CN114015880B - Metal recovery processing method for battery reclaimed material - Google Patents
Metal recovery processing method for battery reclaimed material Download PDFInfo
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- CN114015880B CN114015880B CN202111234782.1A CN202111234782A CN114015880B CN 114015880 B CN114015880 B CN 114015880B CN 202111234782 A CN202111234782 A CN 202111234782A CN 114015880 B CN114015880 B CN 114015880B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention is suitable for providing a method for recovering and treating metal of a battery reclaimed material, which comprises the following steps: s01, low-acid dissolution: dissolving the pretreated battery by using a low-concentration acidic solution to obtain a first leaching solution and first leaching residues, and removing copper from the first leaching solution to obtain a first mixed solution; s02, high-acid dissolution: dissolving the first leaching residue by adopting a high-concentration acidic solution, simultaneously adding a reducing agent for reduction to obtain a second leaching solution, and sequentially removing copper ions, iron ions and aluminum ions from the second leaching solution to obtain a second mixed solution; s03, mixed extraction: regulating the pH value of a third mixed solution formed by mixing the two mixed solutions, removing zinc ions by extraction, and mixing the obtained cobalt washing solution and manganese washing solution to obtain a fourth mixed solution; s04, precipitation and impurity removal: and removing calcium and magnesium ions in the fourth mixed solution by adopting a precipitator to obtain qualified feed liquid. Compared with an extraction method, the method has the advantages of simple process, convenience in operation, low cost and high impurity removal rate.
Description
Technical Field
The invention belongs to the technical field of battery recovery, and particularly relates to a method for recovering and treating metal of a battery recovery material.
Background
A significant increase in the size of the retired battery will occur annually after 2030, which originally came from an electric bus, but after 2024 it will mainly come from an electric passenger car. However, the advent of battery refurbishment technology has delayed the time to retire a partially available battery by approximately five years. The battery recycling market prospect is wide, but in the current battery recycling treatment methods, metal elements such as copper, iron and aluminum in the recycled materials are removed through an extraction method, but the extraction process is complex, the operation is not easy, and the impurity removal rate is low.
Disclosure of Invention
The invention aims to provide a method for recovering and treating metals in a battery reclaimed material, and aims to solve the technical problems that the process for removing metal elements such as copper, iron, aluminum and the like in the reclaimed material by extraction is complicated and the operation is difficult in the prior art.
The invention is realized in such a way that a method for recovering and treating metal of a battery reclaimed material comprises the following steps:
s01, low-acid dissolution: dissolving the pretreated battery reclaimed materials by adopting an acid solution, controlling the end point pH to be 3.5-6.0 to obtain a first leaching solution and first leaching residues, and removing copper from the first leaching solution to obtain a first mixed solution containing cobalt, nickel and manganese ions;
s02, high-acid dissolution: dissolving the first leaching residue by using an acidic solution, controlling the end point pH to be 0.5-1.5, simultaneously adding a reducing agent for reduction to obtain a second leaching solution, and sequentially removing copper ions, iron ions and aluminum ions from the second leaching solution to obtain a second mixed solution containing cobalt ions, nickel ions and manganese ions;
s03, mixed extraction: mixing the first mixed solution and the second mixed solution to form a third mixed solution, adjusting the pH value, extracting by using an extracting agent to remove zinc ions, and mixing cobalt washing solution and manganese washing solution obtained in the extraction and washing process to obtain a fourth mixed solution containing cobalt, nickel and manganese ions;
s04, precipitation and impurity removal: and removing calcium and magnesium ions in the fourth mixed solution by using a precipitator to obtain qualified feed liquid.
In one embodiment, in step S01, the acidic solution is prepared by using sulfuric acid, the liquid-solid ratio of the acidic solution to the pretreated battery is 200-500: 100, the temperature is raised to 85-90 ℃, the pH is controlled to 3.5-6.0 at the end of the reaction, and the first leachate is obtained after the reaction is performed for 2-6 hours.
In one embodiment, in step S02, the acidic solution is 3.6N to 4.0N sulfuric acid, the liquid-solid ratio of the acidic solution to the first leaching residue is 200g to 500g to 100g, and the PH is controlled to be 0.5 to 1.5 at the end of the reaction.
In one embodiment, in step S02, the temperature is first raised to 85 to 90 ℃ for dissolution, the temperature is lowered to 50 to 80 ℃ after the reaction is performed for 2 to 4 hours, then the reducing agent is added, and the temperature is raised to 85 to 90 ℃ for reaction for 1 to 2 hours, so as to obtain the second leaching solution.
In one embodiment, in step S02, the second leaching solution is subjected to a displacement reaction or extraction to remove copper ions, so as to obtain a third leaching solution.
In one embodiment, the pH of the third leaching solution is adjusted to 2.5 to 3.5, and a fourth leaching solution is obtained after filtration.
In one embodiment, the pH of the fourth leaching solution is adjusted to 4.5-5.5, the second mixed solution and the aluminum slag are obtained after filtering, the aluminum slag is dissolved by an alkaline solution to obtain a second leaching slag, and the second leaching slag is returned to the high-acid dissolving step and reacts with the first leaching slag to obtain the second mixed solution.
In one embodiment, in step S03, the extractant is P204.
In one embodiment, in step S03, the third mixed solution is subjected to extraction to remove impurities after the extractant is transformed into cobalt soap or nickel soap.
In one embodiment, in step S04, the precipitating agent is fluoride, and the fluorine removing agent is used to remove the residual fluorine ions, so as to obtain the qualified feed liquid.
Compared with the prior art, the invention has the technical effects that: and obtaining a first leaching solution and a first leaching residue through low-acid dissolution, enriching aluminum ions and iron ions in the first leaching residue, and removing copper ions from the first leaching solution containing cobalt, nickel and manganese ions to obtain a first mixed solution only containing partial calcium ions and magnesium ions. And (3) reducing high-valence ions into low-valence ions by the first leaching residue through high-acid dissolution and reduction reaction of a reducing agent to obtain a second leaching solution, wherein the second leaching solution contains dissolved aluminum ions and iron ions, and then sequentially removing copper ions, iron ions and aluminum ions to obtain a second mixed solution containing cobalt ions, nickel ions and manganese ions and only part of calcium ions and magnesium ions. Therefore, only calcium ions, magnesium ions and trace zinc ions exist in the third mixed solution formed by mixing the first mixed solution and the second mixed solution, the zinc ions are removed through extraction, the calcium ions and the magnesium ions are removed through adding a precipitator, and therefore qualified feed liquid with qualified impurity content is obtained, and the impurity content in the qualified feed liquid meets the impurity content used in precursor production. Compared with an extraction method, the method has the advantages of simple process, convenience in operation, low cost and high impurity removal rate.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention or in the description of the prior art will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a flow chart of a metal recovery processing method for a battery reclaimed material according to an embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative and intended to explain the present invention and should not be construed as limiting the present invention.
Furthermore, the terms "first", "second", "third", "fourth" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", "third", "fourth" may explicitly or implicitly include one or more of the features.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments.
The invention provides a metal recovery processing method for a battery reclaimed material, and the battery can be a binary or ternary lithium ion battery. In this example, LiCoO was included in the recovered battery material 2 、LiNiO 2 、LiMn 2 O 4 。
As shown in fig. 1, the metal recovery processing method of the battery reclaimed material comprises the following steps:
s01, low-acid dissolution: dissolving the pretreated battery reclaimed materials by adopting an acid solution, controlling the end point pH to be 3.5-6.0 to obtain a first leaching solution and first leaching residues, and removing copper from the first leaching solution to obtain a first mixed solution containing cobalt, nickel and manganese ions;
s02, high-acid dissolution: dissolving the first leaching residue by using an acidic solution, controlling the end point pH value to be 0.5-1.5, simultaneously adding a reducing agent for reduction to obtain a second leaching solution, and sequentially removing copper ions, iron ions and aluminum ions from the second leaching solution to obtain a second mixed solution containing cobalt ions, nickel ions and manganese ions;
s03, mixed extraction: mixing the first mixed solution and the second mixed solution to form a third mixed solution, adjusting the pH value, extracting by using an extracting agent to remove zinc ions, and mixing cobalt washing solution and manganese washing solution obtained in the extraction and washing process to obtain a fourth mixed solution containing cobalt, nickel and manganese ions;
s04, precipitation and impurity removal: and removing calcium and magnesium ions in the fourth mixed solution by using a precipitator, and removing residual fluorine ions by using a fluorine removal agent to obtain a qualified mixed solution.
And obtaining a first leaching solution and a first leaching residue through low-acid dissolution, enriching aluminum ions and iron ions in the first leaching residue, and removing copper ions from the first leaching solution containing cobalt, nickel and manganese ions to obtain a first mixed solution only containing partial calcium ions and magnesium ions. And (3) reducing high-valence ions into low-valence ions by the first leaching slag through high-acid dissolution and a reduction reaction of a reducing agent to obtain a second leaching solution, wherein the second leaching solution contains dissolved aluminum ions and iron ions, and then sequentially removing copper ions, iron ions and aluminum ions to obtain a second mixed solution containing cobalt ions, nickel ions and manganese ions and only part of calcium ions and magnesium ions. Therefore, only calcium ions, magnesium ions and trace zinc ions exist in the third mixed solution formed by mixing the first mixed solution and the second mixed solution, the zinc ions are removed through extraction, the calcium ions and the magnesium ions are removed through adding a precipitator, and therefore qualified feed liquid with qualified impurity content is obtained, and the impurity content in the qualified feed liquid meets the impurity content used in precursor production. Compared with an extraction method, the method has the advantages of simple process, convenience in operation, low cost and high impurity removal rate.
In the step S01, the step of pretreating the waste lithium batteries includes crushing, magnetic separation and calcination of the batteries. Specifically, the waste lithium battery is subjected to discharge pretreatment, then the waste battery is crushed, the particle size can be below 40mm, the risk of explosion in subsequent treatment is prevented, the crushed waste lithium battery is roasted under the reducing atmosphere condition, then the roasted waste lithium battery is subjected to fine crushing treatment, and then magnetic separation is performed under the magnetic field intensity, so that valuable metal iron, copper, aluminum and other particles are separated, and the battery after pretreatment is obtained.
In the step S01, the acidic solution is prepared by using sulfuric acid, the liquid-solid ratio of the acidic solution to the battery after pretreatment is 200-500: 100, the end-point pH is controlled to be 3.5-6.0, the temperature is raised to 85-90 ℃, and the first leaching solution is obtained after the reaction is performed for 2-6 hours. And dissolving the pretreated battery under the pH condition, wherein aluminum ions and iron ions exist in a precipitation form to form first leaching slag. The impurity ions in the first leaching solution only comprise part of copper ions, calcium ions and magnesium ions. Wherein the liquid-solid ratio of the acidic solution to the battery after pretreatment is 3:1, the pH is preferably 5.0-5.5, and the reaction time is preferably 4 hours. In the present application, the unit of the liquid-solid ratio is mL/g.
In step S02, 3.6N to 4.0N sulfuric acid is used as the acidic solution, the end point pH is controlled to 0.5 to 1.5, and the liquid-solid ratio of the acidic solution to the first leaching residue is 200 to 500: 100. The acidic solution is used for dissolving copper ions, aluminum ions and iron ions in the first leaching residue. The liquid-solid ratio of the acidic solution having a pH of 1.5 to 2.0 to the first leaching residue is preferably 3: 1.
In the step S02, after the acidic solution is added, the temperature is first raised to 85 to 90 ℃ for dissolution, which is advantageous for improving the dissolution efficiency. Reacting at 85-90 ℃ for 2-4 hours, cooling to 50-80 ℃, adding a reducing agent, heating to 85-90 ℃ and reacting for 1-2 hours to obtain a second leaching solution. Reducing agent is added after cooling to avoid the decomposition of the reducing agent, and the reaction speed can be accelerated by the re-heating reaction. Wherein the temperature reduction is preferably 65 ℃ to 70 ℃.
In the above step S02, the reducing agent may be hydrogen peroxide, sodium sulfite, sodium metabisulfite, oxalic acid, oxalate or the like, and preferably the reducing agent is hydrogen peroxide and oxalic acid to prevent the introduction of new impurity ions. In the leaching process of the reducing agent, the pH is controlled to be 1.5-2.0, so that aluminum ions and iron ions are prevented from being precipitated and separated out. Through the reduction of the reducing agent, high-valence metal ions are reduced into stable low-valence metal ions so as to avoid subsequent reaction with other ions. The reaction equation is as follows:
LiCoO 2 /LiNiO 2 /0.5LiMn 2 O 4 +8.5H + +1.75H 2 O 2 ＝2.5Li + +Co 2+ +Ni 2+ +Mn 2+ +6H 2 O +1.75O 2 ↑
in the step S02, the copper ions may be removed by a displacement reaction or an extraction method, for example, by performing a displacement reaction on manganese powder to displace the copper ions to manganese ions, thereby generating a copper metal precipitate and recovering copper metal. The extraction method can be used for extracting copper ions by using a chelate extractant (LIX984, LIX984N, etc.). And the reaction solution after the copper ions are removed is a third leaching solution.
In the step S02, the method for removing iron ions is to adjust the pH of the third leaching solution to 2.5 to 3.5, at this time, iron ions are precipitated as ferric hydroxide, and the acidic solution can reduce the precipitation of cobalt ions and nickel ions, thereby increasing the recovery rate of iron ions. And filtering the reaction solution without iron ions to obtain a fourth leaching solution. Wherein the pH value of the third leaching solution is 2.8-3.0.
In the step S02, the pH of the fourth leachate is adjusted to 4.5 to 5.5, so that aluminum ions are formed into aluminate and a small amount of remaining iron ions are precipitated, and the second leachate is filtered to obtain the second mixed solution and the aluminum slag, wherein the aluminum slag contains a part of the iron ions. Dissolving the aluminum slag by an alkaline solution to obtain second leaching slag, returning the second leaching slag to the high-acid dissolving step, namely mixing the second leaching slag with the first leaching slag and then dissolving the second leaching slag by high acid, or separately dissolving the second leaching slag by high acid, reducing the second leaching slag by a reducing agent, and then sequentially removing copper ions, iron ions and aluminum ions to obtain a second mixed solution. Therefore, the aluminum slag is subjected to secondary treatment to improve the recovery rate of heavy metal cobalt, nickel and manganese ions and enrich aluminum. Wherein the pH value of the fourth leaching solution is 5.0-5.5.
In the step S03, the extracting agent is P204, and P204 has a strong extracting ability for impurity metal ions. In order to prevent the introduction of sodium ions, the extracting agent is firstly converted into cobalt soap or nickel soap, the third mixed solution is extracted and subjected to impurity removal after the pH is adjusted, trace zinc ions in the third mixed solution are removed, and cobalt washing liquid and manganese washing liquid are respectively obtained. In the extraction process, cobalt ions, nickel ions and magnesium ions can be enriched in the obtained cobalt washing liquid. The manganese ions can be enriched by the obtained manganese washing liquid, the concentration of the manganese ions in the manganese washing liquid is 90-120 g/L, but calcium ions cannot be completely separated out by the manganese washing liquid, and a lot of calcium ions remain, so that the manganese washing liquid is enriched with the manganese ions and the calcium ions. And mixing the manganese washing liquid and the cobalt washing liquid to obtain a fourth mixed liquid.
Wherein, the extraction process adopts a full extraction and full return process, so that part of lithium ions can be discharged along with the mother liquor, and the aim of removing the lithium ions is fulfilled.
In the above step S04, the precipitating agent is a fluoride, such as sodium fluoride, nickel fluoride, cobalt fluoride or manganese fluoride, wherein manganese fluoride is preferably used as the fluoride, and the content of manganese ions is increased by avoiding introducing new impurity ions, and the precipitating agent of the fluoride can precipitate calcium ions and magnesium ions.
Among them, the calcium ion content is high, and therefore, the fluorine ion content in the final reaction solution is low. The reason is that the solubility product is fixed in the process of removing calcium ions and magnesium ions, so the total content of the calcium ions and the magnesium ions is higher, the less the using amount of a precipitator in the impurity removal process is, the lower the pH value of the precipitation end point is, the less the content of residual fluorine ions in the solution after impurity removal is, the less the loss of metal ions carried in the precipitation process is, and the higher the recovery rate of heavy metals is.
In the finally obtained reaction liquid, residual fluorine ions can be removed by adopting a fluorine removal agent, and then qualified liquid which meets the impurity content used in precursor production is obtained.
In the following examples, the results of analyzing the elemental contents of the battery reclaimed materials after pretreatment as the experimental raw materials are shown in table 1 below.
Table 1 unit of elemental content analysis results for experimental raw materials: is based on
| Element(s) | Co | Ni | Cu | Fe | Ca | Mg | Mn | Zn | Cd | Cr | Pb | Al | Li |
| Experimental materials | 4.13 | 14.86 | 1.61 | 2.46 | 0.12 | 0.044 | 6.4 | 0.0015 | 0.0006 | 0.0051 | 0.0063 | 1.66 | 3.4 |
Example one
The embodiment of the invention provides a metal recovery processing method for a battery reclaimed material, which comprises the following steps:
s01, taking 100g of experiment raw materials, adding 400ml of pure water according to a liquid-solid ratio of 4:1 for size mixing, adding 98% concentrated sulfuric acid to adjust the pH value of the solution to 4.8, heating to 85-90 ℃ after the solution is not mixed, preserving heat for reaction for 4 hours, filtering to obtain a first leaching solution and first leaching residues, and adding manganese powder into the first leaching solution by using LIX984N to remove copper ions to obtain a first mixed solution. The contents of the respective elements in the first mixed solution are shown in table 2 below.
Table 2 unit of element content analysis result of the first mixed solution: g/L
| Element(s) | Cu | Fe | Ca | Mg | Zn | Cd | Cr | Pb | Al | Li |
| First mixed liquid | 0.0005 | 0.0005 | 0.039 | 0.016 | 0.0029 | 0.0064 | 0.0005 | 0.0036 | 0.0005 | 2.91 |
S02, adding a 4.0N sulfuric acid solution into the first leaching residue according to a liquid-solid ratio of 4:1 for dissolving, heating to 85-90 ℃, reacting for 4 hours, cooling to 70 ℃, adding hydrogen peroxide to reduce undecomposed high-valence metal oxides, heating to 85-90 ℃ after adding a reducing agent, keeping the temperature, reacting for 2 hours, filtering to obtain a second leaching solution, and performing centralized treatment on the filtered leaching residue which is waste residue. And removing copper ions from the second leaching solution through manganese powder to generate a third leaching solution, removing iron ions from the third leaching solution to generate a fourth leaching solution, wherein the pH value of the iron ions removed is 3.0-3.5, and the filtered iron slag is waste slag and is subjected to centralized treatment. And (3) regulating the pH value of the fourth leaching solution to 4.98 by using a sodium carbonate solution to remove aluminum ions, carrying out centralized treatment and recovery on the filtered aluminum slag, and removing the aluminum ions to obtain a second mixed solution. The contents of the elements in the second mixed solution are shown in table 3 below.
Table 3 unit of element content analysis result of the second mixed solution: g/L
| Element(s) | Cu | Fe | Ca | Mg | Zn | Cd | Cr | Pb | Al | Li |
| The second mixed solution | 0.0027 | 0.0051 | 0.7 | 0.64 | 0.003 | 0.0005 | 0.0005 | 0.0036 | 0.0005 | 2.91 |
And S03, mixing the first mixed solution and the second mixed solution to form a third mixed solution, adjusting the pH value, and then carrying out extraction and impurity removal through P204 to obtain a cobalt washing solution and a manganese washing solution, and mixing to obtain a fourth mixed solution.
S04, precipitating calcium ions and magnesium ions in the fourth mixed solution by using a manganese fluoride solid to obtain a solution after the calcium ions and the magnesium ions are removed, removing the fluorine ions in the solution by using a fluorine removal agent to obtain qualified feed liquid for precursor production, wherein the total concentration of cobalt ions, nickel ions and manganese ions reaches 89.16 g/L. The content of each element in the qualified feed liquid is shown in the following table 4.
Table 4 elemental content analysis results units for qualified feed liquids: g/L
| Element(s) | Cu | Fe | Ca | Mg | Zn | Cd | Cr | Pb | Al | F | Li |
| Qualified feed liquid | 0.0005 | 0.0005 | 0.0012 | 0.003 | 0.0016 | 0.0005 | 0.0005 | 0.001 | 0.0005 | 0.15 | 0.45 |
Example two
The embodiment of the invention provides a metal recovery processing method for a battery reclaimed material, which comprises the following steps:
s01, taking 100g of experiment raw materials, adding 400ml of pure water according to a liquid-solid ratio of 3:1 for size mixing, adding 98% concentrated sulfuric acid for adjusting the pH value of the solution to 4.5, heating to 85-90 ℃ after the solution is not mixed, preserving heat for reaction for 3 hours, filtering to obtain a first leaching solution and first leaching residues, and adding manganese powder into the first leaching solution by using LIX984N for removing copper ions to obtain a first mixed solution. The contents of the respective elements in the first mixed solution are shown in table 5 below.
Table 5 unit of analysis result of element content of first mixed solution: g/L
| Element(s) | Cu | Fe | Ca | Mg | Zn | Cd | Cr | Pb | Al | Li |
| First mixed liquid | 0.001 | 0.0005 | 0.041 | 0.022 | 0.0034 | 0.0069 | 0.0005 | 0.0039 | 0.0006 | 3.11 |
S02, adding 3.6N sulfuric acid solution into the first leaching slag according to the liquid-solid ratio of 4:1 for dissolving, heating to 85-90 ℃ for reaction for 4 hours, cooling to 65 ℃, adding hydrogen peroxide to reduce the undecomposed high-valence metal oxide, heating to 85-90 ℃ after the reducing agent is added, keeping the temperature for reaction for 3 hours, filtering to obtain a second leaching solution, and performing centralized treatment on the filtered leaching slag which is waste slag. Removing copper ions from the second leaching solution through manganese powder to generate a third leaching solution, removing iron ions from the third leaching solution to generate a fourth leaching solution, adjusting the pH value of the iron ions removed to be 3.0-3.5, taking the filtered iron slag as waste slag, performing centralized treatment, adjusting the pH value of the fourth leaching solution to be 5.12 with a sodium carbonate solution to remove aluminum ions, performing centralized treatment and recycling on the filtered aluminum slag, and removing aluminum ions to obtain a second mixed solution. The contents of the respective elements in the second mixed solution are shown in table 6 below.
Table 6 unit of element content analysis result of the second mixed solution: g/L
| Element(s) | Cu | Fe | Ca | Mg | Zn | Cd | Cr | Pb | Al | Li |
| The second mixed solution | 0.0005 | 0.0005 | 0.7 | 0.64 | 0.003 | 0.0005 | 0.0005 | 0.0036 | 0.0005 | 2.91 |
And S03, mixing the first mixed solution and the second mixed solution to form a third mixed solution, adjusting the pH value, and then carrying out extraction and impurity removal through P204 to obtain a cobalt washing solution and a manganese washing solution, and mixing to obtain a fourth mixed solution.
S04, precipitating calcium ions and magnesium ions in the fourth mixed solution by using manganese fluoride solid to obtain calcium ions and magnesium ions removed solution, and removing fluorine ions in the solution by using a fluorine removal agent to obtain qualified feed liquid used for precursor production, wherein the total concentration of cobalt ions, nickel ions and manganese ions reaches 93.6 g/L. The content of each element in the qualified feed liquid is shown in the following table 7.
Table 7 elemental content analysis results units for qualified feed liquids: g/L
| Element(s) | Cu | Fe | Ca | Mg | Zn | Cd | Cr | Pb | Al | F | Li |
| Qualified feed liquid | 0.0005 | 0.0005 | 0.0035 | 0.0038 | 0.0018 | 0.0005 | 0.0005 | 0.001 | 0.0005 | 0.13 | 0.6 |
The foregoing is considered as illustrative only of the preferred embodiments of the invention, and is presented merely for purposes of illustration and description of the principles of the invention and is not intended to limit the scope of the invention in any way. Any modifications, equivalents and improvements made within the spirit and principles of the invention and other embodiments of the invention without the creative effort of those skilled in the art are included in the protection scope of the invention based on the explanation here.
Claims (7)
1. A metal recovery processing method for a battery reclaimed material is characterized by comprising the following steps:
s01, low-acid dissolution: dissolving a pretreated battery reclaimed material by adopting an acid solution, wherein the acid solution is prepared by adopting sulfuric acid, the liquid-solid ratio of the acid solution to the pretreated battery is 200-500: 100, the end point pH is controlled to be 3.5-6.0, the temperature is raised to 85-90 ℃, reacting for 2-6 hours to obtain a first leaching solution and first leaching residues, and removing copper from the first leaching solution to obtain a first mixed solution containing cobalt, nickel and manganese ions;
s02, high-acid dissolution: dissolving the first leaching residue by using an acidic solution, wherein the acidic solution is 3.6-4.0N sulfuric acid, the end point pH is controlled to be 0.5-1.5, the liquid-solid ratio of the acidic solution to the first leaching residue is 200-500: 100, heating to 85-90 ℃ for dissolving, reacting for 2-4 hours, cooling to 50-80 ℃, adding a reducing agent, heating to 85-90 ℃ for reacting for 1-2 hours to obtain a second leaching solution, and sequentially removing copper ions, iron ions and aluminum ions from the second leaching solution to obtain a second mixed solution containing cobalt ions, nickel ions and manganese ions;
s03, mixed extraction: mixing the first mixed solution and the second mixed solution to form a third mixed solution, adjusting the pH value, extracting by using an extracting agent to remove zinc ions, and mixing cobalt washing solution and manganese washing solution obtained in the extraction and washing process to obtain a fourth mixed solution containing cobalt, nickel and manganese ions;
s04, precipitation and impurity removal: and removing calcium and magnesium ions in the fourth mixed solution by using a precipitator to obtain qualified feed liquid.
2. The method according to claim 1, wherein in step S02, the second leachate is subjected to a displacement reaction or extraction to remove copper ions, thereby obtaining a third leachate.
3. The method according to claim 2, wherein the pH of the third leachate is adjusted to 2.5 to 3.5, and the fourth leachate is obtained after filtration.
4. The method according to claim 3, wherein the fourth leachate has a pH of 4.5 to 5.5, and is filtered to obtain the second mixed solution and the aluminum slag, and the aluminum slag is dissolved in an alkaline solution to obtain a second leached slag, and the second leached slag is returned to the high-acid dissolution step and reacted with the first leached slag to obtain the second mixed solution.
5. The battery recycle metal recovery processing method according to any of claims 1 to 4, wherein in step S03, the extractant is P204.
6. The method of claim 1, wherein in step S03, the third mixture is subjected to extraction to remove impurities after the extractant is converted into cobalt soap or nickel soap.
7. The method for recovering and treating the metals in the battery reclaimed materials according to claim 1, wherein in step S04, the precipitating agent is fluoride, and residual fluoride ions are removed by using a fluorine removing agent to obtain qualified feed liquid.
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