Retired lithium battery combined with waste catalyst collaborative smelting and recycling method and application

Abstract

The application relates to a retired lithium battery combined waste catalyst collaborative smelting and recycling method and application, and relates to the technical field of waste resource utilization and metal regeneration. The recycling method can utilize the internal organic matter and graphite in the retired battery as a reducing agent, and can utilize the carrier components (such as Al2O3 and SiO2) rich in the waste catalyst to form an ideal slag system, so that multi-metal synchronous reduction, alloying and by-product recovery can be realized in a single smelting process, overall energy consumption is reduced, and environmental benefits are improved.

Description

Technical Field

[0001] This invention relates to the field of waste resource utilization and metal recycling technology, and in particular to a method and application for the co-smelting and recycling of decommissioned lithium batteries and spent catalysts. Background Technology

[0002] With the large-scale application of new energy vehicles, energy storage systems, and electronic products, the number of retired lithium-ion batteries has increased dramatically, many of which are rich in valuable metals such as nickel (Ni), cobalt (Co), manganese (Mn), and lithium (Li). Traditional recycling methods mainly include pyrometallurgy and hydrometallurgy. Pyrometallurgy has advantages such as simple process, strong adaptability, and the ability to reduce metals such as Ni and Co to form alloys in a single high-temperature smelting process, making it suitable for handling mixed materials. However, high-temperature smelting consumes a lot of energy, some metals (such as lithium and some Mn) tend to remain in the slag, and there are relatively high emissions of CO2 and harmful waste gases. Hydrometallurgy has the characteristics of low process temperature, high recovery rate, and high product purity, but it involves many processes, high consumption of acid and alkali reagents, high waste liquid treatment costs, and difficulty in industrial scale-up. In addition, for spent catalysts, traditional recycling methods mostly use acid leaching, roasting, and wet extraction, but these methods have problems such as high equipment investment, complex processes, and insufficient recovery rates of some precious metals. In existing technologies, the recycling of batteries and catalysts mostly adopts separate processes, which fails to achieve the synergistic utilization of materials and energy among wastes, resulting in resource waste and increased environmental burden.

[0003] In view of this, there is an urgent need for a new recycling method that can directly use retired lithium batteries and waste catalysts as raw materials to deeply recycle and utilize the economically valuable components, save resources, and at the same time reduce the environmental impact of the aforementioned waste. Summary of the Invention

[0004] To address the aforementioned issues, this invention provides a method for the co-smelting and recycling of retired lithium batteries and spent catalysts. This recycling method utilizes the organic matter and graphite inherent in retired batteries as reducing agents, and also utilizes the carrier components (such as Al2O3) abundant in spent catalysts to form an ideal slag system. This enables simultaneous reduction, alloying, and by-product recovery of multiple metals in a single smelting process, reducing overall energy consumption and improving environmental benefits.

[0005] This invention provides a method for the co-smelting and recycling of retired lithium batteries and their associated waste catalysts, comprising the following steps:

[0006] Raw material pretreatment and batching: Discharge, disassemble, and crush retired lithium batteries to obtain battery black powder, dry it to obtain battery powder; crush and dry waste catalyst to obtain catalyst powder; mix battery powder and catalyst powder to obtain a reduction mixture.

[0007] Synergistic reduction and high-temperature melting: Under a protective atmosphere, the reducing mixture is heated to carry out a pre-reduction reaction, and then high-temperature melting is carried out to obtain the reduction-melted product;

[0008] Slag phase control and product separation: Slag conditioner is added to the reduction smelting product to adjust the slag basicity, then cooled and water-quenched to separate the multi-element alloy from the slag, obtaining the multi-element alloy and slag. The slag is then acid-leached, filtered, concentrated, and lithium-precipitated to obtain lithium salt.

[0009] In the above recycling method, after conventional discharge, dismantling, and crushing, retired lithium batteries undergo only low-temperature drying to retain the graphite and organic binders. Waste catalysts are similarly simply crushed and dried, retaining residual grease, which is then mixed with battery powder to form a reduction mixture. This mixture also serves as a combustion heat source. The reduction mixture undergoes a pre-reduction reaction, utilizing the heat and reducing gases generated by the pyrolysis of organic matter and waste oil. High-temperature smelting is then performed to complete metal reduction and alloying, yielding a reduction smelting product. A slag conditioner is added to regulate slag alkalinity, resulting in a multi-element alloy and slag. Finally, lithium salts are recovered from the slag through acid leaching and filtration. This recycling method utilizes the inherent organic matter and graphite in retired batteries as reducing agents and the carrier components (such as Al2O3) abundant in waste catalysts to form an ideal slag system. This allows for simultaneous reduction and alloying of multiple metals and recovery of byproducts (such as lithium salts) in a single smelting process, reducing overall energy consumption and improving environmental benefits. Furthermore, this recycling method features a simple process flow, high energy utilization, and high recovery rate. It is both environmentally friendly and economical, and is applicable to the system treatment of various types of retired lithium-ion batteries and metal-containing waste catalysts, achieving comprehensive recycling of multiple metals and lithium resources.

[0010] The aforementioned spent catalyst is a catalyst that includes a support component, wherein the support component includes Al2O3 and / or SiO2, and the spent catalyst may originate from the hydrotreating process of petroleum or chemical industries.

[0011] In one embodiment, in the raw material pretreatment and batching steps, the drying temperature of the battery black powder is 80-130℃ and the drying time is 0.5-4h; the drying temperature of the waste catalyst is 80-130℃ and the drying time is 0.5-4h; the mass ratio of the battery powder to the catalyst powder is (0.5-4):1.

[0012] In one embodiment, the mass ratio of the battery powder to the catalyst powder is (0.8-3):1.

[0013] In one embodiment, the mass ratio of the battery powder to the catalyst powder is (1.5-2.5):1.

[0014] In one embodiment, in the synergistic reduction and high-temperature melting steps, the temperature of the pre-reduction reaction is 200-800℃, and the time of the pre-reduction reaction is 10-90 min; the high-temperature melting includes: heating to 1000-1800℃ at a rate of 3-20℃ / min and holding at that temperature for 0.3-4 h.

[0015] In one embodiment, the protective atmosphere in the synergistic reduction and high-temperature melting step includes an inert atmosphere or a weak reducing atmosphere.

[0016] In one embodiment, the temperature of the pre-reduction reaction is 300-700°C, and the time of the pre-reduction reaction is 20-60 min; the high-temperature melting includes: heating to 1100-1700°C at a rate of 5-15°C / min and holding at that temperature for 0.5-3 h.

[0017] In one embodiment, the protective gas flow rate for the high-temperature melting is 0.5-5 L / min.

[0018] In one embodiment, the flow rate of the protective gas during high-temperature melting is 1-3 L / min.

[0019] In one embodiment, the high-temperature melting is achieved by a medium-frequency induction furnace, a resistance furnace, or an electric arc furnace.

[0020] In one embodiment, in the slag phase regulation and product separation step, the slag regulator includes at least three of CaO, SiO2, Al2O3, MgO, and Na2O, and the amount of the slag regulator added is 10-110 wt% of the mass of the reduction smelting product; the slag basicity is adjusted to 0.5-2.0.

[0021] In one embodiment, the amount of the slag conditioner added is 15-50 wt% of the mass of the reduction smelting product.

[0022] In one embodiment, the slag alkalinity is adjusted to 0.8-1.5.

[0023] In one embodiment, when the slag conditioner includes CaO, SiO2, and Al2O3, the amounts of CaO, SiO2, and Al2O3 are 30-50 wt%, 30-40 wt%, and 1-20 wt% of the mass of the slag conditioner, respectively.

[0024] When the slag conditioner includes CaO, SiO2, Al2O3, and MgO, the amounts of CaO, SiO2, Al2O3, and MgO are 30-45 wt%, 25-35 wt%, 1-20 wt%, and 3-8 wt% of the mass of the slag conditioner, respectively.

[0025] When the slag conditioner includes CaO, SiO2, Al2O3, MgO, and Na2O, the amounts of CaO, SiO2, Al2O3, MgO, and Na2O are 29-35 wt%, 25-35 wt%, 1-20 wt%, 3-8 wt%, and 1-10 wt% of the mass of the slag conditioner, respectively.

[0026] In one embodiment, in the slag phase control and product separation step, the acid leaching includes acid leaching with sulfuric acid or hydrochloric acid, the solid-liquid ratio of the acid leaching is 1:(5-10), the temperature is 60-90℃, and the time is 1-3h.

[0027] In one embodiment, the water quenching temperature in the slag phase conditioning and product separation step is 20-80℃.

[0028] In one embodiment, the process further includes raw material pretreatment and the addition of an auxiliary carbon source after batching, wherein the auxiliary carbon source includes graphite or waste oil;

[0029] When the auxiliary carbon source includes graphite, the molar ratio of carbon to oxygen in the metal oxide in the reduction mixture after adding graphite is (0.8-2.0):1;

[0030] When the auxiliary carbon source includes waste oil, the amount of waste oil added is 2-25 wt% of the mass of the reduction mixture.

[0031] Understandably, if the aforementioned reducing mixture of battery powder and catalyst powder is insufficient, graphite or waste oil can be added further. Graphite can be derived from retired lithium batteries, and waste oil can be derived from waste oil in spent catalysts or added waste oil. The molar amount of oxygen in the aforementioned metal oxides is calculated from the oxygen content in the metal oxides of retired lithium batteries and spent catalysts, measured in oxide form. The aforementioned waste oil is heavy oil.

[0032] In one embodiment, when the auxiliary carbon source includes graphite, the molar ratio of carbon to metal oxide in the reduction mixture after adding graphite is (1.0-1.5):1.

[0033] In one embodiment, when the auxiliary carbon source includes graphite, the molar ratio of carbon to metal oxide in the reduction mixture after adding graphite is 1.2:1.

[0034] In one embodiment, when the auxiliary carbon source includes waste oil, the amount of waste oil added is 5-20 wt% of the mass of the reducing mixture.

[0035] In one embodiment, when the auxiliary carbon source includes waste oil, the amount of waste oil added is 10-15 wt% of the mass of the reducing mixture.

[0036] In one embodiment, the method for co-smelting and recycling retired lithium batteries and waste catalysts further includes raw material pretreatment and the addition of flux and / or fluxing agent after batching, with the amount added being 4-110 wt% of the mass of the reduction mixture.

[0037] It is understood that those skilled in the art may choose to add or not add flux and / or fluxing agent depending on the high-temperature smelting conditions.

[0038] In one embodiment, the flux includes at least one of CaO and SiO2, the fluxing agent includes Na2CO3, and the amount of flux and / or fluxing agent added is 15-50 wt% of the mass of the reducing mixture.

[0039] This invention also provides the application of the aforementioned method for the co-smelting and recycling of retired lithium batteries and waste catalysts in the preparation of multi-component alloys.

[0040] The present invention also provides the application of the aforementioned method for the co-smelting and recycling of retired lithium batteries and waste catalysts in the recovery of lithium salts.

[0041] The present invention also provides a method for preparing multi-element alloys and / or lithium salts, wherein the retired lithium batteries are treated using the aforementioned method of co-smelting and recycling of retired lithium batteries and waste catalysts.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] This invention relates to a method and application for the co-smelting and recycling of retired lithium batteries and spent catalysts. This recycling method utilizes the organic matter and graphite inherent in retired batteries as reducing agents, and leverages the carrier components (such as Al2O3) abundant in spent catalysts to form an ideal slag system. This allows for simultaneous reduction and alloying of multiple metals during a single smelting process, achieving efficient co-recycling of nickel, cobalt, tungsten, molybdenum, manganese, and other metals. The main metal recovery rate can reach over 95%. After refining, the multi-element alloys can be used as alloy components in the production of high-temperature alloys and special steels. Simultaneously, it also recovers by-products (such as lithium salts). Furthermore, this recycling method utilizes the heat generated by burning the organic components in spent batteries, effectively reducing external energy consumption, thereby reducing overall energy consumption and improving environmental benefits. Moreover, this recycling method has significant environmental advantages, reducing the generation of acid and alkaline waste liquids and eliminating large-scale emissions of harmful gases. The process is simple and easily scalable: the equipment is universal, the process parameters are clear, and industrial-scale production is easily achieved. It also achieves comprehensive resource utilization: through secondary lithium recovery, a resource closed loop is realized. Detailed Implementation

[0044] To facilitate understanding of the present invention, a more complete description will be given below with reference to relevant embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention.

[0045] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0046] Example 1

[0047] A method for the co-smelting and recycling of retired lithium batteries and waste catalysts.

[0048] This method retains carbonaceous components (such as battery graphite, organic binders, and residual catalyst grease) in retired batteries and spent catalysts, and combines this with added slag conditioners to achieve simultaneous reduction and alloying of multiple metals in a single pyrometallurgical smelting process. Furthermore, it recovers byproducts such as lithium salts from the smelting slag. This technical solution is applicable to the secondary resource recovery of nickel, cobalt, manganese, molybdenum, tungsten, lithium, and other valuable metals. The process is simple, highly efficient, and possesses good environmental and economic value. The specific steps of the recovery method are as follows:

[0049] I. Pretreatment of retired batteries and spent catalysts.

[0050] In this embodiment, the retired battery is a lithium-ion battery, which may include one or more of lithium cobalt oxide batteries, lithium nickel oxide batteries, and ternary cathode batteries of all types. Preferably, the retired battery is first discharged, and then disassembled, crushed, and dried sequentially to obtain battery powder with suitable particle size while preserving as much of the graphite and organic binder components in the battery as possible. In a preferred embodiment, the drying temperature is 80℃~120℃, and the time is 0.5-4h. Since this technical solution focuses on preserving carbonaceous reducing agents, high-temperature calcination or complete removal of organic matter is not performed.

[0051] Similarly, for spent catalysts, this technical solution does not involve complete deoiling or deep roasting, but only simple crushing and low-temperature drying to retain residual oil or coke components. In this embodiment, the spent catalyst contains one or more of the following catalysts: W-Mo-Ni / Al2O3, W-Mo-V-Ni / Al2O3, and Mo-Ni / Al2O3. The drying temperature is preferably 80℃~120℃, and the time is 0.5-4h; the catalyst may be rich in active components such as Ni, Co, Mo, W, and V, and the support is mostly Al2O3 or SiO2.

[0052] In this technical solution, the above pretreatment operation can remove excess moisture from the raw materials and obtain a suitable powder particle size, thereby laying the foundation for subsequent mixing, batching, melting and reduction.

[0053] II. Mixing ingredients.

[0054] In this embodiment, during the mixing and batching process, retired battery powder and spent catalyst powder are mixed at a mass ratio of 0.5:1 to 4:1. Preferably, considering the amount of graphite and other carbon sources contained in the battery, the specific ratio can be adjusted according to actual needs. For example, a ratio of 2:1 to 4:1 is more conducive to simultaneously achieving metal recovery rate and reducing agent utilization efficiency.

[0055] During the mixing process, the dried battery powder and catalyst powder can be first placed in a mixer and mixed evenly. If the carbon content in the mixture is found to be insufficient to meet the reduction requirements, an appropriate amount of graphite powder, coal, or coke can be added to maintain the molar ratio of carbon to metal oxide between 0.8:1 and 2.0:1, more preferably between 1.0:1 and 1.5:1. Furthermore, to provide additional calorific value and a reducing atmosphere, 2-25 wt% of waste oil (such as petroleum coke residue) may be added. The above mixing operation can be carried out using conventional mixing equipment, and the mixing time is usually 0.5 h to 3 h, which can ensure that the components are evenly dispersed.

[0056] III. Pre-reduction process.

[0057] In this technical solution, the pre-reduction process refers to placing the mixed materials in an inert or weakly reducing protective gas environment, first heating to 200℃~800℃ and holding for 10~90 minutes to achieve preliminary reduction of some metal oxides, and decomposing the residual organic binder or grease in the catalyst at a lower temperature, providing a certain amount of heat and a reducing atmosphere. Preferably, the present invention can control the pre-reduction temperature at 300℃~700℃ and the holding time at 20~60 minutes, which can reduce energy consumption in the high-temperature stage and fully utilize the reduction effect of battery graphite and grease.

[0058] In a preferred embodiment of the present invention, if the protective atmosphere is an inert gas such as argon or nitrogen, the flow rate can be 0.5 to 5 L / min; if it is nitrogen, 2 to 5 vol% H2 or CO can be added to the nitrogen to enhance the pre-reduction effect.

[0059] IV. High-temperature smelting steps.

[0060] After pre-reduction, the material is heated to 1000℃-1800℃ at a heating rate of 3-20℃ / min and held for 0.3-3 hours to achieve full reduction of the polymetallic oxides and intermetallic alloying. Preferably, the present invention holds the material at 1200℃-1600℃ for 0.5-2 hours, which satisfies both the need for complete reduction of polymetals and energy consumption. At this time, if the smelting furnace is a medium-frequency induction furnace or an electric arc furnace, the gas flow rate inside the furnace can be maintained at 1-3 L / min, ensuring a weak reducing or inert atmosphere, thereby achieving higher metal recovery efficiency.

[0061] In this technical solution, the combustion of graphite from retired batteries and grease from spent catalysts can provide additional heat, while some metal oxides are reduced to elemental metals by carbon. At the same time, different metals can form multi-element alloys such as Ni–Co–Mo, Ni–Co–W, Ni-Co-Mn-W-Mo, and Ni-Co-Mo-Si-V at high temperatures, thereby achieving the goal of one-time alloying treatment.

[0062] V. Slag conditioner and the construction of slag system during smelting.

[0063] During or before the completion of the aforementioned high-temperature smelting process, this technical solution adds ternary, quaternary, or multi-component slag conditioners (Al2O3–SiO2–CaO, ​​Al2O3–SiO2–CaO–MgO, or Al2O3-Na2O-SiO2-CaO-MgO, etc.) to ensure the slag phase possesses a reasonable melting temperature and viscosity, facilitating the smooth separation and sedimentation of valuable metals. This technical solution controls the addition amount of slag conditioner between 10 and 110 wt%, depending on the characteristics of different raw materials. The aforementioned slag conditioner can be selected from common slag conditioner categories; for example, quicklime or fluorite can be used for CaO, and quartz can be used for SiO2. The specific proportions can be referenced within the following range:

[0064] When using a ternary slag system, the CaO content is 30-50 wt%, the SiO2 content is 30-40 wt%, and the Al2O3 content is 1-20 wt%.

[0065] When using a quaternary slag system, an additional 3-8 wt% of MgO is added to the ternary system, that is, CaO content 30-45 wt%, SiO2 content 25-35 wt%, Al2O3 content 1-20 wt%, and MgO content 3-8 wt%.

[0066] When using a multi-element slag system, the CaO content is 29-35 wt%, the Na2O content is 1-10 wt%, the SiO2 content is 25-35 wt%, the Al2O3 content is 1-20 wt%, and the MgO content is 3-8 wt%.

[0067] By adjusting the ratios of CaO / SiO2 and (CaO+MgO) / (SiO2+Al2O3) and (CaO+MgO+Na2O) / (SiO2), the slag basicity R can be controlled between 0.8 and 2.0, preferably between 1.0 and 1.5. Too low a basicity easily leads to high slag viscosity and a decrease in metal recovery; too high a basicity will raise the melting point and exacerbate corrosion of the furnace lining. This invention achieves low viscosity, low melting point, and low encapsulation of metal oxides in the slag within the intermediate range.

[0068] VI. Separation and by-product recovery after smelting.

[0069] After smelting, this technical solution allows for the separation of the metallic phase and the slag phase through high-temperature slag skimming, natural cooling, or water quenching. To accelerate separation and facilitate subsequent lithium extraction, water quenching is preferred; that is, the slag is rapidly immersed in water for cooling and quenching at the end of smelting. This yields a dense metallic alloy ingot and fragmented slag particles (or powder), achieving rapid and thorough phase separation.

[0070] Alloy products: The separated metallic phases can be obtained by ingot casting or secondary refining to produce multi-component alloys. Depending on the raw material ratio and specific process control, the recovery rate of metals such as Ni, Co, Mo, W, and V can generally reach 90-98%, and the alloy composition is uniform, which can be directly used as a master alloy for special alloys or as raw material for subsequent refining and processing.

[0071] Lithium recovery from slag: A key feature of this technical solution is the utilization of lithium resources in slag. Slag particles obtained after water quenching are leached with 0.5–2 mol / L dilute sulfuric acid or hydrochloric acid, held at 60–90℃ for 1–3 hours, with a solid-liquid ratio of 1:5–1:10. After leaching, the solution is filtered to obtain a lithium-rich solution. Subsequently, lithium salt products such as lithium carbonate or lithium chloride can be obtained through conventional methods such as evaporation concentration, precipitation, or extraction; the overall lithium recovery rate can typically reach over 80%.

[0072] In this invention, this post-processing of slag enables the resource to be utilized at a higher value, while avoiding the loss of lithium during high-temperature smelting, thus forming a closed loop for the comprehensive recovery of metals and lithium.

[0073] Example 2

[0074] The recycling method of Example 1 was used to recycle retired ternary lithium batteries, as detailed below.

[0075] After discharging, disassembling, and crushing retired ternary lithium batteries, they were dried at 120℃ for 3 hours to obtain 500g of battery black powder (containing graphite and organic matter). Waste catalyst (W-Mo-Ni / Al2O3) was also dried at 120℃ for 3 hours to obtain 500g of powder (containing waste oil). The battery black powder and waste catalyst powder were mixed at a mass ratio of 1:1 using a mixer to obtain a reduction mixture. Simultaneously, 3wt% CaO and 2wt% SiO2 were added as additives to the reduction mixture. In the reduction mixture, the graphite and organic matter from the batteries and the waste oil from the waste catalyst were used as reducing agents and fuels. Additional graphite was added to achieve a carbon to oxygen molar ratio in the metal oxides of 1.2:1. The total amount of waste oil was controlled to 10wt% of the mixture.

[0076] Under argon protection, the reduction mixture was placed in a medium-frequency induction furnace and pre-reduced at 500℃ for 30 minutes, then heated to 1400℃ at a rate of 10℃ / min and held for 1 hour. During the smelting process, 15wt% of the reduction smelting product was added as an Al2O3-SiO2-CaO slag conditioner (containing 35wt% CaO, 33wt% SiO2, 10wt% Al2O3, and a basicity of 1.06) to regulate the slag phase.

[0077] After smelting, the alloy and slag were separated by water quenching at 70℃. The resulting alloy was a Ni-Co-W-Mo-Mn alloy, with Ni and Co recoveries greater than 98.5%, Mn recovery greater than 90%, and W and Mo recovery greater than 95%. The slag, after water quenching, was acid-leached with a 1 mol / L H₂SO₄ solution (solid-liquid ratio 1:8, 80℃, 2 hours). After filtration, lithium carbonate was prepared by evaporation crystallization, with a lithium recovery rate of 80%.

[0078] Example 3

[0079] The recycling method of Example 1 was used to recycle retired ternary lithium batteries, as detailed below.

[0080] After discharging, disassembling, and crushing retired ternary lithium batteries, they were dried at 120℃ for 3 hours to obtain 400g of battery black powder (containing graphite and organic matter). Waste catalyst (WV-Ni / Al2O3) was dried at 120℃ for 3 hours to obtain 600g of powder (containing waste oil). The battery black powder and waste catalyst powder were mixed at a mass ratio of 2:3 using a mixer to obtain a reduction mixture. In the reduction mixture, the graphite and organic matter from the batteries and the waste oil from the waste catalyst were used as reducing agents and fuels. Additional graphite was added to maintain a carbon to oxygen molar ratio in the metal oxides of 1.0:1. The total amount of waste oil was 10wt% of the reduction mixture.

[0081] Under a weakly reducing atmosphere of argon mixed with 3 vol% CO, the reduction mixture was pre-reduced at 500℃ for 35 minutes, then heated to 1400℃ at a rate of 10℃ / min and held for 45 minutes. During the smelting process, 28 wt% of the reduction smelting product was added as an Al2O3-SiO2-CaO-MgO slag conditioner (containing 40 wt% CaO, 30 wt% SiO2, 8 wt% Al2O3, 5 wt% MgO, and a basicity of 1.33) to regulate the slag phase.

[0082] After smelting, the alloy and slag were separated by water quenching. The resulting alloy showed Ni recovery rates of 97%, Co recovery rate of 96%, W recovery rate of 87%, and V recovery rate of 90%. The slag, after water quenching, was acid-leached with a 1.5 mol / L HCl solution (solid-liquid ratio 1:10, 85℃, 2.5 hours). After filtration, lithium chloride was prepared by concentration and crystallization, achieving a lithium recovery rate of 82%.

[0083] Example 4

[0084] The recycling method of Example 1 was used to recycle retired ternary lithium batteries, as detailed below.

[0085] After discharging, disassembling, and pulverizing retired lithium iron phosphate batteries, the residue was dried at 120°C for 3 hours to obtain 600g of battery black powder (containing graphite and organic matter). Waste Co-Mo / Al₂O₃ catalyst was dried at 120°C for 3 hours to obtain 400g of powder (containing waste oil). The battery black powder and waste catalyst powder were mixed at a mass ratio of 3:2 using a mixer to obtain a reduction mixture. In the reduction mixture, graphite and organic matter from the batteries and waste oil from the waste catalyst were used as reducing agents and fuels. Additional graphite was added to maintain a carbon to oxygen molar ratio in the metal oxides at 1.5:1. The total amount of waste oil was 15wt% of the mixture.

[0086] Under nitrogen atmosphere (with 2 vol% H2 added), the reduction mixture was pre-reduced at 450℃ for 40 minutes, then the temperature was increased to 1300℃ at a rate of 8℃ / min and held for 1.5 hours. During the smelting process, 18 wt% of the reduction smelting product was added as an Al2O3-SiO2-CaO-MgO slag conditioner (containing 35 wt% CaO, 32 wt% SiO2, 1.5 wt% Al2O3, 5 wt% MgO, and an alkalinity of 1.09) to regulate the slag phase.

[0087] After smelting, the alloy and slag were separated by water quenching. The resulting alloy showed Ni recovery rates of 95%, Co recovery rates of 90%, and Mn recovery rates of 88%. The slag, after water quenching, was acid-leached with a 1 mol / L H₂SO₄ solution (solid-liquid ratio 1:8, 80℃, 2 hours). After filtration, lithium carbonate was prepared by evaporation and crystallization, achieving a lithium recovery rate of 85%.

[0088] Example 5

[0089] The recycling method of Example 1 was used to recycle retired ternary lithium batteries, as detailed below.

[0090] Retired ternary lithium batteries were discharged, disassembled, and crushed, then dried at 120°C for 3 hours to obtain 700g of battery black powder (containing graphite and organic matter). Waste catalyst (Mo-Ni / Al2O3) was dried at 120°C for 3 hours to obtain 300g of powder (containing waste oil). The battery black powder and waste catalyst powder were mixed at a mass ratio of 7:3 using a mixer to obtain a reduction mixture. In the reduction mixture, graphite and organic matter from the batteries and waste oil from the waste catalyst were used as reducing agents and fuels. Additional graphite was added to maintain a carbon to oxygen molar ratio of 1.2:1 in the metal oxides. The total amount of waste oil was 10wt% of the mixture.

[0091] Under argon protection, the reduction mixture was pre-reduced at 550℃ for 30 minutes, then heated to 1550℃ at a rate of 8℃ / min and held for 1.2 hours. During the smelting process, 15wt% of the reduction smelting product was added as an Al2O3-SiO2-CaO slag conditioner (containing 32wt% CaO, 35wt% SiO2, 15wt% Al2O3, and a basicity of 0.91) to regulate the slag phase.

[0092] After smelting, the alloy and slag were separated by water quenching. The resulting alloy showed Ni recovery rates of 98%, Co recovery rates of 96%, and Mo recovery rates of 97%. The slag, after water quenching, was acid-leached with a 1 mol / L H₂SO₄ solution (solid-liquid ratio 1:8, 80℃, 2 hours). After filtration, lithium carbonate was prepared by evaporation and crystallization, achieving a lithium recovery rate of 87%.

[0093] Example 6

[0094] The recycling method of Example 1 was used to recycle retired ternary lithium batteries, as detailed below.

[0095] Retired ternary lithium batteries were discharged, disassembled, and crushed, then dried at 120°C for 3 hours to obtain 600g of battery black powder (containing graphite and organic matter). Waste catalyst (W-Mo-Ni / Al2O3) was dried at 120°C for 3 hours to obtain 400g of powder (containing waste oil). The battery black powder and waste catalyst powder were mixed at a mass ratio of 3:2 using a mixer to obtain a reduction mixture. In the reduction mixture, the graphite and organic matter from the batteries and the waste oil from the waste catalyst were used as reducing agents and fuels. Additional graphite was added to maintain a carbon to oxygen molar ratio in the metal oxides of 1.2:1. The total amount of waste oil was 10wt% of the reduction mixture.

[0096] Under a nitrogen atmosphere containing 2 vol% H2, the reduction mixture was pre-reduced at 600℃ for 40 minutes, then the temperature was increased to 1500℃ at a rate of 10℃ / min and held for 1.5 hours. During the smelting process, 20 wt% of the reduction smelting product was added as an Al2O3-SiO2-CaO-MgO slag conditioner (containing 38 wt% CaO, 32 wt% SiO2, 18 wt% Al2O3, 5 wt% MgO, and an alkalinity of 1.19) to regulate the slag phase.

[0097] After smelting, the alloy and slag were separated by water quenching at 80℃. The resulting alloy showed Ni recovery rates of 98%, Co recovery rates of 97%, Mo recovery rates of 96%, and W recovery rates of 95%. The slag, after water quenching, was acid-leached with a 1.5 mol / L HCl solution (solid-liquid ratio 1:10, 85℃, 2.5 hours). After filtration, lithium chloride was prepared by concentration and crystallization, achieving a lithium recovery rate of 92%.

[0098] Example 7

[0099] The recycling method of Example 1 was used to recycle retired ternary lithium batteries, as detailed below.

[0100] After discharging, disassembling, and crushing retired lithium cobalt oxide batteries, they were dried at 125°C for 3 hours to obtain 550g of battery black powder (containing graphite and organic matter). Waste catalyst (W-Mo-Ni / Al2O3) was dried at 110°C for 3 hours to obtain 450g of powder (containing waste oil). The battery black powder and waste catalyst powder were mixed at a mass ratio of 1.1:0.9 using a mixer to obtain a reduction mixture. In the reduction mixture, the graphite and organic matter from the batteries and the waste oil from the waste catalyst were used as reducing agents and fuels. Additional graphite was added to maintain a carbon to oxygen molar ratio in the metal oxides of 1.2:1. The total amount of waste oil was 10wt% of the reduction mixture.

[0101] Under a nitrogen atmosphere containing 2 vol% H2, the reduction mixture was pre-reduced at 600℃ for 40 minutes, then the temperature was increased to 1500℃ at a rate of 10℃ / min and held for 1.5 hours. During the smelting process, 20 wt% of the reduction smelting product was added as an Al2O3-SiO2-CaO-MgO slag conditioner (containing 38 wt% CaO, 32 wt% SiO2, 18 wt% Al2O3, 5 wt% MgO, and an alkalinity of 1.19) to regulate the slag phase.

[0102] After smelting, the alloy and slag were separated by water quenching at 80℃. The resulting alloy showed Ni recovery rates of 96%, Co recovery rates of 98%, Mo recovery rates of 96%, and W recovery rates of 95%. The slag, after water quenching, was acid-leached with a 1.5 mol / L HCl solution (solid-liquid ratio 1:10, 85℃, 2.5 hours). After filtration, lithium chloride was prepared by concentration and crystallization, achieving a lithium recovery rate of 92%.

[0103] Experimental Example 1

[0104] XRF analysis was performed on the smelting products of Examples 2-7.

[0105] Table 1. XRF test results (wt%) of the smelting products from Examples 2-7

[0106]

[0107]

[0108] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0109] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A method for co-metallurgical recovery of retired lithium batteries in combination with spent catalysts, characterized in that, The method comprises the following steps: Raw material pretreatment and batching: the retired lithium battery is discharged, disassembled and crushed to obtain battery black powder, which is dried to obtain battery powder; the waste catalyst is crushed and dried to obtain catalyst powder; the battery powder and the catalyst powder are mixed, and the mass ratio of the battery powder to the catalyst powder is (0.5-4):1, to obtain a reduction mixture; the waste catalyst is derived from a hydrogenation treatment step of petroleum or chemical industry; Synergistic reduction and high-temperature smelting: the reduction mixture is heated in a protective atmosphere to perform a pre-reduction reaction, and then high-temperature smelting is performed to obtain a reduction smelting product; The temperature of the pre-reduction reaction is 200-800 DEG C, and the time of the pre-reduction reaction is 10-90 min; the high-temperature smelting comprises: increasing the temperature to 1000-1800 DEG C at a rate of 3-20 DEG C / min, and maintaining the temperature for 0.3-4 h; Slag phase regulation and product separation: a slag regulator is added to the reduction smelting product, and the addition amount of the slag regulator is 10-110 wt% of the mass of the reduction smelting product; the slag basicity is adjusted to 0.5-2.0, and then the product is cooled, water quenched, separated into a multi-element alloy and a slag, to obtain the multi-element alloy and the slag; the slag is acid leached, filtered, concentrated and lithium precipitated to obtain a lithium salt; the slag regulator comprises at least three of CaO, SiO2, Al2O3, MgO and Na2O.

2. The method according to claim 1, wherein the method is characterized by, In the raw material pretreatment and batching step, the battery black powder is dried at a temperature of 80-130 DEG C for 0.5-4 h; the waste catalyst is dried at a temperature of 80-130 DEG C for 0.5-4 h.

3. The combined scrap catalyst and decommissioned lithium battery smelting and recycling method according to claim 1, characterized in that, In the slag phase regulation and product separation step, the acid leaching comprises using sulfuric acid or hydrochloric acid for acid leaching, the solid-liquid ratio of the acid leaching is 1:(5-10), the temperature is 60-90 DEG C, and the time is 1-3 h.

4. The combined scrap catalyst and decommissioned lithium battery smelting and recycling method according to claim 3, characterized in that, When the slag regulator comprises CaO, SiO2 and Al2O3, the addition amounts of CaO, SiO2 and Al2O3 are 30-50 wt%, 30-40 wt% and 1-20 wt% of the mass of the reduction smelting product, respectively; When the slag regulator comprises CaO, SiO2, Al2O3 and MgO, the addition amounts of CaO, SiO2, Al2O3 and MgO are 30-45 wt%, 25-35 wt%, 1-20 wt% and 3-8 wt% of the mass of the reduction smelting product, respectively; When the slag regulator comprises CaO, SiO2, Al2O3, MgO and Na2O, the addition amounts of CaO, SiO2, Al2O3, MgO and Na2O are 29-35 wt%, 25-35 wt%, 1-20 wt%, 3-8 wt% and 1-10 wt% of the mass of the reduction smelting product, respectively.

5. The method according to any one of claims 1-4, wherein the spent lithium battery is a spent lithium-ion battery. An auxiliary carbon source is further added after the raw material pretreatment and batching, and the auxiliary carbon source comprises graphite or waste oil; When the auxiliary carbon source comprises graphite, the molar ratio of carbon in the reduction mixture after the addition of graphite to oxygen in the metal oxide is (0.8-2.0):1; When the auxiliary carbon source comprises waste oil, the addition amount of the waste oil is 2-25 wt% of the mass of the reduction mixture.

6. Use of the method for co-metallurgical recovery of retired lithium batteries in combination with waste catalysts according to any one of claims 1 to 5 for the preparation of multi-component alloys.

7. Use of the method for co-metallurgical recovery of retired lithium batteries in combination with waste catalysts according to any one of claims 1 to 5 for the recovery of lithium salts.

8. A method for producing a multinary alloy and / or a lithium salt, characterized by, Retired lithium batteries are treated using the method for co-metallurgical recovery of retired lithium batteries in combination with waste catalysts according to any one of claims 1 to 5.

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