock solution to the centrifuge tube using a pipette. Shake at 250 rpm for 1 minute on a shaker. After shaking, place the centrifuge tube in a centrifuge and centrifuge at 3000 rpm for 3 minutes.

[0044] Add the M2EHAG-PAEA containing the adsorbed metal ions to 2 mL of hydrochloric acid, shake at 250 rpm for 10 minutes on a shaker, and after shaking, place the centrifuge tube into a centrifuge and centrifuge at 3000 rpm for 3 minutes.

[0045] According to tests and calculations, M2EHAG-PAEA has an adsorption rate of 77% for Ni ions, 44% for Co ions, and 5% for Mn ions. The desorption rate of hydrochloric acid for Ni, Co, and Mn ions is 100%.

[0046] Example 3

[0047] Synthesis of N-PAAM: 12 g of polyacrylamide (cationic, molecular weight 1800) was poured into a 200 mL round-bottom flask, 100 mL of ethylenediamine was added, and the mixture was stirred with a magnetic stirrer at 800 rpm for 3 days in an oil bath at 110 °C. After the reaction was complete, solid-liquid separation was performed using a funnel. The obtained solid was then washed four times with ethanol and finally dried in a vacuum drying oven at 80 °C for 2 days.

[0048] Synthesis of M2EHAG-PAEA: 3g of N-PAAM was poured into a 100mL round-bottom flask, and 50mL of N,N-dimethylformamide was added as the reaction solvent. 10.98g of M2EHAG (N-[N,N-(2-ethylhexyl)aminocarbonylmethyl]glycine) was dissolved in the N,N-dimethylformamide solution and added dropwise to the flask. The mixture was stirred with a magnetic stirrer at 500rpm for 12 hours in an oil bath at 110℃. After the reaction was complete, the solid was separated through a funnel, washed three times with ethanol, and finally dried in a vacuum drying oven for 2 days at 70℃.

[0049] Characterization of M2EHAG-PAEA synthesis: such as Figure 2 As shown in the FT-IR image, the antisymmetric and symmetric stretching vibration frequencies of -NH2 on polyacrylamide (PAAM) are 3345 cm⁻¹. -1 and 3183cm -1 The peaks of the synthesized N-PAAM and M2EHAG-PAEA were significantly weakened at this wavenumber, indicating that most of the -NH2 groups on the polyacrylamide participated in the reaction. Furthermore, the stretching vibration frequency of C=O was 1650 cm⁻¹. -1 The peak area of ​​C=O on M2EHAG-PAEA is larger than that on N-PAAM, indicating that there is more C=O on M2EHAG-PAEA, meaning that N-PAAM and M2EHAG have undergone a chemical reaction. Figure 3 As shown in the XPS plot of N1s, the binding energies of the -NH and CN peaks on N-PAAM are 400.5 eV and 399.0 eV, respectively, while those on M2EHAG-PAEA are 400.8 eV and 399.2 eV, respectively. Compared to N-PAAM, the peak area of ​​-NH on M2EHAG-PAEA is larger, indicating an increase in the number of -NH peaks. Furthermore, the increased binding energy between -NH and CN indicates a chemical reaction that increases the charge density. In conclusion, this demonstrates that a chemical reaction occurred between M2EHAG and N-PAAM, resulting in the preparation of the target adsorbent M2EHAG-PAEA.

[0050] Preparation of hydrochloric acid leachate stock solution for waste ternary lithium-ion batteries: Manganese dichloride, nickel dichloride, and cobalt dichloride are used as raw materials, dissolved in ultrapure water, and the pH value is adjusted with hydrochloric acid and concentrated ammonia. The Cl ion concentration is adjusted with ammonium chloride to make the pH value 4.0, the Cl ion concentration 0.5mol / L, and the Mn, Ni, and Co ion concentrations 30mg / L, 30mL.

[0051] Preparation of desorption acid solution: prepared by diluting concentrated hydrochloric acid with water, 0.1 mol / L, 500 mL.

[0052] Add 60 mg of M2EHAG-PAEA to a 15 mL centrifuge tube, then add 2 mL of the extract stock solution to the centrifuge tube using a pipette. Shake at 250 rpm for 1 minute on a shaker. After shaking, place the centrifuge tube in a centrifuge and centrifuge at 3000 rpm for 3 minutes.

[0053] Add the M2EHAG-PAEA containing the adsorbed metal ions to 2 mL of hydrochloric acid, shake at 250 rpm for 10 minutes on a shaker, and after shaking, place the centrifuge tube into a centrifuge and centrifuge at 3000 rpm for 3 minutes.

[0054] According to tests and calculations, M2EHAG-PAEA has an adsorption rate of 85% for Ni ions, 50% for Co ions, and 10% for Mn ions. The desorption rate of hydrochloric acid for Ni, Co, and Mn ions is 100%.

[0055] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for separating Ni, Co, Mn metal ions in a leaching stock solution by using adsorbent M2EHAG-PAEA, characterized in that, The method comprises the following steps: Step one: preparation of leaching solution containing Ni, Co and Mn metal ions: dissolve the substance containing Ni, Co and Mn metal ions in water, wherein the concentration of Cl ions in the solution is 0.1 mol / L or more; Step two: selective separation of metal ions Ni, Co and Mn by using adsorbent M2EHAG-PAEA: mix the adsorbent M2EHAG-PAEA with the leaching solution containing Ni, Co and Mn metal ions prepared in step one, shake and centrifuge.

2. The method of claim 1, wherein, The substance containing Ni, Co and Mn metal ions is waste ternary power lithium battery.

3. The method according to claim 1 or 2, characterized in that, The leaching solution is hydrochloric acid leaching solution of waste ternary power lithium battery.

4. The method according to claim 1 or 2, characterized in that, The preparation process of step one is to add the mixture containing nickel dichloride, cobalt dichloride and manganese dichloride in waste ternary power lithium battery into aqueous solution, stir and dissolve, so that the concentration of Ni, Co and Mn ions in the solution is 10-50 mg / L.

5. The method according to claim 1 or 2, characterized in that, In step one, the pH of the leaching solution is adjusted to 3-5 by using hydrochloric acid and ammonia water.

6. The method of claim 1 or 2, wherein, In step one, the concentration of Cl ions is 0.5-6 mol / L.

7. The method of claim 1 or 2, wherein, The shaking in step two is carried out on a shaking table.

8. The method of claim 1 or 2, wherein, The method further comprises step three, which is desorption of the adsorbed metal ions Ni, Co and Mn on the adsorbent M2EHAG-PAEA in step two by using a desorbent; the desorbent is inorganic acid.

9. The method of claim 8, wherein, The desorbent is hydrochloric acid.

10. The method of claim 9, wherein, The concentration of the desorbent is 0.05-0.5 mol / L.

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