Method for auxiliary leaching of waste lithium ion batteries by using sulphide ore

Abstract

The invention belongs to the field of lithium battery material recovery, and particularly relates to a method for leaching a waste lithium ion battery with the assistance of sulphide ore, which comprises the following steps: S1, uniformly mixing sulphide ore and a black powder material of the waste lithium ion battery in a ball mill; s2, leaching the ball-milled mixture in the step S1 by adopting acid leaching, and filtering to obtain leaching residues and leaching liquid; s3, the leaching residues in the step S2 are washed and dried, and a graphite product is obtained; or removing impurities from the leachate obtained in the step S2, and extracting and recovering various metal elements in the leachate. According to the method, the sulphide ore is adopted as an auxiliary leaching additive, high-temperature roasting is not needed, hydrogen peroxide does not need to be used as a leaching agent, and the recovery rate of copper in the sulphide ore is increased while elements in the waste lithium battery are recovered.

Description

Technical Field

[0001] The invention belongs to the field of lithium battery material recovery, and in particular relates to a method for using sulfide ore to assist in leaching of waste lithium-ion batteries. Background Art

[0002] New energy vehicles have been used on a large scale since 2013, and have shown explosive growth since 2014. If calculated based on the average scrap age of new energy electric vehicles of 6 years, the first wave of lithium-ion battery retirement will appear after 2021. Waste lithium-ion batteries contain a large amount of harmful substances, and improper disposal will cause serious pollution to the environment. Therefore, the retirement and recycling of power batteries is a necessary process.

[0003] However, the current traditional recovery process mainly uses sulfuric acid and hydrogen peroxide as a leaching agent to leach the valuable metals in the raw materials. Although hydrogen peroxide is an environmentally friendly redox agent, it is a chemical reagent that is easy to make explosives. During use, strict attention should be paid to its storage and use specifications. The purchased hydrogen peroxide will increase the cost of recycling, and hydrogen peroxide is a substance that is easily decomposed at high temperatures. The utilization rate of hydrogen peroxide in the usual recycling of waste lithium batteries is not high. In the authorization number CN115109933A, sulfide ore is used to leach waste lithium ions, but its process requires 400-1200℃ high-temperature roasting and the use of hydrogen peroxide as a leaching liquid, which increases the danger and energy consumption of the process. In addition, the leaching of sulfide ore in the metallurgical process usually requires high temperature and high pressure conditions. Usually under such conditions, the leaching rate of metals in the sulfide ore cannot reach more than 90%. In the authorization number CN106755999B, microwave-enhanced leaching of chalcopyrite can make the leaching rate of copper reach 75%, but it cannot make the copper completely leached.

[0004] Therefore, how to avoid using high-temperature processes and explosive leaching agents to process and recycle waste lithium-ion batteries and how to improve the recovery rate of metals in sulfide ores while recovering elements from waste lithium batteries are technical problems that urgently need to be solved in this field.

[0005] It should be noted that the above information disclosed in this background technology section is only used to understand the background technology of the present application concept, and therefore, the above description is not considered to constitute information of the prior art. Summary of the invention

[0006] The embodiment of the present disclosure provides a method for using sulfide ore to assist in leaching of waste lithium-ion batteries, comprising the following steps: step S1, mixing the sulfide ore and the waste lithium-ion battery black powder material in a ball mill; step S2, leaching the ball-milled mixture in step S1 by acid leaching, and filtering to obtain leaching residue and leaching liquid; step S3, washing and drying the leaching residue in step S2 with water to obtain a graphite product; or removing impurities and extracting the leaching liquid obtained in step S2 to recover various metal elements therein.

[0007] In an optional embodiment, the sulfide ore in step S1 is one or more of pyrite, chalcopyrite, sphalerite, and cobalt sulfide ore.

[0008] In an optional embodiment, the waste lithium-ion battery black powder material in step S2 includes lithium cobalt oxide black powder, lithium nickel oxide black powder, nickel cobalt manganese oxide black powder, or a mixture of the above.

[0009] In an optional embodiment, the acid in step S3 is sulfuric acid.

[0010] In an optional embodiment, the leaching solution in step S3 is subjected to impurity removal, extraction, etc. to obtain battery-grade cobalt sulfate, nickel sulfate, manganese sulfate, lithium carbonate, etc.

[0011] In an optional embodiment, the sieve used in step S1 has a mesh size of 50 to 300.

[0012] In an optional embodiment, the rotation speed of the materials mixed in the ball mill in step S2 is 400-1000 r / min, the mass ratio of lithium-ion battery waste to sulfide ore during ball milling is 1:0.2-1:1.2, and the ball milling time is 1h-6h.

[0013] In an optional embodiment, the acid leaching temperature in step S3 is 70-90° C., the acid leaching time is 1 h to 6 h, the acid concentration used for acid leaching is 0.1-1.5 mol / L, and the solid-liquid ratio is 1:2 to 1:20.

[0014] The beneficial effects of the present invention are that the present invention uses sulfide ore as an auxiliary leaching additive, does not need to use hydrogen peroxide as a leaching agent, and the temperature of the acid leaching of the entire process is 70-90°C, does not need high-temperature roasting, consumes less energy and is relatively safe. In addition, the present invention improves the recovery rate of metals in sulfide ore while recovering elements in waste lithium batteries. Compared with the microwave-enhanced leaching of chalcopyrite in the authorization number CN106755999B, the recovery rate of copper in the chalcopyrite of the present invention reaches more than 95%.

[0015] Other features and advantages of the present invention will be described in the following description, and partly become apparent from the description, or understood by practicing the present invention. The purpose and other advantages of the present invention are realized and obtained by the structures particularly pointed out in the description, claims and drawings.

[0016] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, preferred embodiments are given below and described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0018] Figure 1 A flow chart of a method for using sulfide ore to assist in leaching of spent lithium-ion batteries provided in an embodiment of the present disclosure. DETAILED DESCRIPTION

[0019] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0020] The terms used herein are only used to describe specific exemplary configurations and are not intended to be limited. As used herein, the singular articles "one", "an" and "the" may also be intended to include plural forms, unless it is clearly indicated above that this is not the case. The terms "comprise", "include" and "have" are inclusive, and therefore specify the presence of features, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, elements, components and / or combinations thereof. The method steps, processes and operations described herein should not be interpreted as necessarily requiring them to be performed in the specific order discussed or shown, unless specifically identified as an execution order. Additional or alternative steps may be adopted.

[0021] As used herein, the phrases "in one embodiment," "according to one embodiment," "in some embodiments," and the like generally refer to the fact that the particular feature, structure, or characteristic following the phrase may be included in at least one embodiment of the present disclosure. Therefore, a particular feature, structure, or characteristic may be included in more than one embodiment of the present disclosure, so that these phrases do not necessarily refer to the same embodiment. As used herein, the terms "example," "exemplary," and the like are used to "serve as an example, instance, or illustration." Any implementation, aspect, or design described herein as "example" or "exemplary" is not necessarily to be construed as preferred or superior to other implementations, aspects, or designs. On the contrary, the use of the terms "example," "exemplary," and the like is intended to present concepts in a concrete manner.

[0022] It has been found through research that the disadvantages of the prior art are: the current traditional recovery process mainly uses sulfuric acid and hydrogen peroxide as a leaching agent to leach the valuable metals in the raw materials. Although hydrogen peroxide is an environmentally friendly redox agent, it is a chemical reagent that is easy to make explosives. During use, strict attention should be paid to its storage and use specifications. The purchased hydrogen peroxide will increase the cost of recycling, and hydrogen peroxide is a substance that is easily decomposed at high temperatures. The utilization rate of hydrogen peroxide in the usual recycling of waste lithium batteries is not high. In addition, the leaching of sulfide ores in the metallurgical process usually requires high temperature and high pressure conditions. Usually, under such conditions, the leaching rate of metals in sulfide ores cannot reach more than 90%. In the authorization number CN106755999B, microwave-enhanced leaching of chalcopyrite can make the leaching rate of copper reach 75%, but it cannot make the copper completely leached.

[0023] Based on the above research, an embodiment of the present disclosure provides a method for using sulfide ore to assist in leaching of waste lithium-ion batteries. The use of sulfide ore as an auxiliary leaching additive reduces the cost of the leaching process and is safer than hydrogen peroxide. At the same time, it solves the problem that sulfide ore is difficult to be leached in the solution and increases the concentration of available metal elements in the leaching solution.

[0024] The defects existing in the above solutions are the results obtained by the inventor after practice and careful research. Therefore, the discovery process of the above problems and the solutions proposed by the present disclosure for the above problems below should be the contributions made by the inventor to the present disclosure during the disclosure process.

[0025] It should be noted that similar reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, further definition and explanation thereof is not required in subsequent drawings.

[0026] Some embodiments of the present invention are described in detail below in conjunction with the accompanying drawings. In the absence of conflict, the following embodiments and features in the embodiments can be combined with each other.

[0027] The embodiment of the present disclosure provides a method for using sulfide ore to assist in leaching of waste lithium-ion batteries, comprising the following steps: step S1, mixing the sulfide ore and the waste lithium-ion battery black powder material in a ball mill; step S2, leaching the ball-milled mixture in step S1 by acid leaching, and filtering to obtain leaching residue and leaching liquid; step S3, washing and drying the leaching residue in step S2 with water to obtain a graphite product; or removing impurities and extracting the leaching liquid obtained in step S2 to recover various metal elements therein.

[0028] In some embodiments, specifically, the sulfide ore in step S1 is one or more of pyrite, chalcopyrite, sphalerite, and cobalt sulfide ore.

[0029] In some embodiments, specifically, the waste lithium-ion battery black powder material in step S2 includes lithium cobalt oxide black powder, lithium nickel oxide black powder, nickel cobalt manganese oxide black powder, or a mixture of the above.

[0030] In some embodiments, specifically, the acid in step S3 is sulfuric acid.

[0031] In some embodiments, specifically, the leaching solution in step S3 is subjected to impurity removal, extraction, etc. to obtain battery-grade cobalt sulfate, nickel sulfate, manganese sulfate, and lithium carbonate.

[0032] In some embodiments, specifically, the sieve used in step S1 is 50-300 mesh.

[0033] In some embodiments, specifically, the rotation speed of the materials mixed in the ball mill in step S2 is 400-1000 r / min, the mass ratio of lithium-ion battery waste to sulfide ore during ball milling is 1:0.2-1:1.2, and the ball milling time is 1h-6h.

[0034] In some embodiments, specifically, in step S3, the acid leaching temperature is 70-90° C., the acid leaching time is 1 h to 6 h, the acid concentration used for acid leaching is 0.1-1.5 mol / L, and the solid-liquid ratio is 1:2 to 1:20.

[0035] The present invention is further described below in conjunction with specific embodiments of the present invention. It should be noted that what is described is only a part of the embodiments of the present invention rather than all the embodiments, and these embodiments shall not be used to interpret the limitation of the protection scope of the claims of this application. Based on the embodiments of the present invention, all other changes or modifications obtained by ordinary technicians in this field without creative work are within the protection scope of the claims of this application.

[0036] Example 1

[0037] The specific steps are as follows:

[0038] The chalcopyrite powder was crushed by a sample preparation machine and then sieved through 200 meshes. The mass ratio of lithium cobalt oxide black powder to the sieved chalcopyrite powder was lithium cobalt oxide black powder: chalcopyrite = 1:0.2. 50 g of lithium ion battery waste was used for batching. The ball mill speed was 600 r / min. After the ball milling time was 4 hours, a sulfuric acid solution with a concentration of 0.5 mol / L was used to leach the mixture. The solid-liquid ratio was 1:10. The leaching time was 4 hours and the leaching temperature was 80°C. A solution rich in valuable metal ions was obtained. The leaching rates of the metals were determined to be Li 97.88%, Co

[0039] 99.26%, Fe 96.35%, Cu 96.22%. The above leaching solution is simply impurity-removed and extracted with P507 to obtain cobalt sulfate. Sodium carbonate is added to the residual extract to evaporate and crystallize to obtain lithium carbonate solid.

[0040] In the case of the same specific steps, by modifying some parameters in Example 1, the effects and performances of Examples 2 and 3 as shown in the following table are obtained:

[0041] Comparative Example 1:

[0042] The difference compared with Example 2 is that the leaching temperature is 20°C.

[0043] Comparative Example 2:

[0044] The difference compared with Example 2 is that the leaching temperature is 60°C.

[0045] Comparative Example 3:

[0046] The difference compared with Example 2 is that hydrogen peroxide is used as an auxiliary leaching agent.

[0047] The results of the embodiments are shown in Table 1:

[0048]

[0049] Referring to Table 1, it is concluded from Examples 1-2 that the sulfide ore is used as an auxiliary leaching agent to leach lithium cobalt oxide black powder, and the recovery rates of Li and Co in the lithium cobalt oxide black powder are both above 97%; wherein, the type of sulfide ore used in Example 1 is chalcopyrite, and the recovery rate of Cu in chalcopyrite reaches 96.22%.

[0050] Continuing to refer to Table 1, it is concluded through Example 3 that the sulfide ore is used as an auxiliary leaching agent to leach the nickel cobalt manganese oxide black powder, and the recovery rates of Li, Ni, Co, and Mn in the nickel cobalt manganese oxide black powder are all above 97%. Due to the excessive proportion of pyrite powder, the recovery rate of iron in this embodiment does not reach above 90%. It can be seen from the above data that the excessive pyrite powder does not affect the recovery of elements in waste lithium batteries, but only affects the recovery rate of iron element in pyrite itself.

[0051] Continuing to refer to Table 1, by comparing Examples 1-3 with Comparative Examples 1-2, when the leaching temperature is lower than 70°C, the recovery rates of elements in waste lithium batteries and metal elements in sulfide ores are not high. This is because the activity of sulfides is not high at lower temperatures and the reaction with lithium-ion battery black powder is incomplete. Therefore, as a preference, the leaching temperature is set to 70°C to 90°C in this process.

[0052] Continuing to refer to Table 1, by comparing Examples 1-3 with Comparative Example 3, under the same conditions, using sulfide ore as an auxiliary agent can well leach the waste lithium-ion battery black powder material, and can also achieve the effect of auxiliary leaching using hydrogen peroxide in the traditional method, and the leaching effect is even slightly better than the traditional method.

[0053] In summary, the present invention uses sulfide ore as an auxiliary leaching additive, does not need to use hydrogen peroxide as a leaching agent, and the temperature of the entire process acid leaching is 70-90°C, does not need high-temperature roasting, consumes less energy and is relatively safe. In addition, the present invention improves the recovery rate of metals in sulfide ore while recovering elements in waste lithium batteries. Compared with the microwave-enhanced leaching of chalcopyrite in the authorization number CN106755999B, the recovery rate of copper in the chalcopyrite of the present invention is 75%, and the recovery rate of copper in the chalcopyrite reaches more than 95%.

[0054] Based on the above ideal embodiments of the present invention, the relevant staff can make various changes and modifications without departing from the technical concept of the present invention through the above description. The technical scope of the present invention is not limited to the contents of the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A method for leaching waste lithium-ion batteries using sulfide ore, characterized in that: The following steps are involved: Step S1, mixing the sulfide ore and the waste lithium-ion battery black powder material in a ball mill; Step S2, leaching the ball-milled mixture in step S1 by acid leaching, and filtering to obtain leached residue and leaching liquid; Step S3, washing and drying the leached residue in step S2 to obtain a graphite product; or, The leaching solution obtained in step S2 is subjected to impurity removal and extraction to recover various metal elements therein.

2. The method for leaching waste lithium-ion batteries using sulfide ore as claimed in claim 1, characterized in that: The sulfide ore in step S1 is one or more of pyrite, chalcopyrite, sphalerite, and cobalt sulfide ore, and is obtained by crushing and screening the sulfide ore.

3. The method for leaching waste lithium-ion batteries using sulfide ore as claimed in claim 1, characterized in that: The waste lithium-ion battery black powder material in step S1 includes one or a mixture of lithium cobalt oxide black powder, lithium nickel oxide black powder, and lithium nickel cobalt manganese oxide black powder.

4. The method for leaching waste lithium-ion batteries using sulfide ore as claimed in claim 1, characterized in that: The acid in step S2 is sulfuric acid.

5. The method for leaching waste lithium-ion batteries using sulfide ore as claimed in claim 1, characterized in that: The leaching solution in step S2 is subjected to impurity removal, extraction, etc. to obtain battery-grade cobalt sulfate, nickel sulfate, manganese sulfate, and lithium carbonate.

6. The method for leaching waste lithium-ion batteries using sulfide ore as claimed in claim 1, characterized in that: The sieve used in step S1 is 50-300 meshes.

7. The method for leaching waste lithium-ion batteries using sulfide ore as claimed in claim 1, characterized in that: In the step S1, the rotation speed of the materials in the ball mill is 400-1000 r / min, the mass ratio of lithium ion battery waste to sulfide ore during ball milling is 1:0.2-1:1.2, and the ball milling time is 1h-6h.

8. The method for leaching waste lithium-ion batteries using sulfide ore as claimed in claim 1, characterized in that: In step S2, the acid leaching temperature is 70-90° C., the acid leaching time is 1 h-6 h, the acid concentration used for the acid leaching is 0.1-1.5 mol / L, and the solid-liquid ratio is 1:2-1:

20.

9. A method for leaching waste lithium-ion batteries using chalcopyrite, characterized in that: The recovery rate of copper in the chalcopyrite is not less than 95%.

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