WO2022206066A1 - Method for recovering valuable metals from waste lithium-ion batteries - Google Patents
Method for recovering valuable metals from waste lithium-ion batteries Download PDFInfo
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- WO2022206066A1 WO2022206066A1 PCT/CN2021/142284 CN2021142284W WO2022206066A1 WO 2022206066 A1 WO2022206066 A1 WO 2022206066A1 CN 2021142284 W CN2021142284 W CN 2021142284W WO 2022206066 A1 WO2022206066 A1 WO 2022206066A1
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- reaction
- leaching
- water
- graphite slag
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 35
- 150000002739 metals Chemical class 0.000 title claims abstract description 25
- 239000002699 waste material Substances 0.000 title claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002893 slag Substances 0.000 claims abstract description 47
- 238000002386 leaching Methods 0.000 claims abstract description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 44
- 229910002804 graphite Inorganic materials 0.000 claims description 44
- 239000010439 graphite Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 238000007654 immersion Methods 0.000 claims description 21
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 7
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 4
- 230000002431 foraging effect Effects 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
-
- 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
-
- 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
-
- 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
-
- 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
Definitions
- the invention belongs to the technical field of resource recovery of waste and used lithium ion batteries, and particularly relates to a method for recovering valuable metals of waste and used lithium ion batteries.
- scrap lithium-ion batteries After a lithium-ion battery undergoes a certain number of cycles of charge and discharge, the structure of the active material will fail due to changes. It is expected that the scrapped and scrapped amount of vehicle power batteries will reach 101GWh in 2030, about 1.16 million tons. Scrap lithium-ion batteries contain a variety of harmful substances, such as heavy metals, organic and inorganic harmful compounds, etc. If they are not disposed of in time, they will easily pollute the environment. At the same time, lithium-ion batteries contain a large amount of nickel, cobalt, manganese, and lithium valuable metals. If they are not recycled in time, it will inevitably lead to waste of resources and pollution to the environment.
- the recovery process of valuable metals in waste lithium batteries is roughly divided into two categories: pyro process and wet process.
- the recovery process based on hydrometallurgy is relatively mature and widely used in the industry.
- the valuable metal liquid is obtained by acid leaching of battery powder, removing copper from iron powder, and removing iron and aluminum.
- the battery powder contains a large amount of organic matter to coat the active material.
- the coating of a large amount of organic matter will reduce the probability of the positive electrode material contacting sulfuric acid and reduce the reaction rate.
- a large amount of organic matter will cause the solution
- the surface tension in the leaching process increases, resulting in a large number of bubbles in the gas released during the leaching process, causing risks such as troughing.
- the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. Therefore, the present invention proposes a method for recovering valuable metals of waste lithium ion batteries, which can simplify the recovery process of valuable metals in waste lithium batteries, reduce production costs, and at the same time avoid the risk of bubbling caused by bubbling of valuable metals in the leaching process of waste lithium batteries. slot problem.
- the pH of the solution after the water immersion reaction is 4.5 or more.
- the pretreatment steps include discharge, crushing and screening.
- step S1 in step S1, the molar ratio of the concentrated sulfuric acid to the positive electrode material in the battery powder is (1-1.5):1, and the mass concentration of the concentrated sulfuric acid is more than 70%.
- step S1 the mass concentration of the concentrated sulfuric acid is 70-80%.
- step S1 the time of the aging reaction is 0.5-5 h.
- step S1 the time of the aging reaction is 0.5-3 hours.
- step S1 the aging reaction process adopts mechanical slow stirring.
- step S2 the mass of the added water is 3-10 times the mass of the battery powder in step S1.
- step S2 the mass of the added water is 3 to 5 times the mass of the battery powder in step S1.
- step S2 the water immersion time is 0.5-10 h, and the temperature is 40-90°C.
- step S2 the water immersion time is 2-4 hours, and the temperature is 50-70°C.
- step S3 the specific process of the acid leaching reaction is to add water to the first graphite slag to make pulp, and then add acid solution to adjust pH to carry out the acid leaching reaction, the first graphite slag
- the solid-liquid ratio with water is 1:(3-10) g/ml, and the pH is adjusted to 0.5-1.5.
- step S3 the temperature of the acid leaching reaction is 40-90° C., and the reaction time is 0.5-10 h.
- the reducing agent is one or more of sodium sulfite, sodium thiosulfate or hydrogen peroxide; the reducing agent and the valuable metal in the first graphite slag
- the molar ratio is (1 ⁇ 1.5):1.
- step S3 the reaction temperature of the redox leaching is 70-80° C., and the reaction time is 4-6 h.
- step S3 the reaction temperature of the redox leaching is 40-90° C., and the reaction time is 0.5-10 h.
- the lye is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, calcium carbonate, calcium bicarbonate, nickel carbonate, and manganese carbonate;
- the pH is adjusted to 4.5-5.
- step S4 the reaction time after adding alkali solution to adjust pH is 1-2h.
- the present invention utilizes the carbonization of concentrated sulfuric acid to carbonize and decompose the organic matter in the battery powder, so as to solve the problems such as foaming and troughing caused by the organic matter in the process of organic matter coating the battery powder active material and water immersion and acid leaching;
- the reaction of sulfuric acid releases a lot of heat during the aging process, and increasing the temperature is conducive to the decomposition of organic substances, providing a heat source for subsequent water immersion, reducing the input of heat source and reducing production costs.
- Water immersion can disperse the active material of battery powder, improve the probability of contact reaction between sulfuric acid and active material, and increase the reaction rate. Moreover, after the water immersion reaction, the pH of the solution is above 4.5, which can precipitate most of the impurity substances in the solution, which can reduce the concentration of the solution in the solution.
- the process flow in the purification process reduces production costs and improves work efficiency.
- Acid leaching can dissolve the positive electrode material in the first graphite slag, and provide an acid leaching environment for redox leaching, improve the recovery rate of valuable metals, reduce the content of valuable metals in graphite slag, and reduce the pollution of graphite slag to the environment .
- the leaching and impurity removal of the present invention are carried out simultaneously, which simplifies the recovery process of the valuable metal of the waste lithium battery and reduces the production cost.
- FIG. 1 is a process flow diagram of Embodiment 1 of the present invention.
- the present embodiment reclaims the valuable metals in the waste lithium-ion battery, and the specific process is as follows:
- first graphite slag as 42 g, make the first graphite slag with 126 ml of water slurry, raise the temperature to 70 °C, add concentrated sulfuric acid dropwise to pH 0.5, add sodium sulfite with 1 times the molar amount of the valuable metal in the graphite slag, react for 4 h, dropwise Add an appropriate amount of sodium hydroxide, adjust the pH of the solution to 4.5, react for 1 h, and filter to obtain the second valuable metal liquid and the second graphite slag.
- the present embodiment reclaims the valuable metals in the waste lithium-ion battery, and the specific process is as follows:
- first graphite slag as 45g, make the first graphite slag with 135ml of water slurry, heat up to 70°C, add concentrated sulfuric acid dropwise to pH 0.5, add sodium sulfite with 1.2 times the molar amount of the valuable metal in the graphite slag, react for 3h, dropwise Add an appropriate amount of sodium hydroxide, adjust the pH of the solution to 4.5, react for 1 h, and filter to obtain the second valuable metal liquid and the second graphite slag.
- the present embodiment reclaims the valuable metals in the waste lithium-ion battery, and the specific process is as follows:
- first graphite slag as 45g, make the first graphite slag with 135ml of water slurry, heat up to 70°C, add concentrated sulfuric acid dropwise to pH 0.5, add sodium sulfite with 1.3 times the molar amount of the valuable metal in the graphite slag, react for 3h, dropwise Add an appropriate amount of sodium hydroxide, adjust the pH of the solution to 4.5, react for 1 h, and filter to obtain the second valuable metal liquid and the second graphite slag.
- the present embodiment reclaims the valuable metals in the waste lithium-ion battery, and the specific process is as follows:
- first graphite slag as 46g, make the first graphite slag with 138ml of water slurry, raise the temperature to 70°C, add concentrated sulfuric acid dropwise to pH 1.0, add sodium sulfite with 1.5 times the molar amount of the valuable metal in the graphite slag, react for 4h, dropwise Add an appropriate amount of sodium hydroxide, adjust the pH of the solution to 4.5, react for 1 h, and filter to obtain the second valuable metal liquid and the second graphite slag.
- the present embodiment reclaims the valuable metals in the waste lithium-ion battery, and the specific process is as follows:
- first graphite slag as 40g, make the first graphite slag with 120ml of water, heat up at 70°C, add concentrated sulfuric acid dropwise to pH 1.0, add sodium sulfite with 1.5 times the molar amount of the valuable metal in the graphite slag, react for 5h, dropwise Add an appropriate amount of sodium hydroxide, adjust the pH of the solution to 4.5, react for 1 h, and filter to obtain the second valuable metal liquid and the second graphite slag.
- Table 1 shows the content of valuable metals in the battery powder used in Examples 1-5.
- Table 3 shows the recovery rate of valuable metals in Examples 1-5.
- Example 1 99.8 97.6 99.3
- Example 2 99.4 99.0 99.6
- Example 3 99.2 99.5 99.1
- Example 4 99.6 99.3 99.0
- Example 5 99.2 99.1 99.7
- the impurity content (Fe 2+ , Al, Cu) of the obtained valuable metal liquid is very low, and the recovery rate of the valuable metal is very high, indicating that the leaching and impurity removal of the present invention are carried out simultaneously.
- the recovery method not only has a simple process and low cost, but also has a good recovery effect.
- Fig. 1 is a process flow diagram of the present invention, the battery powder is added with concentrated sulfuric acid to carry out maturation leaching, then water is added to carry out water leaching, after solid-liquid separation, the first graphite slag is added to dilute sulfuric acid to carry out acid leaching, then a reducing agent is added to carry out reduction leaching, and then Add alkali to precipitate impurities, and finally obtain second graphite slag and second valuable metal liquid by solid-liquid separation.
Abstract
A method for recovering valuable metals from waste lithium-ion batteries, the method comprising first adding concentrated sulfuric acid to battery powder for aging and leaching, then adding water for water leaching, and subjecting same to solid-liquid separation to obtain a first kish slag and a first valuable metal liquid; and adding an acid liquor to the first kish slag for acid leaching, then adding a reducing agent for reduction leaching further adding an alkali for precipitating impurities and finally subjecting same to solid-liquid separation to obtain a second kish slag and a second valuable metal liquid.
Description
本发明属于废旧锂离子电池资源回收技术领域，具体涉及一种回收废旧锂离子电池有价金属的方法。The invention belongs to the technical field of resource recovery of waste and used lithium ion batteries, and particularly relates to a method for recovering valuable metals of waste and used lithium ion batteries.
锂离子电池经过一定次数的循环充放电后，活性材料的结构会因为发生改变而失效，预计2030年车用动力电池报废报废量将达到101GWh，约116万吨。报废的锂离子电池含有多种有害物质，如重金属、有机和无机有害化合物等，如果处理不及时，极易对环境造成污染。同时，锂离子电池中含有大量的镍钴锰锂有价金属，如果不及时回收势必会造成资源的浪费和对环境的污染。After a lithium-ion battery undergoes a certain number of cycles of charge and discharge, the structure of the active material will fail due to changes. It is expected that the scrapped and scrapped amount of vehicle power batteries will reach 101GWh in 2030, about 1.16 million tons. Scrap lithium-ion batteries contain a variety of harmful substances, such as heavy metals, organic and inorganic harmful compounds, etc. If they are not disposed of in time, they will easily pollute the environment. At the same time, lithium-ion batteries contain a large amount of nickel, cobalt, manganese, and lithium valuable metals. If they are not recycled in time, it will inevitably lead to waste of resources and pollution to the environment.
针对废旧锂电池有价金属的回收，国内外研究人员进行了大量的研究。目前废旧锂电池中有价金属的回收工艺大致分为火法和湿法两大类，其中基于湿法冶金的回收工艺相对成熟，行业内应用比较广泛。相关技术中提到用电池粉酸浸、铁粉除铜、除铁铝等步骤得到有价金属液，但是冗长的工艺流程不仅会降低工作效率，也会增加人力物力成本。Domestic and foreign researchers have carried out a lot of research on the recovery of valuable metals from waste lithium batteries. At present, the recovery process of valuable metals in waste lithium batteries is roughly divided into two categories: pyro process and wet process. Among them, the recovery process based on hydrometallurgy is relatively mature and widely used in the industry. In the related art, it is mentioned that the valuable metal liquid is obtained by acid leaching of battery powder, removing copper from iron powder, and removing iron and aluminum.
电池粉中含有大量的有机物包覆活性材料，在回收废旧锂电池有价金属的实际生产中，大量有机物的包覆会减少正极材料与硫酸接触的概率，减低反应速率，大量的有机物会使溶液中的表面张力增加，导致浸出过程释放的气体产生大量气泡，造成冒槽等风险。The battery powder contains a large amount of organic matter to coat the active material. In the actual production of recovering valuable metals from waste lithium batteries, the coating of a large amount of organic matter will reduce the probability of the positive electrode material contacting sulfuric acid and reduce the reaction rate. A large amount of organic matter will cause the solution The surface tension in the leaching process increases, resulting in a large number of bubbles in the gas released during the leaching process, causing risks such as troughing.
发明内容SUMMARY OF THE INVENTION
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种回收废旧锂离子电池有价金属的方法，能够简化废旧锂电池有价金属回收工艺，降低生产成本，同时避免废旧锂电池中有价金属浸出过程冒泡引起的冒槽问题。The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. Therefore, the present invention proposes a method for recovering valuable metals of waste lithium ion batteries, which can simplify the recovery process of valuable metals in waste lithium batteries, reduce production costs, and at the same time avoid the risk of bubbling caused by bubbling of valuable metals in the leaching process of waste lithium batteries. slot problem.
根据本发明的一个方面，提出了一种回收废旧锂离子电池有价金属的方法，包括以 下步骤：According to one aspect of the present invention, there is proposed a method for recycling the valuable metals of waste and used lithium ion batteries, comprising the following steps:
S1：将废旧锂离子电池进行前处理得到电池粉，加入浓硫酸进行熟化反应；S1: pre-processing the waste lithium-ion battery to obtain battery powder, and adding concentrated sulfuric acid to carry out the aging reaction;
S2：向熟化后的电池粉加水进行水浸反应，然后固液分离，得到第一石墨渣与第一有价金属液；S2: adding water to the aged battery powder to carry out water immersion reaction, and then solid-liquid separation to obtain the first graphite slag and the first valuable metal liquid;
S3：向所述第一石墨渣加入酸液进行酸浸反应，再加入还原剂进行氧化还原浸出；S3: adding acid solution to the first graphite slag to carry out acid leaching reaction, and then adding a reducing agent to carry out redox leaching;
S4：向氧化还原浸出后的溶液加入碱液调节pH进行反应，固液分离后得到第二石墨渣和第二有价金属液。S4: adding alkaline solution to the solution after redox leaching to adjust pH to carry out the reaction, and after solid-liquid separation, a second graphite slag and a second valuable metal solution are obtained.
其中，水浸反应后溶液的pH为4.5以上。Here, the pH of the solution after the water immersion reaction is 4.5 or more.
在本发明的一些实施方式中，步骤S1中，所述前处理的步骤包括放电、破碎和筛分。In some embodiments of the present invention, in step S1, the pretreatment steps include discharge, crushing and screening.
在本发明的一些实施方式中，步骤S1中，所述浓硫酸与电池粉中正极材料的摩尔比为(1～1.5)：1，所述浓硫酸的质量浓度为70％以上。In some embodiments of the present invention, in step S1, the molar ratio of the concentrated sulfuric acid to the positive electrode material in the battery powder is (1-1.5):1, and the mass concentration of the concentrated sulfuric acid is more than 70%.
在本发明的一些优选的实施方式中，步骤S1中，所述浓硫酸的质量浓度为70～80％。In some preferred embodiments of the present invention, in step S1, the mass concentration of the concentrated sulfuric acid is 70-80%.
在本发明的一些实施方式中，步骤S1中，所述熟化反应的时间为0.5～5h。In some embodiments of the present invention, in step S1, the time of the aging reaction is 0.5-5 h.
在本发明的一些优选的实施方式中，步骤S1中，所述熟化反应的时间为0.5～3h。In some preferred embodiments of the present invention, in step S1, the time of the aging reaction is 0.5-3 hours.
在本发明的一些实施方式中，步骤S1中，所述熟化反应过程采用机械缓慢搅拌。In some embodiments of the present invention, in step S1, the aging reaction process adopts mechanical slow stirring.
在本发明的一些实施方式中，步骤S2中，所述加水的质量为步骤S1中所述电池粉质量的3～10倍。In some embodiments of the present invention, in step S2, the mass of the added water is 3-10 times the mass of the battery powder in step S1.
在本发明的一些优选的实施方式中，步骤S2中，所述加水的质量为步骤S1中所述电池粉质量的3～5倍。In some preferred embodiments of the present invention, in step S2, the mass of the added water is 3 to 5 times the mass of the battery powder in step S1.
在本发明的一些实施方式中，步骤S2中，所述水浸的时间为0.5～10h，温度为40～90℃。In some embodiments of the present invention, in step S2, the water immersion time is 0.5-10 h, and the temperature is 40-90°C.
在本发明的一些优选的实施方式中，步骤S2中，所述水浸的时间为2～4h，温度为50～70℃。In some preferred embodiments of the present invention, in step S2, the water immersion time is 2-4 hours, and the temperature is 50-70°C.
在本发明的一些实施方式中，步骤S3中，所述酸浸反应的具体过程是将所述第一 石墨渣加水制浆，再加酸液调节pH进行酸浸反应，所述第一石墨渣与水的固液比为1：(3～10)g/ml，所述pH调至0.5～1.5。In some embodiments of the present invention, in step S3, the specific process of the acid leaching reaction is to add water to the first graphite slag to make pulp, and then add acid solution to adjust pH to carry out the acid leaching reaction, the first graphite slag The solid-liquid ratio with water is 1:(3-10) g/ml, and the pH is adjusted to 0.5-1.5.
在本发明的一些实施方式中，步骤S3中，所述酸浸反应的温度为40～90℃，反应的时间为0.5～10h。In some embodiments of the present invention, in step S3, the temperature of the acid leaching reaction is 40-90° C., and the reaction time is 0.5-10 h.
在本发明的一些实施方式中，步骤S3中，所还原剂为亚硫酸钠、硫代硫酸钠或过氧化氢中的一种或多种；所述还原剂与所述第一石墨渣中有价金属的摩尔比为(1～1.5)：1。In some embodiments of the present invention, in step S3, the reducing agent is one or more of sodium sulfite, sodium thiosulfate or hydrogen peroxide; the reducing agent and the valuable metal in the first graphite slag The molar ratio is (1～1.5):1.
在本发明的一些实施方式中，步骤S3中，所述氧化还原浸出的反应温度为70～80℃，反应时间为4～6h。In some embodiments of the present invention, in step S3, the reaction temperature of the redox leaching is 70-80° C., and the reaction time is 4-6 h.
在本发明的一些优选的实施方式中，步骤S3中，所述氧化还原浸出的反应温度为40～90℃，反应时间为0.5～10h。In some preferred embodiments of the present invention, in step S3, the reaction temperature of the redox leaching is 40-90° C., and the reaction time is 0.5-10 h.
在本发明的一些实施方式中，步骤S4中，所述碱液为氢氧化钠、碳酸钠、碳酸氢钠、氨水、碳酸钙、碳酸氢钙、碳酸镍、碳酸锰的一种或多种；步骤S4中，所述pH调至4.5～5。In some embodiments of the present invention, in step S4, the lye is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, calcium carbonate, calcium bicarbonate, nickel carbonate, and manganese carbonate; In step S4, the pH is adjusted to 4.5-5.
在本发明的一些实施方式中，步骤S4中，加入碱液调节pH后反应的时间为1-2h。In some embodiments of the present invention, in step S4, the reaction time after adding alkali solution to adjust pH is 1-2h.
根据本发明的一种优选的实施方式，至少具有以下有益效果：According to a preferred embodiment of the present invention, it has at least the following beneficial effects:
1、本发明利用浓硫酸的碳化作用，碳化分解电池粉中的有机物，解决有机物包覆电池粉活性物质和水浸、酸浸过程中由于有机物质引起的起泡、冒槽等问题；并且浓硫酸在熟化过程中反应释放大量的热，升高温度有利于有机物质分解，为后续水浸提供热源，减少热源的输入从而减少生产成本。1. The present invention utilizes the carbonization of concentrated sulfuric acid to carbonize and decompose the organic matter in the battery powder, so as to solve the problems such as foaming and troughing caused by the organic matter in the process of organic matter coating the battery powder active material and water immersion and acid leaching; The reaction of sulfuric acid releases a lot of heat during the aging process, and increasing the temperature is conducive to the decomposition of organic substances, providing a heat source for subsequent water immersion, reducing the input of heat source and reducing production costs.
2、本发明在进行水浸反应时将大部分低价态的有价金属浸出，余下少量高价态的有价金属残留在第一石墨渣中参与后续氧化还原浸出，由于氧化还原浸出时加入了还原剂，将高价难溶的有价金属氧化成低价的易溶有价金属，这样能够提高还原剂的利用率，水浸时无需加入还原剂，避免高浓度的金属溶液影响还原剂的利用率。另外，加碱调pH值能够沉淀溶液中的铁铝杂质。2. In the present invention, most of the low-valence valuable metals are leached during the water leaching reaction, and a small amount of the high-valence valuable metals remain in the first graphite slag to participate in subsequent redox leaching. Reducing agent, which oxidizes high-priced and insoluble valuable metals into low-priced soluble valuable metals, which can improve the utilization rate of reducing agent. There is no need to add reducing agent during water immersion, so as to avoid the impact of high concentration metal solution on the utilization of reducing agent. Rate. In addition, adding alkali to adjust the pH value can precipitate iron and aluminum impurities in the solution.
3、水浸能够分散电池粉活性物质，提高硫酸与活性物质接触反应概率，提高反应速率，而且水浸反应后溶液pH在4.5以上，可以将溶液中的大部分杂质物质沉淀，可以减少溶液在净化过程中工艺流程，减少生产成本，提高工作效率。3. Water immersion can disperse the active material of battery powder, improve the probability of contact reaction between sulfuric acid and active material, and increase the reaction rate. Moreover, after the water immersion reaction, the pH of the solution is above 4.5, which can precipitate most of the impurity substances in the solution, which can reduce the concentration of the solution in the solution. The process flow in the purification process reduces production costs and improves work efficiency.
4、酸浸能够溶解第一石墨渣中的正极材料，并为氧化还原浸出提供一个酸浸环境，提高有价金属的回收率，减少石墨渣中有价金属含量，减少石墨渣对环境的污染。4. Acid leaching can dissolve the positive electrode material in the first graphite slag, and provide an acid leaching environment for redox leaching, improve the recovery rate of valuable metals, reduce the content of valuable metals in graphite slag, and reduce the pollution of graphite slag to the environment .
5、本发明的浸出与除杂同步进行，简化了废旧锂电池有价金属回收工艺，降低了生产成本。5. The leaching and impurity removal of the present invention are carried out simultaneously, which simplifies the recovery process of the valuable metal of the waste lithium battery and reduces the production cost.
下面结合附图和实施例对本发明做进一步的说明，其中：The present invention will be further described below in conjunction with the accompanying drawings and embodiments, wherein:
图1为本发明实施例1的工艺流程图。FIG. 1 is a process flow diagram of Embodiment 1 of the present invention.
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。The concept of the present invention and the technical effects produced will be clearly and completely described below with reference to the embodiments, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative efforts are all within the scope of The scope of protection of the present invention.
实施例1Example 1
本实施例回收了废旧锂离子电池中的有价金属，具体过程为：The present embodiment reclaims the valuable metals in the waste lithium-ion battery, and the specific process is as follows:
取100g电池粉，加入106ml质量浓度为70％的浓硫酸，机械缓慢搅拌0.5h，加入300g水，水浴加热70℃，水浸反应2h，水浸反应后溶液pH为5.0，过滤得到第一有价金属液和第一石墨渣；Take 100g of battery powder, add 106ml of concentrated sulfuric acid with a mass concentration of 70%, slowly stir mechanically for 0.5h, add 300g of water, heat at 70°C in a water bath, and perform a water immersion reaction for 2 hours. After the water immersion reaction, the pH of the solution is 5.0. Valence molten metal and first graphite slag;
称得第一石墨渣为42g，将第一石墨渣与126ml水制浆，升温70℃，滴加浓硫酸至pH 0.5，加入石墨渣中有价金属摩尔量1倍的亚硫酸钠，反应4h，滴加适量氢氧化钠，将溶液pH调至4.5，反应1h，过滤得到第二有价金属液和第二石墨渣。Weigh the first graphite slag as 42 g, make the first graphite slag with 126 ml of water slurry, raise the temperature to 70 °C, add concentrated sulfuric acid dropwise to pH 0.5, add sodium sulfite with 1 times the molar amount of the valuable metal in the graphite slag, react for 4 h, dropwise Add an appropriate amount of sodium hydroxide, adjust the pH of the solution to 4.5, react for 1 h, and filter to obtain the second valuable metal liquid and the second graphite slag.
实施例2Example 2
本实施例回收了废旧锂离子电池中的有价金属，具体过程为：The present embodiment reclaims the valuable metals in the waste lithium-ion battery, and the specific process is as follows:
取100g电池粉，加入99ml质量浓度为75％的浓硫酸，机械缓慢搅拌0.5h，加入300g水，水浴加热70℃，水浸反应2h，水浸反应后溶液pH为5.0，过滤得到第一有价金属液和第一石墨渣；Take 100g of battery powder, add 99ml of concentrated sulfuric acid with a mass concentration of 75%, slowly stir mechanically for 0.5h, add 300g of water, heat at 70°C in a water bath, and perform a water immersion reaction for 2 hours. After the water immersion reaction, the pH of the solution is 5.0. Valence molten metal and first graphite slag;
称得第一石墨渣为45g，将第一石墨渣与135ml水制浆，升温70℃，滴加浓硫酸至pH 0.5，加入石墨渣中有价金属摩尔量1.2倍的亚硫酸钠，反应3h，滴加适量氢氧化钠，将溶液pH调至4.5，反应1h，过滤得到第二有价金属液和第二石墨渣。Weigh the first graphite slag as 45g, make the first graphite slag with 135ml of water slurry, heat up to 70°C, add concentrated sulfuric acid dropwise to pH 0.5, add sodium sulfite with 1.2 times the molar amount of the valuable metal in the graphite slag, react for 3h, dropwise Add an appropriate amount of sodium hydroxide, adjust the pH of the solution to 4.5, react for 1 h, and filter to obtain the second valuable metal liquid and the second graphite slag.
实施例3Example 3
本实施例回收了废旧锂离子电池中的有价金属，具体过程为：The present embodiment reclaims the valuable metals in the waste lithium-ion battery, and the specific process is as follows:
取100g电池粉，加入93ml质量浓度为80％的浓硫酸，机械缓慢搅拌0.5h，加入300g水，水浴加热70℃，水浸反应2h，水浸反应后溶液pH为5.0，过滤得到第一有价金属液和第一石墨渣；Take 100g of battery powder, add 93ml of concentrated sulfuric acid with a mass concentration of 80%, slowly stir mechanically for 0.5h, add 300g of water, heat at 70°C in a water bath, and perform a water immersion reaction for 2 hours. After the water immersion reaction, the pH of the solution is 5.0. Valence molten metal and first graphite slag;
称得第一石墨渣为45g，将第一石墨渣与135ml水制浆，升温70℃，滴加浓硫酸至pH 0.5，加入石墨渣中有价金属摩尔量1.3倍的亚硫酸钠，反应3h，滴加适量氢氧化钠，将溶液pH调至4.5，反应1h，过滤得到第二有价金属液和第二石墨渣。Weigh the first graphite slag as 45g, make the first graphite slag with 135ml of water slurry, heat up to 70°C, add concentrated sulfuric acid dropwise to pH 0.5, add sodium sulfite with 1.3 times the molar amount of the valuable metal in the graphite slag, react for 3h, dropwise Add an appropriate amount of sodium hydroxide, adjust the pH of the solution to 4.5, react for 1 h, and filter to obtain the second valuable metal liquid and the second graphite slag.
实施例4Example 4
本实施例回收了废旧锂离子电池中的有价金属，具体过程为：The present embodiment reclaims the valuable metals in the waste lithium-ion battery, and the specific process is as follows:
取100g电池粉，加入106ml质量浓度为70％的浓硫酸，机械缓慢搅拌0.5h，加入300g水，水浴加热70℃，水浸反应4h，水浸反应后溶液pH为5.5，过滤得到第一有价金属液和第一石墨渣；Take 100g of battery powder, add 106ml of concentrated sulfuric acid with a mass concentration of 70%, stir slowly mechanically for 0.5h, add 300g of water, heat at 70°C in a water bath, and perform a water immersion reaction for 4 hours. After the water immersion reaction, the pH of the solution is 5.5. Valence molten metal and first graphite slag;
称得第一石墨渣为46g，将第一石墨渣与138ml水制浆，升温70℃，滴加浓硫酸至pH 1.0，加入石墨渣中有价金属摩尔量1.5倍的亚硫酸钠，反应4h，滴加适量氢氧化钠，将溶液pH调至4.5，反应1h，过滤得到第二有价金属液和第二石墨渣。Weigh the first graphite slag as 46g, make the first graphite slag with 138ml of water slurry, raise the temperature to 70°C, add concentrated sulfuric acid dropwise to pH 1.0, add sodium sulfite with 1.5 times the molar amount of the valuable metal in the graphite slag, react for 4h, dropwise Add an appropriate amount of sodium hydroxide, adjust the pH of the solution to 4.5, react for 1 h, and filter to obtain the second valuable metal liquid and the second graphite slag.
实施例5Example 5
本实施例回收了废旧锂离子电池中的有价金属，具体过程为：The present embodiment reclaims the valuable metals in the waste lithium-ion battery, and the specific process is as follows:
取100g电池粉，加入106ml质量浓度为70％的浓硫酸，机械缓慢搅拌0.5h，加入 300g水，水浴加热70℃，水浸反应4h，水浸反应后溶液pH为5.0，过滤得到第一有价金属液和第一石墨渣；Take 100g of battery powder, add 106ml of concentrated sulfuric acid with a mass concentration of 70%, stir slowly mechanically for 0.5h, add 300g of water, heat at 70°C in a water bath, and perform a water immersion reaction for 4 hours. After the water immersion reaction, the pH of the solution is 5.0. Valence molten metal and first graphite slag;
称得第一石墨渣为40g，将第一石墨渣与120ml水制浆，升温70℃，滴加浓硫酸至pH 1.0，加入石墨渣中有价金属摩尔量1.5倍的亚硫酸钠，反应5h，滴加适量氢氧化钠，将溶液pH调至4.5，反应1h，过滤得到第二有价金属液和第二石墨渣。Weigh the first graphite slag as 40g, make the first graphite slag with 120ml of water, heat up at 70°C, add concentrated sulfuric acid dropwise to pH 1.0, add sodium sulfite with 1.5 times the molar amount of the valuable metal in the graphite slag, react for 5h, dropwise Add an appropriate amount of sodium hydroxide, adjust the pH of the solution to 4.5, react for 1 h, and filter to obtain the second valuable metal liquid and the second graphite slag.
试验例Test example
实施例1-5所用电池粉中有价金属含量如表1所示。Table 1 shows the content of valuable metals in the battery powder used in Examples 1-5.
表1Table 1
| 元素element | NiNi | CoCo | MnMn |
| 含量content | 18％18% | 8％8% | 4％4% |
测得实施例1-5中第一有价金属液与第二有价金属液的元素含量如表2所示。The measured element contents of the first valuable metal liquid and the second valuable metal liquid in Examples 1-5 are shown in Table 2.
表2Table 2
表3为实施例1-5有价金属的回收率情况。Table 3 shows the recovery rate of valuable metals in Examples 1-5.
表3table 3
| 元素element | Ni(％)Ni(%) | Co(％)Co(%) | Mn(％)Mn(%) |
| 实施例1Example 1 | 99.899.8 | 97.697.6 | 99.399.3 |
| 实施例2Example 2 | 99.499.4 | 99.099.0 | 99.699.6 |
| 实施例3Example 3 | 99.299.2 | 99.599.5 | 99.199.1 |
| 实施例4Example 4 | 99.699.6 | 99.399.3 | 99.099.0 |
| 实施例5Example 5 | 99.299.2 | 99.199.1 | 99.799.7 |
由表2和表3可以看出，所得有价金属液的杂质含量(Fe
2+、Al、Cu)很低，有价金属的回收率很高，表明采用本发明浸出与除杂同步进行的回收方法不但工艺简单成本低，而且回收效果佳。
As can be seen from Table 2 and Table 3, the impurity content (Fe 2+ , Al, Cu) of the obtained valuable metal liquid is very low, and the recovery rate of the valuable metal is very high, indicating that the leaching and impurity removal of the present invention are carried out simultaneously. The recovery method not only has a simple process and low cost, but also has a good recovery effect.
图1是本发明的工艺流程图，电池粉加入浓硫酸进行熟化浸出，再加水进行水浸，固液分离后将第一石墨渣加入稀硫酸进行酸浸，然后加入还原剂进行还原浸出，再加碱沉淀杂质，最后固液分离得到第二石墨渣和第二有价金属液。Fig. 1 is a process flow diagram of the present invention, the battery powder is added with concentrated sulfuric acid to carry out maturation leaching, then water is added to carry out water leaching, after solid-liquid separation, the first graphite slag is added to dilute sulfuric acid to carry out acid leaching, then a reducing agent is added to carry out reduction leaching, and then Add alkali to precipitate impurities, and finally obtain second graphite slag and second valuable metal liquid by solid-liquid separation.
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。The embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned embodiments, and within the scope of knowledge possessed by those of ordinary skill in the art, various Variety. Furthermore, the embodiments of the present invention and features in the embodiments may be combined with each other without conflict.
Claims (10)
- 一种回收废旧锂离子电池有价金属的方法，其特征在于，包括以下步骤：A method for recycling valuable metals of waste and used lithium ion batteries, comprising the following steps:S1：将废旧锂离子电池进行前处理得到电池粉，加入浓硫酸进行熟化反应；S1: pre-processing the waste lithium-ion battery to obtain battery powder, and adding concentrated sulfuric acid to carry out the aging reaction;S2：向熟化后的电池粉加水进行水浸反应，然后固液分离，得到第一石墨渣与第一有价金属液；S2: adding water to the aged battery powder to carry out water immersion reaction, and then solid-liquid separation to obtain the first graphite slag and the first valuable metal liquid;S3：向所述第一石墨渣加入酸液进行酸浸反应，再加入还原剂进行氧化还原浸出；S3: adding acid solution to the first graphite slag to carry out acid leaching reaction, and then adding a reducing agent to carry out redox leaching;S4：向氧化还原浸出后的溶液加入碱液调节pH进行反应，固液分离后得到第二石墨渣和第二有价金属液。S4: adding alkaline solution to the solution after redox leaching to adjust pH to carry out the reaction, and after solid-liquid separation, a second graphite slag and a second valuable metal solution are obtained.
- 根据权利要求1所述的方法，其特征在于，步骤S1中，所述浓硫酸与电池粉中正极材料的摩尔比为(1～1.5)：1，所述浓硫酸的质量浓度为70％以上。The method according to claim 1, wherein in step S1, the molar ratio of the concentrated sulfuric acid to the positive electrode material in the battery powder is (1-1.5):1, and the mass concentration of the concentrated sulfuric acid is more than 70% .
- 根据权利要求1所述的方法，其特征在于，步骤S1中，所述熟化反应的时间为0.5～5h。The method according to claim 1, characterized in that, in step S1, the time of the aging reaction is 0.5-5h.
- 根据权利要求1所述的方法，其特征在于，步骤S2中，所述加水的质量为步骤S1中所述电池粉质量的3～10倍。The method according to claim 1, wherein in step S2, the mass of the added water is 3-10 times the mass of the battery powder in step S1.
- 根据权利要求1所述的方法，其特征在于，步骤S2中，所述水浸反应的时间为0.5～10h，温度为40～90℃。The method according to claim 1, characterized in that, in step S2, the time of the water immersion reaction is 0.5-10 h, and the temperature is 40-90°C.
- 根据权利要求1所述的方法，其特征在于，步骤S3中，所述酸浸反应的过程是将所述第一石墨渣加水制浆，再加酸液调节pH进行酸浸反应，所述第一石墨渣与水的固液比为1：(3～10)g/ml，所述pH调至0.5～1.5。The method according to claim 1, wherein in step S3, the process of the acid leaching reaction is to add water to the first graphite slag to make pulp, and then add acid solution to adjust the pH to carry out the acid leaching reaction, and the first graphite slag A solid-liquid ratio of graphite slag to water is 1:(3-10) g/ml, and the pH is adjusted to 0.5-1.5.
- 根据权利要求1所述的方法，其特征在于，步骤S3中，所述酸浸反应的温度为40～90℃，反应的时间为0.5～10h。The method according to claim 1, characterized in that, in step S3, the temperature of the acid leaching reaction is 40-90° C., and the reaction time is 0.5-10 h.
- 根据权利要求1所述的方法，其特征在于，步骤S3中，所还原剂为亚硫酸钠、硫代硫酸钠或过氧化氢中的一种或多种；所述还原剂与所述第一石墨渣中有价金属的摩尔比为(1～1.5)：1。The method according to claim 1, wherein, in step S3, the reducing agent is one or more of sodium sulfite, sodium thiosulfate or hydrogen peroxide; the reducing agent and the first graphite slag The molar ratio of the middle valuable metal is (1-1.5):1.
- 根据权利要求1所述的方法，其特征在于，步骤S3中，所述氧化还原浸出的反应 温度为40～90℃，反应时间为0.5～10h。The method according to claim 1, characterized in that, in step S3, the reaction temperature of the redox leaching is 40-90°C, and the reaction time is 0.5-10h.
- 根据权利要求1所述的方法，其特征在于，步骤S4中，所述碱液为氢氧化钠、碳酸钠、碳酸氢钠、氨水、碳酸钙、碳酸氢钙、碳酸镍、碳酸锰的一种或多种；步骤S4中，所述pH调至4.5～5。The method according to claim 1, is characterized in that, in step S4, described lye is a kind of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammoniacal liquor, calcium carbonate, calcium bicarbonate, nickel carbonate, manganese carbonate or more; in step S4, the pH is adjusted to 4.5-5.
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| CN114317968A (en) * | 2021-11-24 | 2022-04-12 | 深圳供电局有限公司 | Recycling method and application of waste lithium iron phosphate battery |
| WO2023188489A1 (en) * | 2022-03-31 | 2023-10-05 | Ｊｘ金属株式会社 | Metal leaching method and metal recovery method |
| CN115805001A (en) * | 2023-02-10 | 2023-03-17 | 湖南五创循环科技股份有限公司 | Method for treating organic waste gas in waste power battery black powder roasting process |
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