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WO2011035916A1 - Procédé de valorisation de métaux à partir de batteries hev ou ev - Google Patents

Procédé de valorisation de métaux à partir de batteries hev ou ev Download PDF

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Publication number
WO2011035916A1
WO2011035916A1 PCT/EP2010/005841 EP2010005841W WO2011035916A1 WO 2011035916 A1 WO2011035916 A1 WO 2011035916A1 EP 2010005841 W EP2010005841 W EP 2010005841W WO 2011035916 A1 WO2011035916 A1 WO 2011035916A1
Authority
WO
WIPO (PCT)
Prior art keywords
batteries
slag
furnace
charge
recovery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2010/005841
Other languages
English (en)
Inventor
Karel Verscheure
Mieke Campforts
Maurits Van Camp
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Umicore NV SA
Original Assignee
Umicore NV SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Umicore NV SA filed Critical Umicore NV SA
Publication of WO2011035916A1 publication Critical patent/WO2011035916A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C22B7/001—Dry processes
    • C22B7/003—Dry processes only remelting, e.g. of chips, borings, turnings; apparatus used therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C22B23/021—Obtaining nickel or cobalt by dry processes by reduction in solid state, e.g. by segregation processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C22B23/023—Obtaining nickel or cobalt by dry processes with formation of ferro-nickel or ferro-cobalt
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/16—Making or repairing linings ; Increasing the durability of linings; Breaking away linings
    • F27D1/1678—Increasing the durability of linings; Means for protecting
    • 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 disclosed invention concerns a recycling process for recovery of metals from HEV (hybrid electric vehicles) or EV (electric vehicles) batteries.
  • NiMH batteries nickel-metal hydrides
  • Li-ion batteries will prevail in the near future. This is especially true for electric vehicles (EV), where a high gravimetric energy density of the embarked batteries is key to success.
  • the objective of the present invention is to overcome these problems by using a bath smelting process where the feed is directly introduced into a molten bath .
  • the invented process is particularly adapted for treating metallurgical charges mainly constituted by Li-ion and/or NiMH batteries of the type used in electric vehicles and hybrids.
  • the invention concerns a process for the recovery of Ni and/or Co from such batteries, comprising the steps of:
  • the fraction of batteries, expressed as weight % of the metallurgical charge, is at least equal to 40%;
  • bath furnace is equipped with means to provide freeze lining of the slag.
  • the frozen slag layer lining the furnace as measured at the level of the surface of the molten slag, has a thickness of at least 10 mm, preferably at least 20 mm.
  • the invented process is also particularly adapted for treating metallurgical charges mainly constituted by Li-ion batteries.
  • This embodiment concerns an autogenous process for the recovery of Co, which is present in an oxidized form, from Li-ion batteries also containing Al and C, which is present as graphite or in organic matter, comprising the steps of:
  • a metallurgical charge comprising CaO, and preferably Si0 2 , as slag formers, and Li-ion batteries;
  • the fraction of Li-ion batteries expressed as weight % of the metallurgical charge, is at least equal to 153% - 3.5 (Al% + 0.6 C%), Al% and C% being the weight % of Al and C in the batteries. No additional reducing agent or fuel is needed in this particular embodiment.
  • a bath furnace requires only a basic charge preparation as the morphology of the feed is far less critical than with a shaft furnace. Also, the burden of gas cleaning is considerably lightened as no additional plasma torch is needed for the post combustion of the exhaust gasses with secondary air. When combining this with the known principle of post- combustion of the CO above the bath, the energy efficiency of the process is even further enhanced.
  • Batteries such as those found in portable devices can be fed as such to the furnace, i.e. without dismantling or shredding. The risk of explosion is then mitigated as the individual cells are sufficiently small.
  • directly feeding large (H)EV batteries or battery packs requires additional protection measures in the furnace, in particular when the relative amount of batteries in the charge exceeds about 40% by weight.
  • the use of freeze lining then becomes necessary from an economic point of view. Freeze lining is known for protecting the fire-bricks of furnaces against chemical attack. It however also appears suitable to protect against the mechanical attack from exploding batteries, thanks to its regenerating nature.
  • (H)EV batteries are thus directly fed to a bath smelter.
  • the batteries do not need to be shredded in a preliminary process.
  • Such batteries typically contain large cells, which are susceptible to explode violently when undergoing a rapid heating cycle. This can be detrimental to the lining of the furnace, unless special precautionary measures are taken. It appears that combining a bath smelter with freeze lining at the bath level, i.e. where the batteries contact the bath and tend to float for some time, is essential in protecting the lining.
  • the excellent reduction kinetics and yields that are achieved are believed to be due to the proximity of metallic Al and oxidized metallic elements (such as Co, Ni and Mn) within the Li-batteries themselves. This characteristic is preserved, even if the batteries are pre-processed, such as by shredding and lixiviation, as long as the Al and the oxidized metals retain their proximity.
  • metallic Al and oxidized metallic elements such as Co, Ni and Mn
  • the invented process results in the reduction of Ni and/or Co, which, together with the Cu that is most of the time also present in such charges, forms a metallic bullion.
  • This bullion can then be further processed according to known ways for the separation and recovery of the metals.
  • Mn is mostly sent to the slag.
  • Li is partially fumed and partially slagged. Li could be recovered from slag or fume using known processes, especially if the economic value of Li would rise further to its increased world consumption.
  • Al is generally present in its metallic form; C is typically present in the inorganic graphite anode, but also in the organic material in and around the cells.
  • Organic C participates to the reduction and to the enthalpy in a similar way as graphite, allowing the total amount of C to be considered for applying the formula.
  • oxidized form is meant not only oxides but also compounds wherein the metal is an electron donor.
  • metalurgical charge comprising a fraction of Li-ion batteries is meant a charge comprising the said relative amount of batteries, either as such, or after physical processing, such as after dismantling, shredding, and selection by floatation. It is however clear that the invented process is specially adapted for processing charges containing sealed cells, as only such cells are susceptible to explode violently when heated.
  • Batteryies may be actual cells, packs of cells, or assemblies.
  • a batch consisting of unprocessed Li batteries, fluxes and other raw materials containing valuable metals is fed in a bath smelting furnace.
  • the furnace consists of three zones, the gas zone, the slag zone and the alloy zone. Oxygen is injected in the slag zone.
  • the Li batteries are rapidly heated, detonate, and the residues react rapidly thanks to the good contact between reduction agents (such as the electrolyte, the plastics and the Al), and the oxides (such as LiCo0 2 ) in the batteries.
  • reduction agents such as the electrolyte, the plastics and the Al
  • oxides such as LiCo0 2
  • a freeze lining consists of solidified process material, in this case mostly slag. This freeze lining is self regenerating. Thus, as a part of the freeze lining is deteriorated by explosions, fresh layers are rapidly grown.
  • the Li-ion based charge shown in Table 1 is smelted according to the invention in a small furnace with a diameter of 1.5 m lined with chrome-magnesia bricks, the lining having a thickness of 300 mm.
  • HEV batteries and battery packs weighing up to 50 kg are dropped into the molten bath from a height of 8 m.
  • the furnace is operated in a mode allowing for freeze lining. Freeze lining is established by applying intensive cooling in of the slag zone, using water-cooled copper blocks according to known ways. Essentially no degradation of the refractory over time is observed.
  • This feed corresponds to an amount of batteries that is markedly higher than 40%. This means that freeze-lining is necessary to insure the economic viability of the furnace lining.
  • the weighted mean Al and C content of the Li-ion fraction can be calculated as respectively 9.4 and 32.3% by weight. According to the preferred formula, which is applicable when a relatively small furnace is used or when the furnace has high thermal losses, a minimum of 62.9% of Li-ion material is needed to sustain the autogenous combustion of the charge in this case.
  • the feed comprises 64.4% by weight of Li-ion material. This being slightly higher than the minimum required, the process indeed appears to be autogenous indeed.
  • a bath temperature of 1450 °C is obtained without additional cokes or gas.
  • 0 2 is blown through a submerged tuyere at a rate of 265 Nm3/h.
  • a furnace similar to the furnace of Example 1 is used in continuous service.
  • the degradation of the refractory can be partly attributed to chemical erosion and, mainly, to mechanical erosion due to the lumps of material scraping against the walls and to the impact of the exploding cells.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé de recyclage pour récupérer des métaux à partir de batteries HEV (de véhicules électriques hybrides) ou EV (de véhicules électriques). L'invention concerne plus particulièrement, un procédé pour récupérer Ni et/ou Co à partir de batteries de véhicules électriques ou de véhicules hybrides, consistant à : - utiliser un four à bain équipé de moyens d'injection de O2 ; - utiliser une charge métallique comprenant CaO en tant que moule de laitier , et les batteries Li-ion ; la fraction de batteries exprimée en pourcent en poids de la charge métallique est au moins égale à 40% ; - alimenter le four en charge métallurgique tout en injectant O2, au moins une partie de Ni et/ou de Co étant réduite et collectée en phase métallique ; et - séparer le laitier de la phase métallique par coulage. Le procédé est caractérisé en ce que le four à bain est équipé de moyens de garniture de refroidissement du laitier. Ce procédé présente des avantages sur le procédé de l'état de la technique, à savoir l'utilisation d'un four à cuve offrant une grande tolérance envers la morphologie de la charge, une efficacité énergétique élevée et des exigences de nettoyage de dégagement gazeux simplifiées.
PCT/EP2010/005841 2009-09-25 2010-09-24 Procédé de valorisation de métaux à partir de batteries hev ou ev Ceased WO2011035916A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP09012194.8 2009-09-25
EP09012194 2009-09-25
US27253009P 2009-10-05 2009-10-05
US61/272,530 2009-10-05

Publications (1)

Publication Number Publication Date
WO2011035916A1 true WO2011035916A1 (fr) 2011-03-31

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015096945A1 (fr) * 2013-12-23 2015-07-02 Umicore Procédé de recyclage de batteries li-ion
CN106756042A (zh) * 2016-12-19 2017-05-31 先进储能材料国家工程研究中心有限责任公司 一种废旧镍氢电池的回收处理工艺
CN106803607A (zh) * 2017-02-22 2017-06-06 兰州金川科力远电池有限公司 废旧镍氢电池的回收处理工艺
WO2019092951A1 (fr) * 2017-11-09 2019-05-16 株式会社Ｓｕｂａｒｕ Procédé d'élimination
CN110010993A (zh) * 2019-05-17 2019-07-12 清华大学 一种采用高铁炉渣原位吸附废弃锂电池中氟化物的方法
CN114761587A (zh) * 2019-11-27 2022-07-15 尤米科尔公司 用于回收镍、锰和钴的火法冶金方法
WO2023157397A1 (fr) * 2022-02-21 2023-08-24 住友金属鉱山株式会社 Procédé de production de métaux valorisables
WO2023162361A1 (fr) * 2022-02-22 2023-08-31 住友金属鉱山株式会社 Procédé de production de métaux valorisables
US12146205B2 (en) * 2016-10-21 2024-11-19 Umicore Process for recycling cobalt-bearing materials

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SU1629341A1 (ru) * 1988-08-25 1991-02-23 Институт проблем литья АН УССР Способ выплавки лигатуры
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EP1589121A1 (fr) 2004-04-19 2005-10-26 Umicore Recyclage d'une pile

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015096945A1 (fr) * 2013-12-23 2015-07-02 Umicore Procédé de recyclage de batteries li-ion
AU2014372796B2 (en) * 2013-12-23 2018-09-13 Umicore Process for recycling Li-ion batteries
US10164302B2 (en) 2013-12-23 2018-12-25 Umicore Process for recycling li-ion batteries
US12146205B2 (en) * 2016-10-21 2024-11-19 Umicore Process for recycling cobalt-bearing materials
CN106756042A (zh) * 2016-12-19 2017-05-31 先进储能材料国家工程研究中心有限责任公司 一种废旧镍氢电池的回收处理工艺
CN106803607A (zh) * 2017-02-22 2017-06-06 兰州金川科力远电池有限公司 废旧镍氢电池的回收处理工艺
CN106803607B (zh) * 2017-02-22 2019-02-12 兰州金川科力远电池有限公司 废旧镍氢电池的回收处理工艺
WO2019092951A1 (fr) * 2017-11-09 2019-05-16 株式会社Ｓｕｂａｒｕ Procédé d'élimination
CN110010993B (zh) * 2019-05-17 2021-03-09 清华大学 一种采用高铁炉渣原位吸附废弃锂电池中氟化物的方法
CN110010993A (zh) * 2019-05-17 2019-07-12 清华大学 一种采用高铁炉渣原位吸附废弃锂电池中氟化物的方法
CN114761587A (zh) * 2019-11-27 2022-07-15 尤米科尔公司 用于回收镍、锰和钴的火法冶金方法
CN114761587B (zh) * 2019-11-27 2023-11-28 尤米科尔公司 用于回收镍、锰和钴的火法冶金方法
WO2023157397A1 (fr) * 2022-02-21 2023-08-24 住友金属鉱山株式会社 Procédé de production de métaux valorisables
WO2023162361A1 (fr) * 2022-02-22 2023-08-31 住友金属鉱山株式会社 Procédé de production de métaux valorisables
JP2023122149A (ja) * 2022-02-22 2023-09-01 住友金属鉱山株式会社 有価金属の製造方法
JP7342989B2 (ja) 2022-02-22 2023-09-12 住友金属鉱山株式会社 有価金属の製造方法

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