WO2023029575A1 - Method for removing copper fluoride from battery powder leachate - Google Patents

Method for removing copper fluoride from battery powder leachate Download PDF

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Publication number
WO2023029575A1
WO2023029575A1 PCT/CN2022/092493 CN2022092493W WO2023029575A1 WO 2023029575 A1 WO2023029575 A1 WO 2023029575A1 CN 2022092493 W CN2022092493 W CN 2022092493W WO 2023029575 A1 WO2023029575 A1 WO 2023029575A1
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WIPO (PCT)
Prior art keywords
aluminum
powder
copper
battery powder
solution
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PCT/CN2022/092493
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French (fr)
Chinese (zh)
Inventor
余海军
钟应声
李爱霞
谢英豪
张学梅
李长东
Original Assignee
广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
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Publication of WO2023029575A1 publication Critical patent/WO2023029575A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • 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 recycling waste batteries, in particular to a method for removing copper fluoride from battery powder leachate.
  • the mainstream lithium battery recycling technology is: high temperature roasting + wet acid leaching to recover lithium batteries.
  • the high-temperature method mechanical crushing is performed first, so that the metal casing of the waste lithium battery is broken into small particles, and the battery powder falls off from the waste electrode sheet through sieving, and the organic binder (such as polyvinylidene fluoride) of the battery powder is pyrolyzed at the same time. , polytetrafluoroethylene), conductive agent (lithium hexafluorophosphate), organic solvent, etc. Since the battery powder contains more fluorine and copper impurities, some fluoride remains in the battery powder due to incomplete heating after high-temperature pyrolysis, and copper cannot be removed at high temperature.
  • the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a kind of method for removing copper fluorine in battery powder leaching solution.
  • propose a kind of method for removing copper fluorine in battery powder leachate comprise the following steps:
  • step S1 the temperature of the calcination is 600-1200° C., and the calcination time is 2-8 hours.
  • the calcination is carried out under air or oxygen atmosphere.
  • step S1 the solid-to-liquid ratio of the battery powder to the alcohol solution is 1: (0.5-10) kg/L, and the volume fraction of alcohol in the alcohol solution is 0.1-40% .
  • the alcohol solution is one or more of methanol, ethanol or propanol.
  • the number of times of preferred alcohol washing is 2-5 times.
  • step S1 the solid-to-liquid ratio of the alcohol-washed battery powder to the acid solution is 1: (1-30) kg/L, and the concentration of H + in the acid solution is 0.1-30 mol/L L.
  • the acid solution is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or perchloric acid.
  • the leaching time is 2-10 hours.
  • the aluminum powder is derived from aluminum foil obtained by crushing and screening waste lithium batteries.
  • the aluminum foil is crushed into aluminum powder, and the aluminum powder is less than 300 ⁇ m.
  • the impurity in the aluminum powder is the battery powder that is not completely separated when the waste battery is broken, so there is no need to consider its influence on the leachate of the battery powder.
  • Using aluminum powder to remove fluorine can realize the recycling of aluminum foil, and aluminum can be easily removed from battery powder leachate.
  • step S2 the ratio of the mass of the added aluminum powder to the mass of copper in the leaching solution is (40-60): (180-250), preferably (55-60): (190 -200).
  • the liquid-solid ratio of the filtrate to the ammonium salt is 1: (0.1-40) L/g, and the pH is 2.5-6.0.
  • the liquid-solid ratio of the filtrate to the ammonium salt is 1:(0.5-2) L/g, and the pH is 3.5-5.0.
  • the ammonium salt is one or more of ammonium sulfate, ammonia water, ammonium chloride, ammonium carbonate, ammonium bicarbonate or ammonium nitrate, preferably ammonium sulfate, ammonia water .
  • step S3 the temperature for removing ammonia by heating is 100-400°C; preferably, the time for removing ammonia is 2-5h.
  • step S3 further includes: heating and drying the aluminum hydroxide precipitate to obtain alumina, which can be mixed with the aluminum powder in step S2 for defluorination.
  • the heating temperature is 100-200°C and the heating time is 0.5-2h.
  • step S2 further includes: adding dilute acid to dissolve the copper fluoride slag, and separating to obtain copper-containing solution and aluminum fluoride.
  • the solid-to-liquid ratio of the copper fluoride slag to the dilute acid is 1: (2-12) kg/L, and the concentration of H + in the dilute acid is 0.01-5 mol/L.
  • a method for removing copper fluoride in battery powder leaching solution the specific process is:
  • Battery powder waste lithium batteries are crushed and sieved to obtain battery powder, miscellaneous aluminum foil, copper foil, and miscellaneous aluminum foil is crushed to obtain miscellaneous aluminum powder, and the battery powder is roasted in a kiln through an oxidant;
  • the aluminum powder is ⁇ 300 ⁇ m
  • the battery powder is roasted at 740°C for 4 hours
  • the oxidant is air
  • Battery powder leaching battery powder is washed with alcohol solution, battery powder is washed with alcohol solution, filtered to obtain alcohol washed battery powder, filtrate alcohol washing solution is evaporated to recover alcohol, battery powder is leached with acid, heated and stirred to obtain leachate , adding a certain proportion of miscellaneous aluminum powder, heating, stirring, and separating to obtain fluorine-removing copper leaching solution and fluorine-copper insoluble slag;
  • the solid-liquid ratio of battery powder/alcohol solution is 1:1.5kg/L
  • the volume fraction of alcohol in the alcohol solution is 13%
  • the alcohol is ethanol
  • the alcohol is washed twice
  • the battery powder:acid solid-liquid ratio is 1:7.5kg/L L
  • the acid is 9.3mol/L sulfuric acid
  • the heating temperature is 65°C
  • the mass ratio of the aluminum powder added to the copper in the leaching solution is 55:200
  • the total leaching time is controlled within 6h;
  • a method for removing copper fluoride in battery powder leaching solution the specific process is:
  • Battery powder waste lithium batteries are crushed and sieved to obtain battery powder, miscellaneous aluminum foil, copper foil, and miscellaneous aluminum foil is crushed to obtain miscellaneous aluminum powder, and the battery powder is roasted in a kiln through an oxidant;
  • the aluminum powder is ⁇ 300 ⁇ m
  • the battery powder is roasted at 740°C for 3.5h
  • the oxidant is air
  • Battery powder leaching battery powder is washed with alcohol solution, battery powder is washed with alcohol solution, filtered to obtain alcohol washed battery powder, filtrate alcohol washing solution is evaporated to recover alcohol, battery powder is leached with acid, heated and stirred to obtain leachate , adding a certain proportion of miscellaneous aluminum powder, heating, stirring, and separating to obtain fluorine-removing copper leaching solution and fluorine-copper insoluble slag;
  • the solid-liquid ratio of battery powder/alcohol solution is 1:1.5kg/L
  • the volume fraction of alcohol in the alcohol solution is 13%
  • the alcohol is ethanol
  • the alcohol is washed twice
  • the battery powder:acid solid-liquid ratio is 1:7.5kg/L L
  • the acid is 9.3mol/L sulfuric acid
  • the heating temperature is 65°C
  • the mass ratio of the aluminum powder added to the copper in the leaching solution is 60:217
  • the total leaching time is controlled within 7h;
  • a method for removing copper fluoride in battery powder leaching solution the specific process is:
  • Battery powder waste lithium batteries are crushed and sieved to obtain battery powder, miscellaneous aluminum foil, copper foil, and miscellaneous aluminum foil is crushed to obtain miscellaneous aluminum powder, and the battery powder is roasted in a kiln through an oxidant;
  • the aluminum powder is ⁇ 300 ⁇ m
  • the battery powder is roasted at 740°C for 3.5h
  • the oxidant is air
  • Battery powder leaching battery powder is washed with alcohol solution, battery powder is washed with alcohol solution, filtered to obtain alcohol washed battery powder, filtrate alcohol washing solution is evaporated to recover alcohol, battery powder is leached with acid, heated and stirred to obtain leachate , adding a certain proportion of miscellaneous aluminum powder, heating, stirring, and separating to obtain fluorine-removing copper leaching solution and fluorine-copper insoluble slag;
  • the solid-liquid ratio of battery powder/alcohol solution is 1:1.5kg/L
  • the volume fraction of alcohol in the alcohol solution is 13%
  • the alcohol is ethanol
  • the alcohol is washed twice
  • the battery powder:acid solid-liquid ratio is 1:11.2kg/L L
  • the acid is 9.3mol/L sulfuric acid
  • the heating temperature is 65°C
  • the mass ratio of the aluminum powder added to the copper in the leaching solution is 55:224
  • the total leaching time is controlled within 3h;
  • a method for removing copper fluoride in battery powder leaching solution the specific process is:
  • Battery powder waste lithium batteries are crushed and sieved to obtain battery powder, miscellaneous aluminum foil, copper foil, and miscellaneous aluminum foil is pulverized to obtain miscellaneous aluminum powder, and the battery powder is roasted in a kiln through an oxidant;
  • the aluminum powder is ⁇ 300 ⁇ m
  • the battery powder is roasted at 740°C for 3.5h
  • the oxidant is air
  • Battery powder leaching battery powder is added with acid to leach battery powder, heated and stirred to obtain a leachate, adding a certain proportion of miscellaneous aluminum powder, heated, stirred, and separated to obtain fluorine-removing copper leachate and fluorine-copper insoluble slag.
  • the battery powder:acid-solid-liquid ratio is 1:7.5kg/L
  • the acid is 9.3mol/L sulfuric acid
  • the heating temperature is 65°C
  • the mass ratio of the aluminum powder added to the copper in the leaching solution is 50:235
  • the total leaching time is controlled within 3 hours;
  • a method for removing copper fluoride in battery powder leaching solution the specific process is:
  • Battery powder waste lithium batteries are crushed and sieved to obtain battery powder, miscellaneous aluminum foil, copper foil, and miscellaneous aluminum foil is crushed to obtain miscellaneous aluminum powder, and the battery powder is roasted in a kiln through an oxidant;
  • the aluminum powder is ⁇ 300 ⁇ m
  • the battery powder is roasted at 740°C for 3.5h
  • the oxidant is air
  • Battery powder leaching battery powder is added with acid to leach battery powder, heated and stirred to obtain a leachate, adding a certain proportion of miscellaneous aluminum powder, heated, stirred, and separated to obtain fluorine-removing copper leachate and fluorine-copper insoluble slag.
  • the battery powder:acid-solid-liquid ratio is 1:7.5kg/L
  • the acid is 9.3mol/L sulfuric acid
  • the heating temperature is 65°C
  • the mass ratio of the aluminum powder added to the copper in the leaching solution is 50:196
  • the total leaching time is controlled within 3 hours;
  • Recycling treatment add ammonia water to the fluorine-removing copper leaching solution to control pH, obtain aluminum hydroxide precipitation, remove the precipitation, obtain aluminum-removing leaching solution, heat the aluminum-removing leaching solution to remove ammonia, recycle ammonia to obtain ammonia water, and remove ammonia leaching solution;
  • the mass fraction of ammonia in the ammonia water is 2.73%, the pH is controlled to be 4.8, and the heating temperature for removing ammonia is 350°C;
  • Table 1 embodiment 1-3 and comparative example 1-2 each stage fluorine and copper content situation

Abstract

Disclosed in the present invention is a method for removing copper fluoride from a battery powder leachate. The method comprises: roasting a battery powder, then washing with an alcohol solution; adding an acid solution to the alcohol-washed battery powder for leaching, so as to obtain a leachate; adding aluminum powder into the leachate for reaction; performing solid-liquid separation to obtain a filtrate and a copper fluoride slag; adding an ammonium salt into the filtrate to adjust the pH; separating to obtain an aluminum-removed solution and an aluminum hydroxide precipitate; and heating to remove ammonia from the aluminum-removed solution. The battery powder of the present invention still has remaining fluorine impurities after being roasted. Thus, by means of using an alcohol solution to wash away part of the fluorine impurities and then adding aluminum powder is to react with the fluorine to obtain insoluble aluminum fluoride, a dual defluorination effect is achieved, and the added aluminum powder can reduce the copper in the leachate, thereby allowing better defluorination. Adding aluminum also achieves copper reduction in the leachate. The process for removing copper fluoride of the present invention has a high removal rate and simple steps for removing copper fluoride.

Description

电池粉浸出液中除氟铜的方法Method for removing copper fluoride from battery powder leaching solution 技术领域technical field
本发明属于废旧电池回收技术领域，具体涉及一种电池粉浸出液中除氟铜的方法。The invention belongs to the technical field of recycling waste batteries, in particular to a method for removing copper fluoride from battery powder leachate.
背景技术Background technique
目前，主流的锂电池回收技术为：高温法焙烧+湿法酸浸回收锂电池。在高温法中，先机械破碎，使得废旧锂电池金属外壳碎成小颗粒，通过筛分处理，电池粉从废极片上脱落，同时热解掉电池粉的有机粘结剂(例如聚偏氟乙烯、聚四氟乙烯)、导电剂(六氟磷酸锂)、有机溶剂等。由于电池粉中含氟、铜杂质较多，高温热解后因受热不完全导致部分氟化物仍残留在电池粉中，而铜高温不能除去。因此有相关技术利用除氟剂与电池粉直接混合，去除电池粉中的氟，但除氟剂并不能完全和电池粉中含氟物质反应除去，同时电池粉中也将引入除氟剂中钙镁杂质，但电池粉在后续湿法工艺通常用酸浸出电池粉，因此氟化物、钙镁进入到浸出液中，除杂工艺进一步复杂化。也有相关技术将电池粉LiHCO 3浸出液加入除氟剂去除含氟物质，但除氟剂中铝、锆溶液水解，并不能生成稳定的碳酸盐进行回收，也忽略了铜粉的存在，因此除氟剂、铜也会残留在LiHCO 3浸出液中。电池粉中含氟物质，不仅影响废弃锂电池正极材料的纯度，也对设备产生损害，对电极材料处理环境增加不安全因素。除氟工艺中，必须考虑除氟剂、电池粉中残留的铜以及引入新的杂质可能性，否则增大了后续萃取除杂工艺的复杂程度。 At present, the mainstream lithium battery recycling technology is: high temperature roasting + wet acid leaching to recover lithium batteries. In the high-temperature method, mechanical crushing is performed first, so that the metal casing of the waste lithium battery is broken into small particles, and the battery powder falls off from the waste electrode sheet through sieving, and the organic binder (such as polyvinylidene fluoride) of the battery powder is pyrolyzed at the same time. , polytetrafluoroethylene), conductive agent (lithium hexafluorophosphate), organic solvent, etc. Since the battery powder contains more fluorine and copper impurities, some fluoride remains in the battery powder due to incomplete heating after high-temperature pyrolysis, and copper cannot be removed at high temperature. Therefore, there is a related technology that directly mixes the fluorine-removing agent with the battery powder to remove the fluorine in the battery powder, but the fluorine-removing agent cannot completely react with the fluorine-containing substances in the battery powder to remove it, and at the same time, calcium in the fluoride-removing agent will also be introduced into the battery powder Magnesium impurities, but the battery powder is usually leached with acid in the subsequent wet process, so fluoride, calcium and magnesium enter the leaching solution, and the impurity removal process is further complicated. There is also a related technology that adds battery powder LiHCO 3 leaching solution to a defluoridation agent to remove fluorine-containing substances, but the hydrolysis of aluminum and zirconium solutions in the defluorination agent cannot generate stable carbonate for recovery, and the existence of copper powder is also ignored. Fluoride and copper will also remain in the LiHCO 3 leaching solution. The fluorine-containing substances in the battery powder not only affect the purity of the positive electrode material of the discarded lithium battery, but also cause damage to the equipment and increase the unsafe factor to the electrode material processing environment. In the defluorination process, the possibility of introducing new impurities must be considered in the defluorination agent, copper residue in the battery powder, otherwise the complexity of the subsequent extraction and impurity removal process will be increased.
发明内容Contents 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，本发明提出一种电池粉浸出液中除氟铜的方法。The present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a kind of method for removing copper fluorine in battery powder leaching solution.
根据本发明的一个方面，提出了一种电池粉浸出液中除氟铜的方法，包括以下步骤：According to one aspect of the present invention, propose a kind of method for removing copper fluorine in battery powder leachate, comprise the following steps:
S1：电池粉经过焙烧后用醇溶液醇洗，向醇洗后的电池粉中加入酸液进行浸出得到浸出液；S1: After the battery powder is roasted, it is washed with an alcohol solution, and acid solution is added to the battery powder after alcohol washing to obtain a leachate;
S2：向所述浸出液中加入铝粉进行反应，固液分离得到滤液和氟铜渣；S2: adding aluminum powder to the leaching solution for reaction, and separating solid and liquid to obtain filtrate and copper fluoride slag;
S3：向所述滤液中加入铵盐调节pH，分离得到除铝后液和氢氧化铝沉淀，对所述除铝后液进行加热除氨。S3: adding ammonium salt to the filtrate to adjust the pH, separating and obtaining the aluminum-removed liquid and aluminum hydroxide precipitation, and heating the aluminum-removed liquid to remove ammonia.
在本发明的一些实施方式中，步骤S1中，所述焙烧的温度为600-1200℃，焙烧的时间为2-8h。所述焙烧在空气或氧气气氛下进行。In some embodiments of the present invention, in step S1, the temperature of the calcination is 600-1200° C., and the calcination time is 2-8 hours. The calcination is carried out under air or oxygen atmosphere.
在本发明的一些实施方式中，步骤S1中，所述电池粉与醇溶液的固液比为1：(0.5-10)kg/L，所述醇溶液中醇的体积分数为0.1-40％。In some embodiments of the present invention, in step S1, the solid-to-liquid ratio of the battery powder to the alcohol solution is 1: (0.5-10) kg/L, and the volume fraction of alcohol in the alcohol solution is 0.1-40% .
在本发明的一些实施方式中，步骤S1中，所述醇溶液为甲醇、乙醇或丙醇中的一种或几种。优选醇洗的次数为2-5次。In some embodiments of the present invention, in step S1, the alcohol solution is one or more of methanol, ethanol or propanol. The number of times of preferred alcohol washing is 2-5 times.
在本发明的一些实施方式中，步骤S1中，醇洗后的电池粉与酸液的固液比为1：(1-30)kg/L，酸液中H +的浓度为0.1-30mol/L。 In some embodiments of the present invention, in step S1, the solid-to-liquid ratio of the alcohol-washed battery powder to the acid solution is 1: (1-30) kg/L, and the concentration of H + in the acid solution is 0.1-30 mol/L L.
在本发明的一些实施方式中，步骤S1中，所述酸液为盐酸、硫酸、硝酸、磷酸或高氯酸中的一种或几种。In some embodiments of the present invention, in step S1, the acid solution is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or perchloric acid.
在本发明的一些实施方式中，步骤S1中，所述浸出的时间为2-10h。In some embodiments of the present invention, in step S1, the leaching time is 2-10 hours.
在本发明的一些实施方式中，步骤S2中，所述铝粉来源于废旧锂电池破碎筛分得到的铝箔。铝箔粉碎成铝粉，铝粉<300μm。铝粉中杂质为废旧电池破碎时未分离完全的电池粉，因此不需要考虑其对电池粉浸出液的影响。用铝粉除氟能够实现铝箔的回收利用，且铝从电池粉浸出液中容易除去。In some embodiments of the present invention, in step S2, the aluminum powder is derived from aluminum foil obtained by crushing and screening waste lithium batteries. The aluminum foil is crushed into aluminum powder, and the aluminum powder is less than 300μm. The impurity in the aluminum powder is the battery powder that is not completely separated when the waste battery is broken, so there is no need to consider its influence on the leachate of the battery powder. Using aluminum powder to remove fluorine can realize the recycling of aluminum foil, and aluminum can be easily removed from battery powder leachate.
在本发明的一些实施方式中，步骤S2中，所加入铝粉的质量与浸出液中铜的质量之比为(40-60)：(180-250)，优选为(55-60)：(190-200)。In some embodiments of the present invention, in step S2, the ratio of the mass of the added aluminum powder to the mass of copper in the leaching solution is (40-60): (180-250), preferably (55-60): (190 -200).
在本发明的一些实施方式中，步骤S3中，所述滤液与铵盐的液固比为1：(0.1-40)L/g，所述pH为2.5-6.0。优选的，所述滤液与铵盐的液固比为1：(0.5-2)L/g，所述pH为3.5-5.0。用铵盐除铝后只需加热即可除氨，不会重新引入新的杂质。In some embodiments of the present invention, in step S3, the liquid-solid ratio of the filtrate to the ammonium salt is 1: (0.1-40) L/g, and the pH is 2.5-6.0. Preferably, the liquid-solid ratio of the filtrate to the ammonium salt is 1:(0.5-2) L/g, and the pH is 3.5-5.0. After removing aluminum with ammonium salt, it only needs to be heated to remove ammonia, and no new impurities will be reintroduced.
在本发明的一些实施方式中，步骤S3中，所述铵盐为硫酸铵、氨水、氯化铵、碳酸铵、碳酸氢铵或硝酸铵中的一种或几种，优选为硫酸铵、氨水。In some embodiments of the present invention, in step S3, the ammonium salt is one or more of ammonium sulfate, ammonia water, ammonium chloride, ammonium carbonate, ammonium bicarbonate or ammonium nitrate, preferably ammonium sulfate, ammonia water .
在本发明的一些实施方式中，步骤S3中，所述加热除氨的温度为100-400℃；优选 的，除氨的时间为2-5h。In some embodiments of the present invention, in step S3, the temperature for removing ammonia by heating is 100-400°C; preferably, the time for removing ammonia is 2-5h.
在本发明的一些实施方式中，步骤S3中，还包括：所述氢氧化铝沉淀经加热干燥得到氧化铝，氧化铝可与步骤S2中的铝粉混合用于除氟。优选的，加热的温度为100-200℃，时间为0.5-2h。In some embodiments of the present invention, step S3 further includes: heating and drying the aluminum hydroxide precipitate to obtain alumina, which can be mixed with the aluminum powder in step S2 for defluorination. Preferably, the heating temperature is 100-200°C and the heating time is 0.5-2h.
在本发明的一些实施方式中，步骤S2中，还包括：所述氟铜渣加入稀酸溶解，分离得到含铜溶液和氟化铝。优选的，氟铜渣与稀酸的固液比为1：(2-12)kg/L，所述稀酸中H +在浓度为0.01-5mol/L。 In some embodiments of the present invention, step S2 further includes: adding dilute acid to dissolve the copper fluoride slag, and separating to obtain copper-containing solution and aluminum fluoride. Preferably, the solid-to-liquid ratio of the copper fluoride slag to the dilute acid is 1: (2-12) kg/L, and the concentration of H + in the dilute acid is 0.01-5 mol/L.
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:
本发明的电池粉焙烧后仍然残留氟杂质，因此利用醇溶液洗去部分氟杂质，再加入铝粉与氟反应得到不溶的氟化铝，具有双重除氟的作用，且加入的过量的铝粉，除氟比较彻底；废电池破碎成电池粉后，往往含有部分杂质铜粉，因此铜粉也将酸溶解，进入到浸出液成铜离子，浸出液检测分析发现，除氟浸出液中铜含量减少，氟化铝不溶渣中含有部分铜，因此加入铝粉能将浸出液中铜还原出来，通过本发明的除氟铜工艺，去除率高，除氟铜步骤简单，除氟铜工艺反应方程式如下：After the battery powder of the present invention is roasted, fluorine impurities still remain, so alcohol solution is used to wash away part of fluorine impurities, and then aluminum powder is added to react with fluorine to obtain insoluble aluminum fluoride, which has double defluorination effect, and the excessive aluminum powder added , the removal of fluorine is relatively thorough; after the waste battery is broken into battery powder, it often contains some impurity copper powder, so the copper powder will also be dissolved in acid and enter the leaching solution to form copper ions. The aluminum insoluble slag contains part of copper, so the addition of aluminum powder can reduce the copper in the leaching solution. Through the copper fluoride removal process of the present invention, the removal rate is high, and the copper fluoride removal step is simple. The reaction equation of the copper fluoride removal process is as follows:
2Al+6H +→2Al 3++3H 2，Al 3++3F -→AlF 3 2Al+6H + →2Al 3+ +3H 2 , Al 3+ +3F - →AlF 3
Cu+2H +→Cu 2++H 2，2Al+3Cu 2+→2Al 3++3Cu。 Cu+2H + →Cu 2+ +H 2 , 2Al+3Cu 2+ →2Al 3+ +3Cu.
具体实施方式Detailed ways
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 conception and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments, so as to fully understand the purpose, features and effects of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, rather than all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative efforts belong to The protection scope of the present invention.
实施例1Example 1
一种电池粉浸出液中除氟铜的方法，具体过程为：A method for removing copper fluoride in battery powder leaching solution, the specific process is:
(1)电池粉：废旧锂电池破碎筛分得到电池粉、含杂铝箔、铜箔，含杂铝箔粉碎得到含杂铝粉，电池粉通氧化剂下窑炉焙烧；(1) Battery powder: waste lithium batteries are crushed and sieved to obtain battery powder, miscellaneous aluminum foil, copper foil, and miscellaneous aluminum foil is crushed to obtain miscellaneous aluminum powder, and the battery powder is roasted in a kiln through an oxidant;
其中，铝粉<300μm，电池粉740℃下，焙烧4h，氧化剂为空气；Among them, the aluminum powder is <300μm, the battery powder is roasted at 740°C for 4 hours, and the oxidant is air;
(2)电池粉浸出：电池粉加醇溶液醇洗，电池粉加醇溶液醇洗，过滤得醇洗电池粉，滤液醇洗液蒸发回收醇，加酸浸出电池粉，加热，搅拌，得浸出液，加入一定比例的含杂铝粉，加热，搅拌，分离得到除氟铜浸出液、氟铜不溶渣；(2) Battery powder leaching: battery powder is washed with alcohol solution, battery powder is washed with alcohol solution, filtered to obtain alcohol washed battery powder, filtrate alcohol washing solution is evaporated to recover alcohol, battery powder is leached with acid, heated and stirred to obtain leachate , adding a certain proportion of miscellaneous aluminum powder, heating, stirring, and separating to obtain fluorine-removing copper leaching solution and fluorine-copper insoluble slag;
其中，电池粉/醇溶液的固液比在1：1.5kg/L，醇溶液中醇体积分数13％，醇为乙醇，醇洗2次，电池粉：酸固液比为1：7.5kg/L，酸为9.3mol/L硫酸，加热温度65℃，铝粉加入的质量与浸出液中铜的质量比为55：200，总的浸出时间控制在6h内；Among them, the solid-liquid ratio of battery powder/alcohol solution is 1:1.5kg/L, the volume fraction of alcohol in the alcohol solution is 13%, the alcohol is ethanol, and the alcohol is washed twice, and the battery powder:acid solid-liquid ratio is 1:7.5kg/L L, the acid is 9.3mol/L sulfuric acid, the heating temperature is 65°C, the mass ratio of the aluminum powder added to the copper in the leaching solution is 55:200, and the total leaching time is controlled within 6h;
(3)回收处理：除氟铜浸出液加入硫酸铵调pH，得氢氧化铝沉淀，去除沉淀，得到除铝浸出液，除铝浸出液加热除氨，回收氨得除氨浸出液；(3) Recycling treatment: add ammonium sulfate to the fluoride-removing copper leaching solution to adjust pH, obtain aluminum hydroxide precipitation, remove the precipitation, obtain aluminum removal leaching solution, heat the aluminum removal leaching solution to remove ammonia, and recover ammonia to obtain ammonia removal leaching solution;
其中，1L除氟铜浸出液加入0.74g硫酸铵，控制pH＝3.7，除氨加热温度在300℃；Among them, 0.74 g of ammonium sulfate was added to 1 L of fluorine-removing copper leaching solution to control pH = 3.7, and the heating temperature for ammonia removal was 300 ° C;
(4)回收氢氧化铝：氢氧化铝沉淀加热50min，在145℃下得到氧化铝，氟铜不溶渣与0.45mol/L硫酸按固液比1：4.5kg/L混合，溶解得沉淀为氟化铝，氢氧化铝与步骤(1)中的含杂铝粉混合用于除氟。(4) Recovery of aluminum hydroxide: Aluminum hydroxide precipitation is heated for 50 minutes to obtain alumina at 145°C. Fluorine copper insoluble slag is mixed with 0.45mol/L sulfuric acid at a solid-to-liquid ratio of 1:4.5kg/L to dissolve and precipitate into fluorine Aluminum chloride, aluminum hydroxide and the miscellaneous aluminum powder in the step (1) are mixed for defluorination.
实施例2Example 2
一种电池粉浸出液中除氟铜的方法，具体过程为：A method for removing copper fluoride in battery powder leaching solution, the specific process is:
(1)电池粉：废旧锂电池破碎筛分得到电池粉、含杂铝箔、铜箔，含杂铝箔粉碎得到含杂铝粉，电池粉通氧化剂下窑炉焙烧；(1) Battery powder: waste lithium batteries are crushed and sieved to obtain battery powder, miscellaneous aluminum foil, copper foil, and miscellaneous aluminum foil is crushed to obtain miscellaneous aluminum powder, and the battery powder is roasted in a kiln through an oxidant;
其中，铝粉<300μm，电池粉740℃下，焙烧3.5h，氧化剂为空气；Among them, the aluminum powder is <300μm, the battery powder is roasted at 740°C for 3.5h, and the oxidant is air;
(2)电池粉浸出：电池粉加醇溶液醇洗，电池粉加醇溶液醇洗，过滤得醇洗电池粉，滤液醇洗液蒸发回收醇，加酸浸出电池粉，加热，搅拌，得浸出液，加入一定比例的含杂铝粉，加热，搅拌，分离得到除氟铜浸出液、氟铜不溶渣；(2) Battery powder leaching: battery powder is washed with alcohol solution, battery powder is washed with alcohol solution, filtered to obtain alcohol washed battery powder, filtrate alcohol washing solution is evaporated to recover alcohol, battery powder is leached with acid, heated and stirred to obtain leachate , adding a certain proportion of miscellaneous aluminum powder, heating, stirring, and separating to obtain fluorine-removing copper leaching solution and fluorine-copper insoluble slag;
其中，电池粉/醇溶液的固液比在1：1.5kg/L，醇溶液中醇体积分数13％，醇为乙醇，醇洗2次，电池粉：酸固液比为1：7.5kg/L，酸为9.3mol/L硫酸，加热温度65℃，铝粉加入的质量与浸出液中铜的质量比为60：217，总的浸出时间控制在7h内；Among them, the solid-liquid ratio of battery powder/alcohol solution is 1:1.5kg/L, the volume fraction of alcohol in the alcohol solution is 13%, the alcohol is ethanol, and the alcohol is washed twice, and the battery powder:acid solid-liquid ratio is 1:7.5kg/L L, the acid is 9.3mol/L sulfuric acid, the heating temperature is 65°C, the mass ratio of the aluminum powder added to the copper in the leaching solution is 60:217, and the total leaching time is controlled within 7h;
(3)回收处理：除氟铜浸出液加入硫酸铵调pH，得氢氧化铝沉淀，去除沉淀，得 到除铝浸出液，除铝浸出液加热除氨，回收氨得除氨浸出液；(3) Recycling treatment: add ammonium sulfate to the fluorine-removing copper leaching solution to adjust pH, obtain aluminum hydroxide precipitation, remove the precipitation, obtain the leaching solution for removing aluminum, heat the leaching solution for removing aluminum and remove ammonia, reclaim ammonia to obtain the leaching solution for removing ammonia;
其中，1L除氟铜浸出液加入1.13g硫酸铵，控制pH＝3.3，除氨加热温度在340℃；Among them, add 1.13g of ammonium sulfate to 1L of fluorine-removing copper leaching solution, control the pH=3.3, and the heating temperature for removing ammonia is 340°C;
(4)回收氢氧化铝：氢氧化铝沉淀加热50min，在155℃下得到氧化铝，氟铜不溶渣与0.45mol/L硫酸按固液比1：4.5kg/L混合，溶解得沉淀为氟化铝，氢氧化铝与步骤(1)中的含杂铝粉混合用于除氟。(4) Recovery of aluminum hydroxide: heat aluminum hydroxide precipitation for 50 minutes, obtain alumina at 155 ° C, mix fluorine copper insoluble residue with 0.45mol/L sulfuric acid at a solid-to-liquid ratio of 1:4.5kg/L, dissolve and precipitate into fluorine Aluminum chloride, aluminum hydroxide and the miscellaneous aluminum powder in the step (1) are mixed for defluorination.
实施例3Example 3
一种电池粉浸出液中除氟铜的方法，具体过程为：A method for removing copper fluoride in battery powder leaching solution, the specific process is:
(1)电池粉：废旧锂电池破碎筛分得到电池粉、含杂铝箔、铜箔，含杂铝箔粉碎得到含杂铝粉，电池粉通氧化剂下窑炉焙烧；(1) Battery powder: waste lithium batteries are crushed and sieved to obtain battery powder, miscellaneous aluminum foil, copper foil, and miscellaneous aluminum foil is crushed to obtain miscellaneous aluminum powder, and the battery powder is roasted in a kiln through an oxidant;
其中，铝粉<300μm，电池粉740℃下，焙烧3.5h，氧化剂为空气；Among them, the aluminum powder is <300μm, the battery powder is roasted at 740°C for 3.5h, and the oxidant is air;
(2)电池粉浸出：电池粉加醇溶液醇洗，电池粉加醇溶液醇洗，过滤得醇洗电池粉，滤液醇洗液蒸发回收醇，加酸浸出电池粉，加热，搅拌，得浸出液，加入一定比例的含杂铝粉，加热，搅拌，分离得到除氟铜浸出液、氟铜不溶渣；(2) Battery powder leaching: battery powder is washed with alcohol solution, battery powder is washed with alcohol solution, filtered to obtain alcohol washed battery powder, filtrate alcohol washing solution is evaporated to recover alcohol, battery powder is leached with acid, heated and stirred to obtain leachate , adding a certain proportion of miscellaneous aluminum powder, heating, stirring, and separating to obtain fluorine-removing copper leaching solution and fluorine-copper insoluble slag;
其中，电池粉/醇溶液的固液比在1：1.5kg/L，醇溶液中醇体积分数13％，醇为乙醇，醇洗2次，电池粉：酸固液比为1：11.2kg/L，酸为9.3mol/L硫酸，加热温度65℃，铝粉加入的质量与浸出液中铜的质量比为55：224，总的浸出时间控制在3h内；Among them, the solid-liquid ratio of battery powder/alcohol solution is 1:1.5kg/L, the volume fraction of alcohol in the alcohol solution is 13%, the alcohol is ethanol, and the alcohol is washed twice, and the battery powder:acid solid-liquid ratio is 1:11.2kg/L L, the acid is 9.3mol/L sulfuric acid, the heating temperature is 65°C, the mass ratio of the aluminum powder added to the copper in the leaching solution is 55:224, and the total leaching time is controlled within 3h;
(3)回收处理：除氟铜浸出液加入硫酸铵调pH，得氢氧化铝沉淀，去除沉淀，得到除铝浸出液，除铝浸出液加热除氨，回收氨得除氨浸出液；(3) Recycling treatment: add ammonium sulfate to the fluoride-removing copper leaching solution to adjust pH, obtain aluminum hydroxide precipitation, remove the precipitation, obtain aluminum removal leaching solution, heat the aluminum removal leaching solution to remove ammonia, and recover ammonia to obtain ammonia removal leaching solution;
其中，1L除氟铜浸出液加入1.47g硫酸铵，控制pH＝4.2，除氨加热温度在350℃；Among them, 1.47 g of ammonium sulfate was added to 1 L of fluorine-removing copper leaching solution to control pH = 4.2, and the heating temperature for ammonia removal was 350 ° C;
(4)回收氢氧化铝：氢氧化铝沉淀加热50min，在155℃下得到氧化铝，氟铜不溶渣与0.45mol/L硫酸按固液比1：4.5kg/L混合，溶解得沉淀为氟化铝，氢氧化铝与步骤(1)中的含杂铝粉混合用于除氟。(4) Recovery of aluminum hydroxide: heat aluminum hydroxide precipitation for 50 minutes, obtain alumina at 155 ° C, mix fluorine copper insoluble residue with 0.45mol/L sulfuric acid at a solid-to-liquid ratio of 1:4.5kg/L, dissolve and precipitate into fluorine Aluminum chloride, aluminum hydroxide and the miscellaneous aluminum powder in the step (1) are mixed for defluorination.
对比例1Comparative example 1
一种电池粉浸出液中除氟铜的方法，具体过程为：A method for removing copper fluoride in battery powder leaching solution, the specific process is:
(1)电池粉：废旧锂电池破碎筛分得到电池粉、含杂铝箔、铜箔，含杂铝箔粉碎得 到含杂铝粉，电池粉通氧化剂下窑炉焙烧；(1) Battery powder: waste lithium batteries are crushed and sieved to obtain battery powder, miscellaneous aluminum foil, copper foil, and miscellaneous aluminum foil is pulverized to obtain miscellaneous aluminum powder, and the battery powder is roasted in a kiln through an oxidant;
其中，铝粉<300μm，电池粉740℃下，焙烧3.5h，氧化剂为空气；Among them, the aluminum powder is <300μm, the battery powder is roasted at 740°C for 3.5h, and the oxidant is air;
(2)电池粉浸出：电池粉加酸浸出电池粉，加热，搅拌，得浸出液，加入一定比例的含杂铝粉，加热，搅拌，分离得到除氟铜浸出液、氟铜不溶渣。(2) Battery powder leaching: battery powder is added with acid to leach battery powder, heated and stirred to obtain a leachate, adding a certain proportion of miscellaneous aluminum powder, heated, stirred, and separated to obtain fluorine-removing copper leachate and fluorine-copper insoluble slag.
其中，电池粉：酸固液比为1：7.5kg/L，酸9.3mol/L硫酸，加热温度65℃，铝粉加入质量与浸出液中铜的质量比为50：235，总的浸出时间控制在3h内；Among them, the battery powder:acid-solid-liquid ratio is 1:7.5kg/L, the acid is 9.3mol/L sulfuric acid, the heating temperature is 65°C, the mass ratio of the aluminum powder added to the copper in the leaching solution is 50:235, and the total leaching time is controlled within 3 hours;
(3)回收处理：除氟铜浸出液加入硫酸铵调pH，得氢氧化铝沉淀，去除沉淀，得到除铝浸出液，除铝浸出液加热除氨，回收氨得除氨浸出液；(3) Recycling treatment: add ammonium sulfate to the fluoride-removing copper leaching solution to adjust pH, obtain aluminum hydroxide precipitation, remove the precipitation, obtain aluminum removal leaching solution, heat the aluminum removal leaching solution to remove ammonia, and recover ammonia to obtain ammonia removal leaching solution;
其中，1L除氟铜浸出液加入1.85g硫酸铵，控制pH＝4.2，除氨加热温度在350℃；Among them, 1.85 g of ammonium sulfate was added to 1 L of fluorine-removing copper leaching solution to control pH = 4.2, and the heating temperature for ammonia removal was 350 ° C;
(4)回收氢氧化铝：氢氧化铝沉淀加热50min，在155℃下得到氧化铝，氟铜不溶渣与0.45mol/L硫酸按固液比1：4.5kg/L混合，溶解得沉淀为氟化铝，氢氧化铝与步骤(1)中的含杂铝粉混合用于除氟。(4) Recovery of aluminum hydroxide: heat aluminum hydroxide precipitation for 50 minutes, obtain alumina at 155 ° C, mix fluorine copper insoluble residue with 0.45mol/L sulfuric acid at a solid-to-liquid ratio of 1:4.5kg/L, dissolve and precipitate into fluorine Aluminum chloride, aluminum hydroxide and the miscellaneous aluminum powder in the step (1) are mixed for defluorination.
对比例2Comparative example 2
一种电池粉浸出液中除氟铜的方法，具体过程为：A method for removing copper fluoride in battery powder leaching solution, the specific process is:
(1)电池粉：废旧锂电池破碎筛分得到电池粉、含杂铝箔、铜箔，含杂铝箔粉碎得到含杂铝粉，电池粉通氧化剂下窑炉焙烧；(1) Battery powder: waste lithium batteries are crushed and sieved to obtain battery powder, miscellaneous aluminum foil, copper foil, and miscellaneous aluminum foil is crushed to obtain miscellaneous aluminum powder, and the battery powder is roasted in a kiln through an oxidant;
其中，铝粉<300μm，电池粉740℃下，焙烧3.5h，氧化剂为空气；Among them, the aluminum powder is <300μm, the battery powder is roasted at 740°C for 3.5h, and the oxidant is air;
(2)电池粉浸出：电池粉加酸浸出电池粉，加热，搅拌，得浸出液，加入一定比例的含杂铝粉，加热，搅拌，分离得到除氟铜浸出液、氟铜不溶渣。(2) Battery powder leaching: battery powder is added with acid to leach battery powder, heated and stirred to obtain a leachate, adding a certain proportion of miscellaneous aluminum powder, heated, stirred, and separated to obtain fluorine-removing copper leachate and fluorine-copper insoluble slag.
其中，电池粉：酸固液比为1：7.5kg/L，酸9.3mol/L硫酸，加热温度65℃，铝粉加入质量与浸出液中铜的质量比为50：196，总的浸出时间控制在3h内；Among them, the battery powder:acid-solid-liquid ratio is 1:7.5kg/L, the acid is 9.3mol/L sulfuric acid, the heating temperature is 65°C, the mass ratio of the aluminum powder added to the copper in the leaching solution is 50:196, and the total leaching time is controlled within 3 hours;
(3)回收处理：除氟铜浸出液加入氨水控制pH，得氢氧化铝沉淀，去除沉淀，得到除铝浸出液，除铝浸出液加热除氨，回收氨得氨水、除氨浸出液；(3) Recycling treatment: add ammonia water to the fluorine-removing copper leaching solution to control pH, obtain aluminum hydroxide precipitation, remove the precipitation, obtain aluminum-removing leaching solution, heat the aluminum-removing leaching solution to remove ammonia, recycle ammonia to obtain ammonia water, and remove ammonia leaching solution;
其中，氨水中氨质量分数为2.73％，控制pH＝4.8，除氨加热温度为350℃；Wherein, the mass fraction of ammonia in the ammonia water is 2.73%, the pH is controlled to be 4.8, and the heating temperature for removing ammonia is 350°C;
(4)回收氢氧化铝：氢氧化铝沉淀加热50min，在155℃下得到氧化铝，氟铜不溶 渣与0.45mol/L硫酸按固液比1：9.3kg/L混合，溶解得沉淀为氟化铝，氢氧化铝与步骤(1)中的含杂铝粉混合用于除氟。(4) Recovery of aluminum hydroxide: heat aluminum hydroxide precipitation for 50 minutes, obtain alumina at 155 ° C, mix fluorine copper insoluble slag with 0.45mol/L sulfuric acid at a solid-to-liquid ratio of 1:9.3kg/L, dissolve and precipitate into fluorine Aluminum chloride, aluminum hydroxide and the miscellaneous aluminum powder in the step (1) are mixed for defluorination.
表1实施例1-3与对比例1-2各阶段氟和铜含量情况Table 1 embodiment 1-3 and comparative example 1-2 each stage fluorine and copper content situation
Figure PCTCN2022092493-appb-000001
Figure PCTCN2022092493-appb-000001
从表1可以看到，实施例1-3经过醇洗后，烘干后电池粉的氟含量明显降低了，对 比例1和对比例2未经过醇洗，加酸后的浸出液中的氟含量明显比实施例1-3高，表明醇洗具有一定的除氟效果。另外，加入铝粉后，所得到的除氟铜浸出液的氟含量和铜含量非常低，表明本工艺的氟铜去除率高。It can be seen from Table 1 that the fluorine content of the battery powder after drying in Examples 1-3 was significantly reduced after alcohol washing, and the fluorine content in the leachate after adding acid was not washed in Comparative Example 1 and Comparative Example 2. Obviously higher than that of Examples 1-3, showing that alcohol washing has a certain defluoridation effect. In addition, after adding aluminum powder, the fluorine content and copper content of the fluorine-removing copper leaching solution obtained are very low, indicating that the removal rate of copper fluoride in this process is high.
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 of those of ordinary skill in the art, various modifications can be made without departing from the spirit of the present invention. Variety. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other if there is no conflict.

Claims (10)

  1. 一种电池粉浸出液中除氟铜的方法，其特征在于，包括以下步骤：A method for removing copper fluoride in battery powder leachate, characterized in that it comprises the following steps:
    S1：电池粉经过焙烧后用醇溶液醇洗，向醇洗后的电池粉中加入酸液进行浸出得到浸出液；S1: After the battery powder is roasted, it is washed with an alcohol solution, and acid solution is added to the battery powder after alcohol washing to obtain a leachate;
    S2：向所述浸出液中加入铝粉进行反应，固液分离得到滤液和氟铜渣；S2: adding aluminum powder to the leaching solution for reaction, and separating solid and liquid to obtain filtrate and copper fluoride slag;
    S3：向所述滤液中加入铵盐调节pH，分离得到除铝后液和氢氧化铝沉淀，对所述除铝后液进行加热除氨。S3: adding ammonium salt to the filtrate to adjust the pH, separating and obtaining the aluminum-removed liquid and aluminum hydroxide precipitation, and heating the aluminum-removed liquid to remove ammonia.
  2. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述焙烧的温度为600-1200℃，焙烧的时间为2-8h。The method according to claim 1, characterized in that, in step S1, the temperature of the calcination is 600-1200° C., and the calcination time is 2-8 hours.
  3. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述电池粉与醇溶液的固液比为1：(0.5-10)kg/L，所述醇溶液中醇的体积分数为0.1-40％。The method according to claim 1, characterized in that, in step S1, the solid-to-liquid ratio of the battery powder to the alcohol solution is 1: (0.5-10) kg/L, and the volume fraction of alcohol in the alcohol solution is 0.1-40%.
  4. 根据权利要求1所述的方法，其特征在于，步骤S1中，醇洗后的电池粉与酸液的固液比为1：(1-30)kg/L，酸液中H +的浓度为0.1-30mol/L。 The method according to claim 1, characterized in that in step S1, the solid-to-liquid ratio of the alcohol-washed battery powder to the acid solution is 1: (1-30) kg/L, and the concentration of H in the acid solution is 0.1-30mol/L.
  5. 根据权利要求1所述的方法，其特征在于，步骤S2中，所述铝粉来源于废旧锂电池破碎筛分得到的铝箔。The method according to claim 1, characterized in that, in step S2, the aluminum powder is derived from aluminum foil obtained by crushing and screening waste lithium batteries.
  6. 根据权利要求1所述的方法，其特征在于，步骤S2中，所加入铝粉的质量与浸出液中铜的质量之比为(40-60)：(180-250)。The method according to claim 1, characterized in that, in step S2, the ratio of the mass of the added aluminum powder to the mass of copper in the leaching solution is (40-60):(180-250).
  7. 根据权利要求1所述的方法，其特征在于，步骤S3中，所述滤液与铵盐的液固比为1：(0.1-40)L/g，所述pH为2.5-6.0。The method according to claim 1, characterized in that, in step S3, the liquid-solid ratio of the filtrate to the ammonium salt is 1: (0.1-40) L/g, and the pH is 2.5-6.0.
  8. 根据权利要求1所述的方法，其特征在于，步骤S3中，所述加热除氨的温度为100-400℃；优选的，除氨的时间为2-5h。The method according to claim 1, characterized in that, in step S3, the temperature for removing ammonia by heating is 100-400° C.; preferably, the time for removing ammonia is 2-5 hours.
  9. 根据权利要求1所述的方法，其特征在于，步骤S3中，还包括：所述氢氧化铝沉淀经加热干燥得到氧化铝，氧化铝可与步骤S2中的铝粉混合用于除氟。The method according to claim 1, characterized in that, in step S3, further comprising: heating and drying the precipitated aluminum hydroxide to obtain alumina, which can be mixed with the aluminum powder in step S2 for defluorination.
  10. 根据权利要求1所述的方法，其特征在于，步骤S2中，还包括：所述氟铜渣加入稀酸溶解，分离得到含铜溶液和氟化铝。The method according to claim 1, characterized in that, in step S2, further comprising: adding dilute acid to dissolve the copper fluoride slag, and separating to obtain copper-containing solution and aluminum fluoride.
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