WO2016141875A1 - 一种废旧电池的回收处理方法 - Google Patents

一种废旧电池的回收处理方法 Download PDF

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WO2016141875A1
WO2016141875A1 PCT/CN2016/075924 CN2016075924W WO2016141875A1 WO 2016141875 A1 WO2016141875 A1 WO 2016141875A1 CN 2016075924 W CN2016075924 W CN 2016075924W WO 2016141875 A1 WO2016141875 A1 WO 2016141875A1
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slag
content
battery
waste
recycling
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PCT/CN2016/075924
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English (en)
French (fr)
Inventor
肖松文
任国兴
潘炳
樊友奇
夏星
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长沙矿冶研究院有限责任公司
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=56879156&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2016141875(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from CN201510105916.8A external-priority patent/CN104789778B/zh
Priority claimed from CN201510105915.3A external-priority patent/CN104674013B/zh
Application filed by 长沙矿冶研究院有限责任公司 filed Critical 长沙矿冶研究院有限责任公司
Priority to EP16761102.9A priority Critical patent/EP3269832B2/en
Publication of WO2016141875A1 publication Critical patent/WO2016141875A1/zh

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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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry 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
    • 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
    • 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 relates to the technical field of resource recovery and environmental protection, in particular to a recycling and disposal method of a waste lithium ion battery and related materials.
  • Lithium-ion batteries have been widely used in portable digital devices such as mobile phones, MP3s, and cameras because of their high energy density, high operating voltage, and no memory effect. With the replacement of digital products, a large number of discarded aluminum-shell lithium-ion batteries have been produced. Lithium-ion batteries are rich in cobalt, nickel, and copper valuable metals, of which cobalt and nickel are as high as 10 wt.%. Improper handling of a large number of used lithium-ion batteries not only causes huge waste of resources, but also rich heavy metals and organic matter can cause serious environmental problems. Therefore, it is necessary to develop advanced recycling technology for used batteries.
  • the waste lithium ion battery has significant differences in composition and recovery value due to differences in its positive electrode and shell materials.
  • the steel shell lithium ion battery has a Fe content of 30%, an Al content of only about 5%, and an aluminum shell lithium ion battery with an Al content of up to 30%, and almost no Fe; at present, a portable battery uses a small battery with lithium cobaltate.
  • Lithium nickel cobaltate or nickel-cobalt-manganese/aluminum ternary cathode materials are mainly composed of high cobalt and nickel, low manganese content and high recovery value.
  • nickel-cobalt-manganese ternary cathode materials with high efficiency, large capacity ( ⁇ 150mAh/g), long life (>2000 times), and high safety are expected to be widely used. Further profoundly change the composition and recovery value of existing waste lithium-ion batteries. According to the survey, in 2013, the output of nickel-cobalt-manganese ternary materials was 23,000 tons, an increase of more than 50% compared with 2012. Therefore, the waste lithium ion battery recycling technology developed needs to adapt to changes in the composition of battery materials under the new situation.
  • waste lithium ion batteries mainly focuses on the recovery of valuable metals such as cobalt, nickel and copper.
  • the specific processes are wet and fire.
  • the wet process includes steps of disassembly, sorting, leaching, solution purification, metal extraction, etc.
  • the typical process is disclosed in U.S. Patent No. 5,888,463 and the like, which has the advantages of good product quality and controllable environmental effects, but the wet process
  • the treatment of specific constituent materials cannot adapt to the rapid changes of the battery components, and produces a large amount of waste water and unstable waste residue, which is likely to cause secondary pollution of the environment.
  • the waste battery or its dismantled material is subjected to high-temperature slag smelting treatment, and the valuable metals such as cobalt, nickel and copper are enriched in the gold and separated from the slag, and the alloy is further processed to recover the cobalt therein. , nickel, copper.
  • a typical process can be found in the U.S. Patent Publication No. US2005/0235775A1 and CN103526035A, CN103924088A, CN103370427A, CN103459623A, CN103380218A and CN103459624A.
  • the above-mentioned waste lithium ion battery fire smelting treatment process has the advantages of large raw material processing capacity, simple operation, stable slag structure and no secondary pollution.
  • the above processes are all proposed for the treatment of Mn-free lithium-ion batteries, and cannot solve the recycling process of a large number of waste lithium-ion batteries containing Mn.
  • the above processes all adopt the CaO-Al 2 O 3 -SiO 2 ternary system.
  • FeO-CaO-SiO 2 -Al 2 O 3 quaternary system and FeO-SiO 2 -Al 2 O 3 ternary slag type smelting the slag phase valuable metal content is extremely low, basically no reuse value, can only be used as The use of building materials, the economic benefits of the process need to be further improved.
  • the technical problem to be solved by the present invention is to overcome the deficiencies and defects mentioned in the above background art, and to provide a recycling and disposal method for a waste battery with higher comprehensive economic benefits and better environmental benefits.
  • the technical solution proposed by the present invention is a recycling processing method for a used battery, comprising the following steps:
  • the various materials prepared above are put into a melting furnace for melting, and the alloy containing Co and/or Ni, the Mn-containing slag and the soot are produced by melting; by controlling the oxygen partial pressure, the melting temperature and the melting time in the melting furnace Therefore, the Mn content in the Mn-containing slag produced by the smelting is ⁇ 15 wt.%, the Fe content ⁇ 5 wt.%, the Al 2 O 3 content ⁇ 30 wt.%; and 0.2 ⁇ Mn/SiO 2 ⁇ 3.0.
  • the first is a recycling process for used batteries containing Co and/or Ni, including the following steps:
  • the waste battery contains almost no Mn, for example, the Mn content is 3 wt.% or less, or even 1 wt.% or less
  • a slag forming agent is prepared, in the slag forming agent. Containing at least 10 wt.% of Mn and Si;
  • the various materials prepared above are put into a melting furnace for melting, and the alloy containing Co and/or Ni, the Mn-containing slag and the soot are produced by melting; by controlling the oxygen partial pressure, the melting temperature and the melting time in the melting furnace
  • the high-valence manganese oxide (such as manganese carbonate, MnO 2 , etc.) in the slag forming agent is converted into a low-value manganese oxide (such as MnO) which is easily leached by sulfuric acid in the Mn-containing slag, and the smelting output is contained.
  • Mn content in the Mn slag ⁇ 15wt.%, Fe content ⁇ 5wt.%, Al 2 O 3 content ⁇ 30wt.%; and 0.2 ⁇ Mn / SiO 2 ⁇ 3.0; that is, the slag is MnO-SiO 2 -Al 2 O 3 ternary smelting slag type, and the main components in the Mn containing slag are MnO, SiO 2 and Al 2 O 3 ; the majority (more than 90%) of Fe contained in the smelting material enters the Co and/or In the alloy of Ni.
  • the recycling treatment method of the above-mentioned Co-containing and/or Ni waste battery of the present invention is mainly based on the following idea: in the above-mentioned recycling treatment method of the Co-containing and/or Ni waste battery, we adopt MnO-SiO 2 -Al 2 O 3
  • the new smelting slag type of the elementary system this is not necessary in the slag forming material corresponding to the conventionally used CaO-SiO 2 -Al 2 O 3 slag type or FeO-SiO 2 -Al 2 O 3 slag type.
  • the slag composition of the present invention contains a large amount of Mn, and the existing smelting slag type contains almost no Mn or Mn content (Mn content ⁇ 10%, existing The slag is generally only used as a building material).
  • the new smelting slag type we used is mainly composed of MnO, SiO 2 and Al 2 O 3 . Since the battery itself has almost no Mn and Si, the added slag-forming agent is effective.
  • the slag element needs to contain Mn and Si, and in order to reduce the use amount of the slag-forming agent and improve the economical efficiency of the process, the added slag-forming agent must contain at least 10 wt.% of Mn and Si;
  • the slag has a high MnO content and a low Fe content, which is beneficial to the recovery and reuse of Mn in the subsequent slag, thereby achieving the reuse effect of the slag, improving its value, and further improving the economics of the process.
  • the technical solution is to mix the waste battery containing Co and/or Ni with the slagging agent containing Mn and Si, and it is preferable to put a small amount of metallurgical coke together into the melting furnace (preferably electric furnace) for melting;
  • the oxygen partial pressure is such that at least 90% of Co and/or Ni and at least 90% of Fe in the mixture enter the alloy, and almost all of the Si and most of the Mn enter the slag as oxides, and the high price in the raw materials
  • Manganese oxides such as MnO 2
  • low-value manganese oxides such as MnO
  • the control of the partial pressure of oxygen in the furnace is achieved by adjusting the amount of reducing agent (metallurgical coke or metal aluminum in the battery) and/or oxidant (oxygen or metal oxide) in the furnace material.
  • reducing agent metallic coke or metal aluminum in the battery
  • oxidant oxygen or metal oxide
  • a suitable partial pressure of oxygen may be such that the Mn content in the slag is ⁇ 15 wt.%, the Fe content is ⁇ 5 wt.%, the Al 2 O 3 content is ⁇ 30 wt.%; and 0.2 ⁇ Mn / SiO 2 ⁇ 3.0.
  • the waste battery containing Co and/or Ni includes a used battery such as a waste lithium ion battery or a used nickel hydrogen battery, but is preferably applied to waste lithium ions in the present invention.
  • the waste lithium ion battery refers to a discarded or failed lithium ion battery, a battery packaging material or other battery products, regardless of its mechanical or electrical integrity, which may specifically be one of Cu, Co, and Ni. Or waste materials produced in the manufacture of used lithium-ion batteries or lithium-ion batteries.
  • the spent lithium ion battery preferably comprises one or more of a waste aluminum shell lithium ion battery, a waste polymer lithium ion battery, and a waste steel shell lithium ion battery.
  • the present invention since the present invention only adds a slag-forming agent containing Mn and Si effective slag-forming elements, smelting-forming Mn-containing slag containing manganese olivine as a main component, and The Fe content in the Mn slag is low, and the Fe content is ⁇ 5%.
  • MnO 2 which cannot be leached by sulfuric acid in the slag forming agent is converted into MnO which is easily leached by sulfuric acid in the slag; on the other hand, more than 90% of Fe contained in the smelting material enters the alloy, and the output contains
  • the Fe content in the Mn slag is ⁇ 5%, which effectively reduces the burden of removing iron from the manganese leaching solution of the slag, and is beneficial to the recovery of manganese in the subsequent slag; in addition, when the Al 2 O 3 content in the slag is as high as 25%, the melting temperature exceeds 1400 ° C.
  • the fluidity of the slag is still very good, which shows that the invention is very suitable for treating waste lithium ion batteries with high aluminum content (for example, Al content ⁇ 5 wt.%), such as waste aluminum shell lithium ion batteries or Al content of 10 About 0.1% (for example, 8% to 15%) of waste polymer lithium-ion batteries, and when dealing with such waste batteries with high aluminum content, the slag can be effectively reduced due to the high solubility of Al 2 O 3 in the slag. Quantity, which in turn reduces the processing cost of the process.
  • waste lithium ion batteries with high aluminum content for example, Al content ⁇ 5 wt.%
  • the slag can be effectively reduced due to the high solubility of Al 2 O 3 in the slag. Quantity, which in turn reduces the processing cost of the process.
  • the Si-containing material if only the Si-containing material is added to the slag-forming agent, it is difficult to produce a manganese-rich slag having a high Mn content (Mn content ⁇ 25%) in one-step smelting.
  • Mn content ⁇ 25% Mn content
  • the effective slagging element in the slag forming agent contains both Mn and Si.
  • the slagging agent is not additionally added with Fe, but the slag forming agent generally inevitably contains a small amount of Fe.
  • the smelting process of the present invention employs a MnO-SiO 2 -Al 2 O 3 slag type, under the action of a slag reducing atmosphere
  • the Fe oxide in the material will be reduced to the metal iron into the alloy, and the Fe content in the slag can be controlled below 5%, which fully indicates that Fe is not the main component of the slag and does not affect the main properties of the slag.
  • increasing the content of the effective slag-forming element Si in the slag-forming agent can significantly reduce the amount of slag-forming agent and improve the economics of the process.
  • manganese ore is more preferably used as the slagging agent, and more preferably, the manganese ore has a Mn content of ⁇ 10% and an Fe content of 5% or more.
  • the Fe content is higher than 5%, and it is difficult for such manganese ore to recover manganese in a cost-effective manner.
  • the existing manganese ore smelting technology adopts a hydrometallurgical process.
  • the manganese in the manganese ore is converted into a manganese sulfate solution, and then the impurities are removed by purification and the manganese is recovered by an electrolytic process.
  • high-valence manganese such as MnO 2
  • the recovery rate of manganese ore direct leaching is not high.
  • the following two measures are generally used to increase the leaching rate of manganese ore: 1) adding a reducing agent such as pyrite, ferrous sulfate, etc.
  • the manganese leaching solution contains a large amount of Fe, and the subsequent leaching solution has a very heavy iron burden; 2) the high-valent manganese oxide is pre-reduced to a low-priced manganese oxide by a reduction roasting process, and then the sulfuric acid is leached, and the method requires equipment and energy.
  • the process control conditions are more complicated. For example, the roasting ore needs to be insulated from air and rapidly cooled to prevent secondary oxidation of manganese. However, in the present invention, such manganese ore is used as a slagging agent of the present process.
  • MnO 2 manganese oxide
  • metal aluminum in the battery is oxidized to Al 2 O 3 ; the transformed MnO and Al 2 O 3 are slag together with SiO 2 in the slagging agent to form MnO-SiO 2 -Al 2 O 3 slag.
  • the manganese content in the smelting slag can be significantly increased, reaching more than 25%, and the Fe content is significantly reduced, less than 3%, and the manganese content is high.
  • the slag with low iron content, in the subsequent hydrometallurgical extraction of manganese requires almost no iron removal process, and is therefore very suitable for subsequent manganese recovery. Therefore, this process not only recovers the valuable metals Co, Ni, and Cu in the used batteries, but also recovers the Mn in the refractory manganese ore, and its comprehensive economic and environmental benefits are more significant.
  • the slag has a Mn content of ⁇ 25 wt.% (more preferably more than 35 wt.%), a Fe content of ⁇ 3 wt.%, and 0.8 ⁇ Mn/SiO. 2 ⁇ 2.5; and the high-valence manganese oxide in the material is converted into low-priced manganese oxide MnO.
  • the quality requirement of the manganese-rich slag is reached in the country, and the existence form of Mn is easy to be leached and recovered by wet leaching, which provides favorable conditions for the subsequent recycling of manganese, which makes The comprehensive economic advantage of the process is more obvious, that is, the output slag and alloy are materials rich in valuable metals, both of which have high economic value, and at the same time recover and utilize manganese ore resources and used batteries.
  • the amount of the slag-forming agent added is Co-containing And / or Ni waste battery quality of more than 0.25 times, or even more than 0.4 times. Under the premise of ensuring the smooth progress of the smelting process, it is beneficial to further improve the economic benefits of the process by reducing the amount of slag-forming agent as much as possible.
  • the slag forming agent contains a certain amount of CaO to improve the foaming property of the slag, contribute to mass transfer and heat transfer of the melt, and improve the smelting effect (ie, The Mn-containing slag is MnO-SiO 2 -Al 2 O 3 -CaO quaternary smelting slag type), but excessive CaO promotes the reduction of Mn, which reduces the content of Mn in the slag, which is not conducive to the production of manganese-rich slag. Therefore, CaO in the slag is preferably controlled to a reasonable level.
  • the above slag has a CaO content ⁇ 15% and/or CaO/SiO 2 ⁇ 0.8, and more preferably, the slag has a CaO content ⁇ 10% and/or CaO/SiO 2 . ⁇ 0.5.
  • the CaO content is low.
  • the second method is a recycling method for Mn-containing used batteries, including the following steps:
  • the various materials prepared above are put into a melting furnace for melting, and the alloy containing Co and/or Ni, the Mn-containing slag and the soot are produced by melting; by controlling the oxygen partial pressure, the melting temperature and the melting time in the melting furnace , the Mn content in the Mn-containing slag produced by the smelting is ⁇ 15wt.%, the Fe content ⁇ 5wt.%, the Al 2 O 3 content ⁇ 30wt.%; and 0.2 ⁇ Mn/SiO 2 ⁇ 3.0; that is, the slag is MnO - SiO 2 -Al 2 O 3 ternary smelting slag type, and the main components in the Mn-containing slag are MnO, SiO 2 and Al 2 O 3 .
  • the above-mentioned recycling treatment method of the Mn-containing waste battery of the present invention is mainly based on the following ideas:
  • we adopt a new smelting slag type of MnO-SiO 2 -Al 2 O 3 ternary system Compared with the conventionally used CaO-SiO 2 -Al 2 O 3 slag type or FeO-SiO 2 -Al 2 O 3 slag type, the corresponding slag forming material of the present invention does not need to contain CaO, and does not need to contain Fe;
  • the slag composition of the present invention contains a large amount of Mn, and the existing smelting slag type contains almost no Mn or Mn content (Mn content ⁇ 10%, and the existing slag is generally only used as a building material).
  • the new smelting slag type we use is mainly composed of MnO, SiO 2 and Al 2 O 3 . Since the battery itself has almost no Si, the added slag-forming agent is effective for slag-forming elements. It is necessary to contain Si, and in order to reduce the use amount of the slag-forming agent and improve the economical efficiency of the process, the added slag-forming agent must contain at least 10 wt.% of Si; in addition, the slag produced by the smelting has a high MnO content.
  • the technical solution is to mix the Mn-containing waste battery with the Si-containing slag-forming agent, and preferably, a small amount of metallurgical coke is put into the smelting furnace (preferably an electric furnace) for melting; and the mixture is controlled by a suitable oxygen partial pressure in the furnace to make the mixture At least 90% of the Co and/or Ni and at least 90% of the Fe enters the alloy, while almost all of the Si and most of the Mn enter the slag as an oxide.
  • the control of the partial pressure of oxygen in the furnace is achieved by adjusting the amount of reducing agent (metallurgical coke or metal aluminum in the battery) and/or oxidant (oxygen or metal oxide) in the furnace material.
  • reducing agent metallic coke or metal aluminum in the battery
  • oxidant oxygen or metal oxide
  • a suitable partial pressure of oxygen may be such that the Mn content in the slag is ⁇ 15 wt.%, the Fe content is ⁇ 5 wt.%, the Al 2 O 3 content is ⁇ 30 wt.%, and 0.2 ⁇ Mn / SiO 2 ⁇ 3.0.
  • the Mn-containing used batteries include used lithium-ion batteries, used nickel-hydrogen batteries, and waste batteries including Mn dry batteries, but are preferably applied to used lithium ion batteries in the present invention.
  • the waste lithium ion battery refers to a discarded or failed lithium ion battery, a battery packaging material or other battery products, regardless of its mechanical or electrical integrity, which may specifically be one of Cu, Co, and Ni. Or waste materials produced in the manufacture of used lithium-ion batteries or lithium-ion batteries.
  • the spent lithium ion battery preferably comprises one or more of a waste aluminum shell lithium ion battery, a waste polymer lithium ion battery, and a waste steel shell lithium ion battery.
  • the Mn-containing waste battery is a waste lithium ion battery having a Mn content of 15 wt.% or more (may be about 20 wt.%), or a waste lithium ion battery having the above-mentioned waste lithium ion battery and a Mn content of 3 wt.% or less. the mix of.
  • the present invention since the present invention only adds the slag-forming agent containing the Si effective slag-forming element, the Mn-containing slag containing the manganite as the main component is smelted, and the Fe content in the Mn-containing slag is low. , Fe content ⁇ 5%.
  • Ion batteries such as waste aluminum-clad lithium-ion batteries or waste polymer lithium-ion batteries with an Al content of about 10% (for example, 8% to 15%), and when dealing with such high-capacity waste batteries, due to slag Al 2 O 3 has high dissolving ability, which can effectively reduce the amount of slag-forming agent used, thereby reducing the processing cost of the process.
  • the treated Mn-containing waste battery materials generally have a high Mn/Al value. If only the Si-containing materials are added to the slag-forming agent, it is difficult to melt one step. A manganese-rich slag having a high Mn content (Mn content ⁇ 35%) is produced. However, if the slag forming agent contains both Mn and Si, the total Mn/Al value in the smelting material can be lowered, thereby ensuring the production of manganese-rich slag containing Mn ⁇ 35%.
  • the effective slagging element in the slagging agent contains both Mn and Si. No additional Fe is added to the slag forming agent, but the slag forming agent generally inevitably contains a small amount of Fe. Since the smelting process of the present invention uses the MnO-SiO 2 -Al 2 O 3 slag type, the Fe content in the slag is controlled at 5%. Hereinafter, this fully indicates that Fe is not a main component of the slag and does not affect the main properties of the slag. In addition, increasing the content of the effective slag-forming element Si in the slag-forming agent can significantly reduce the amount of slag-forming agent and improve the economics of the process.
  • manganese ore is more preferably used as the slagging agent, and more preferably, the manganese ore has a Mn content of ⁇ 10% and an Fe content of 5% or more.
  • the Fe content is higher than 5%, and it is difficult for such manganese ore to recover manganese in a cost-effective manner.
  • the manganese ore is used as the slagging agent of the process.
  • the slag has a Mn content of ⁇ 25 wt.% (more preferably more than 35 wt.%), an Fe content of ⁇ 3 wt.%, and 0.8 ⁇ Mn/SiO 2 ⁇ 2.5.
  • the content of the material in the controlled slag reaches this range, the quality requirements of the state for manganese-rich slag are reached, which provides favorable conditions for the subsequent recycling of manganese, which makes the comprehensive economic advantage of the process more obvious, that is, output.
  • Both slag and alloys are materials rich in valuable metals, both of which have high economic value, and at the same time recover and utilize manganese ore resources and used batteries.
  • the slag-forming agent is added in an amount of 0.3 times or more, or even 0.5 times or more, the mass of the Mn-containing waste battery.
  • the slag-forming agent is added in an amount of 0.3 times or more, or even 0.5 times or more, the mass of the Mn-containing waste battery.
  • a certain amount of CaO in the slag-forming agent can improve the foaming performance of the slag, contribute to mass transfer and heat transfer of the melt, and improve the smelting effect (ie, the Mn-containing slag is MnO-SiO 2 -Al 2 O 3 -CaO quaternary smelting slag type), but excessive CaO promotes the reduction of Mn, which reduces the content of Mn in the slag, which is not conducive to the production of manganese-rich slag. Therefore, in the slag
  • the CaO is preferably controlled at a reasonable level.
  • the above slag has a CaO content ⁇ 15% and/or CaO/SiO 2 ⁇ 0.8, and more preferably, the slag has a CaO content ⁇ 10% and/or CaO/SiO 2 . ⁇ 0.5.
  • the CaO content is low.
  • the recycling treatment method of the invention has simple operation and high process efficiency, and is not only very suitable for large-scale treatment of waste batteries containing carbon and/or Ni and manganese ore, but also very suitable for treatment of waste batteries with high Mn content;
  • the recycling treatment method of the invention not only realizes the recycling and reuse of high-value Co and Ni in the used battery, but also solves the problem of recycling and reuse of Mn in the battery, and also solves the problem of recycling and recycling of the difficult-selected manganese ore.
  • the value of the invention in the circular economy is improved, and the comprehensive benefits are significant;
  • the refractory smelting manganese ore as a slag forming agent, the characteristics of the battery's self-reducing material (metal aluminum and carbon) are excessively utilized, and the high-valent manganese in the manganese ore is utilized.
  • the oxide is reduced to a low-cost MnO which can be dissolved by sulfuric acid; and the slag-forming agent manganese ore has a high content of Mn and SiO 2 .
  • Manganese oxide is used to adjust the atmosphere in the furnace; SiO 2 is used to adjust the slag properties, so that the slag has suitable smelting performance (low melting point, low viscosity, low Co, Ni and other valuable metal solubility), and smelting yields rich Manganese slag (Mn content ⁇ 25% or even ⁇ 35%, Fe content ⁇ 3%), the subsequent Mn resources can be recovered economically and efficiently, that is, smelting slag and alloy are valuable materials, and the value is high, which greatly improves The economic benefit of the invention.
  • the invention fully utilizes the characteristics and complementary advantages of each raw material, and achieves the unification of economic benefits and social benefits of smelting.
  • a recycling treatment method for a waste battery containing Co and/or Ni of the present invention comprises the following steps:
  • the waste battery containing Co and/or Ni used in this embodiment is a waste aluminum shell lithium ion battery containing Co and Ni (Cu 8 wt.%, Co 16 wt.%, Ni 2 wt.%, Al 33 wt.%, Fe 1 wt .%, Mn 0.1 wt.%, C 10 wt.%).
  • the slag forming agent in this embodiment is pyrolusite (Mn 33 wt.%, Fe 7 wt.%, SiO 2 33 wt.%, Al 2 O 3 3.5 wt.%, CaO 3.3 wt.%; Mn exists in the form of MnO 2 )
  • the effective slag-forming elements are Mn and Si, but the pyrolusite inevitably contains Fe.
  • the slag forming agent is used in an amount of 3.0 times that of the waste battery containing Co and/or Ni.
  • the various materials prepared above are put into an electric furnace for melting, and various materials smelted into the melting furnace also include separately added metallurgical coke, and the oxygen partial pressure in the electric furnace is controlled by adjusting the reducing agent in the furnace material and / or the amount of oxidant to achieve; by controlling the partial pressure of oxygen in the electric furnace, control the melting temperature of 1500 ° C, the melting time is 15 min, the slag and the alloy melt are completely separated, the high temperature alloy and slag are released from the alloy port and the slag outlet respectively An alloy containing Cu, Co, and Ni, a Mn-containing slag, and soot are obtained.
  • the recoveries of Co, Ni, Cu and Fe were 96.8%, 97.5%, 95.8% and 96.30%, respectively (more than 90% of Fe entered into the alloy containing Co and/or Ni);
  • the high-iron content pyrolusite (Fe content: 7 wt.%) is converted into a raw material suitable for hydrous metallurgical recovery of manganese - high manganese slag (very low iron content, only 2.3 wt.%), and The Mn in the slag exists in the form of MnO, which can be directly leached by sulfuric acid, and the comprehensive economic benefit of the process is remarkable.
  • a recycling treatment method for a waste battery containing Co and/or Ni of the present invention comprises the following steps:
  • the waste battery containing Co and/or Ni used in this embodiment consists of a waste steel shell lithium ion battery (Cu 8 wt.%, Co 7 wt.%, Ni 8 wt.%, Al 5 wt.%, Fe 35 wt.%, Mn 0.1). Wt.%, C 10wt.%) and waste aluminum shell lithium ion battery (Cu 8wt.%, Co 16wt.%, Ni 2wt.%, Al 35wt.%, Fe 1wt.%, Mn 0.1wt.%, C 10wt .%) mixed, of which, the waste aluminum shell lithium-ion battery accounted for 15%.
  • the slag-forming agent in this embodiment is only pyrolusite (Mn 38 wt.%, Fe 7 wt.%, SiO 2 33 wt.%, Al 2 O 3 3.5 wt.%, CaO 2.9 wt.%; Mn exists in the form of MnO 2
  • the effective slagging agent elements are Mn and Si, and the additional Fe is not a slagging element and does not affect the properties of the subsequent slag.
  • the slag forming agent is used in an amount of 0.55 times the mass of the waste battery containing Co and/or Ni (or the total battery material).
  • the various materials prepared above are put into an electric furnace for melting, and the partial pressure of oxygen in the electric furnace is controlled by adjusting the amount of reducing agent and/or oxidant in the furnace material; controlling the melting by controlling the partial pressure of oxygen in the electric furnace
  • the temperature is 1450 ° C
  • the melting time is 20 min
  • the slag and the alloy melt are completely separated, and the high-temperature alloy and the slag are discharged from the alloy port and the slag outlet respectively to obtain an alloy containing Cu, Co, Ni, Mn-containing slag and soot.
  • the recoveries of Co, Ni, Cu and Fe were 96.3%, 96.8%, 96.6% and 98.01%, respectively (more than 90% of Fe entered into the alloy containing Co and/or Ni);
  • the Mn content of the smelting slag is high, reaching 40.6%, and the Fe content is less than 3%, which meets the quality requirements of the state for the manganese-rich slag, that is, the slag and the alloy are valuable materials, and the value is high, comprehensive
  • the economic benefits have increased significantly.
  • a recycling treatment method for a waste battery containing Co and/or Ni of the present invention comprises the following steps:
  • the waste battery containing Co and/or Ni used in this embodiment consists of a waste polymer lithium ion battery (Cu 9 wt.%, Co 16 wt.%, Ni 0.1 wt.%, Al 15 wt.%, Fe 1 wt.%, Mn 0.1wt.%, C 29wt.%) and waste aluminum shell lithium ion battery (Cu 8wt.%, Co 16wt.%, Ni 2wt.%, Al 35wt.%, Fe 1wt.%, Mn 0.1wt.%, C 10wt.%) is mixed, wherein the waste polymer lithium ion battery accounts for 50%.
  • the slag forming agent in this embodiment is high iron manganese ore (Mn 31wt.%, Fe 27wt.%, SiO 2 35wt.%, Al 2 O 3 4.5wt.%, CaO 8.3wt.%), and lean manganese ore (Mn 16wt. %, Fe 11wt.%, SiO 2 18wt.%, Al 2 O 3 3.6wt.%, CaO 5.6wt.%; Mn in the form of MnCO 3 and MnO 2 ) and a mixture of silica (SiO 2 98wt.%), Among them, high-iron manganese ore accounts for 55%, lean manganese ore accounts for 35%, and silica accounts for 10%.
  • the effective slagging agent elements are Mn and Si, but the additional Fe is not a slagging element and does not affect the properties of the subsequent slag.
  • the slagging agent is used in an amount of 2.6 times the mass of the waste battery (or total battery material) containing Co and/or Ni.
  • the various materials prepared above are put into an electric furnace for melting, and the partial pressure of oxygen in the electric furnace is controlled by adjusting the amount of reducing agent and/or oxidant in the furnace material; controlling the melting by controlling the partial pressure of oxygen in the electric furnace
  • the temperature is 1425 ° C
  • the melting time is 30 min
  • the slag and the alloy melt are completely separated, and the high-temperature alloy and the slag are respectively discharged from the alloy port and the slag outlet to obtain an alloy containing Cu, Co, Ni, containing Mn slag and soot.
  • the recoveries of Co, Ni, Cu and Fe were 96.9%, 97.5%, 97.2% and 98.02%, respectively (more than 90% of Fe entered into the alloy containing Co and/or Ni);
  • the Mn content of the smelting slag is high, reaching 32.15%, and the Fe content is less than 3%, which meets the quality requirements of the state for the manganese-rich slag, that is, the slag and the alloy are valuable materials, and the value is high, comprehensive
  • the economic benefits have increased significantly.
  • a recycling treatment method for a Mn-containing waste battery of the present invention comprises the following steps:
  • the Mn-containing waste battery used in this embodiment is composed of a Mn-containing waste polymer lithium ion battery (Cu 9 wt.%, Co 5 wt.%, Ni 1 wt.%, Al 15 wt.%, Fe 1 wt.%, Mn 22 wt.%). , C 19wt.%) and almost no Mn waste steel shell lithium ion battery (Cu 8wt.%, Co 15wt.%, Ni 2wt.%, Al 5wt.%, Fe 30wt.%, Mn 0.2wt.%, C 11wt.%) is mixed, of which lithium-ion batteries containing Mn waste polymer account for 70%.
  • the slag forming agent in this embodiment consists of copper smelting slag (Cu 0.8 wt.%, Fe 36.9 wt.%, SiO 2 34.5 wt.%, Al 2 O 3 4.5 wt.%, CaO 8.5 wt.%) and silica ( SiO 2 98wt.%) is mixed, in which copper slag accounts for 57% and silica accounts for 43%.
  • the effective slag-forming element is only Si, but copper smelting slag inevitably contains Fe.
  • the amount of the slag forming agent is 0.4 times the mass of the Mn-containing waste battery (or the total battery material).
  • the various materials prepared above are put into an electric furnace for melting, and various materials smelted into the melting furnace also include separately added metallurgical coke, and the oxygen partial pressure in the electric furnace is controlled by adjusting the reducing agent in the furnace material and / or the amount of oxidant to achieve; by controlling the partial pressure of oxygen in the electric furnace, control the melting temperature of 1500 ° C, the melting time is 15 min, the slag and the alloy melt are completely separated, the high temperature alloy and slag are released from the alloy port and the slag outlet respectively An alloy containing Cu, Co, and Ni, a Mn-containing slag, and soot are obtained.
  • the recoveries of Co, Ni, Cu and Fe were 97.5%, 97.9%, 95.5% and 95.60%, respectively;
  • the amount of the slag-forming agent is only 0.4 times that of the Mn-containing waste battery, which is far lower than the consumption of the slag-forming agent in the prior art; the Cu content in the slag is only 0.50%, and the battery and copper are recovered at the same time.
  • the copper in the smelting slag has significant economic benefits.
  • a recycling treatment method for a Mn-containing waste battery of the present invention comprises the following steps:
  • the Mn-containing waste battery used in this embodiment is composed of a Mn-containing waste polymer lithium ion battery (Cu 9 wt.%, Co 5 wt.%, Ni 1 wt.%, Al 15 wt.%, Fe 1 wt.%, Mn 22 wt.%). , C 19wt.%) and waste aluminum shell lithium ion battery with almost no Mn (Cu 8wt.%, Co 16wt.%, Ni 2wt.%, Al 35wt.%, Fe 1wt.%, Mn 0.1wt.%, C 10wt.%) is mixed, wherein the lithium-containing battery containing Mn waste polymer accounts for 50%.
  • the slag forming agent in this embodiment is only manganese ore (Mn 33wt.%, Fe 7wt.%, SiO 2 33wt.%, Al 2 O 3 3.5wt.%, CaO 2.9wt.%), and its effective slagging agent element It is Mn and Si, but the additional Fe is not a slagging element and does not affect the properties of the subsequent slag.
  • the amount of the slag forming agent is twice the mass of the Mn-containing waste battery (or the total battery material).
  • the various materials prepared above are put into an electric furnace for melting, and the partial pressure of oxygen in the electric furnace is controlled by adjusting the amount of reducing agent and/or oxidant in the furnace material; controlling the melting by controlling the partial pressure of oxygen in the electric furnace
  • the temperature is 1450 ° C
  • the melting time is 20 min
  • the slag and the alloy melt are completely separated, and the high-temperature alloy and the slag are discharged from the alloy port and the slag outlet respectively to obtain an alloy containing Cu, Co, Ni, Mn-containing slag and soot.
  • the recoveries of Co, Ni, Cu and Fe were 96.5%, 97.8%, 95.1% and 96.08%, respectively;
  • the Mn content of the smelting slag is high, reaching 39.2%, and the Fe content is less than 3%, which meets the quality requirements of the state for the manganese-rich slag, that is, the slag and the alloy are valuable materials, and the value is high, comprehensive
  • the economic benefits have increased significantly.
  • a recycling treatment method for a Mn-containing waste battery of the present invention comprises the following steps:
  • the Mn-containing waste battery used in this embodiment is composed of a Mn-containing waste polymer lithium ion battery (Cu 9 wt.%, Co 5 wt.%, Ni 1 wt.%, Al 15 wt.%, Fe 1 wt.%, Mn 22 wt.%). , C 19wt.%) and waste aluminum shell lithium ion battery with almost no Mn (Cu 8wt.%, Co 16wt.%, Ni 2wt.%, Al 35wt.%, Fe 1wt.%, Mn 0.1wt.%, C 10wt.%) is mixed, wherein the Mn-containing waste polymer lithium ion battery material accounts for 50%.
  • the slag-forming agent in this embodiment is pyrolusite (Mn 33wt.%, Fe 7wt.%, SiO 2 33wt.%, Al 2 O 3 3.5wt.%, CaO 3.3wt.%), and lean manganese ore (Mn 16wt.
  • the amount of the slag forming agent is 2.6 times that of the Mn-containing waste battery (or the total battery material).
  • the various materials prepared above are put into an electric furnace for melting, and the partial pressure of oxygen in the electric furnace is controlled by adjusting the amount of reducing agent and/or oxidant in the furnace material; controlling the melting by controlling the partial pressure of oxygen in the electric furnace
  • the temperature is 1425 ° C
  • the melting time is 30 min
  • the slag and the alloy melt are completely separated, and the high-temperature alloy and the slag are respectively discharged from the alloy port and the slag outlet to obtain an alloy containing Cu, Co, Ni, containing Mn slag and soot.
  • the recoveries of Co, Ni, Cu and Fe were 97.3%, 98.3%, 96.2% and 96.68%, respectively;
  • the Mn content of the smelting slag is high, reaching 38.25%, and the Fe content is less than 3%, which meets the quality requirements of the state for the manganese-rich slag, that is, the slag and the alloy are valuable materials, and the value is high, comprehensive
  • the economic benefits have increased significantly.

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Abstract

一种废旧电池的回收处理方法，包括以下步骤：（1）准备废旧电池，另外准备造渣剂，造渣剂中至少含10wt.%的Si和/或Mn；（2）将准备的各种物料投入到熔炼炉中熔炼，熔炼产出含Co和/或Ni的合金、含Mn炉渣及烟尘；通过控制熔炼炉内的氧分压、熔炼温度和熔炼时间，使得熔炼产出的含Mn炉渣中Mn含量≥15wt.%、Fe含量≤5wt.%、Al2O3含量≤30wt.%；且0.2≤Mn/SiO2≤3.0。

Description

一种废旧电池的回收处理方法 技术领域
本发明涉及资源回收与环境保护技术领域，尤其涉及一种废旧锂离子电池及相关材料的回收处理方法。
背景技术
锂离子电池因其能量密度高、工作电压高、无记忆效应等优点，目前已广泛应用于手机、MP3、相机等便携数码设备中。随着数码产品的更新换代，随之产生大量的废旧铝壳锂离子电池。锂离子电池富含钴、镍、铜有价金属，其中钴、镍含量高达10wt.％。大量废旧锂离子电池的不当处理，不仅造成资源的巨大浪费，而且富含的重金属及有机物也会造成严重的环境问题。因此，开发先进的废旧电池回收再利用技术十分必要。
另外，废旧锂离子电池因其正极及壳体材料差异，组成成分及回收价值差异显著。如钢壳锂离子电池Fe含量达到30％，Al含量仅有5％左右；而铝壳锂离子电池Al含量高达30％，而几乎无Fe；目前，便携数码设备采用的小型电池以钴酸锂、镍钴酸锂或镍钴锰/铝三元正极材料为主，其钴、镍含量高，锰含量低，回收价值高。但是，随着电动汽车产业的发展，具有高效率、大容量(≥150mAh/g)、长寿命(>2000次)、安全性高等特点的镍钴锰三元系正极材料必将得到广泛应用，进而深刻改变现有废旧锂离子电池成分构成及回收价值。调查显示，2013年镍钴锰酸锂三元材料产量2.3万吨，较2012年增长达50％以上。因此，开发的废旧锂离子电池回收再利用技术需适应新形势下电池材料组成成分的变化。
目前，废旧锂离子电池回收处理技术主要着眼于钴、镍、铜等有价金属的回收，具体工艺有湿法和火法两类。湿法工艺包括拆解、分选、浸出、溶液净化、金属提取等步骤，典型工艺在US5888463号等美国专利文献中有公开，其优点是产品质量好、环境影响可控，但湿法处理工艺普遍针对特定组成物料的处理，无法适应电池成分的急剧变化，并且产出大量废水和不稳定废渣，极易造成环境的二次污染。火法工艺则是将废旧电池或其拆解物料进行高温造渣熔炼处理，将其中的钴、镍、铜等有价金属富集合金中，并与炉渣分离，合金则进一步处理回收其中的钴、镍、铜。目前，典型的工艺可参见公开号为US2005/0235775A1的美国专利文献以及CN103526035A、CN103924088A、CN103370427A、CN103459623A、CN103380218A和CN103459624A号中国专利文献。上述废旧锂离子电池火法熔炼处理工艺，均具有原料处理能力大、操作较简单、产出炉渣结构稳定且无二次污染等优势。
然而，上述工艺均是针对无Mn废旧锂离子电池提出的处理工艺，无法解决大量含Mn 的废旧锂离子电池的回收处理，此外，上述工艺均采用CaO-Al2O3-SiO2三元系、FeO-CaO-SiO2-Al2O3四元系和FeO-SiO2-Al2O3三元系渣型熔炼，炉渣相有价金属含量极低，基本无再利用价值，仅可作为建筑材料使用，工艺的经济效益有待进一步提高。
发明内容
本发明所要解决的技术问题是，克服以上背景技术中提到的不足和缺陷，提供一种综合经济效益更高、环境效益更好的废旧电池的回收处理方法。
为解决上述技术问题，本发明提出的技术方案为一种废旧电池的回收处理方法，包括以下步骤：
(1)准备废旧电池，另外准备造渣剂，所述造渣剂中至少含10wt.％的Si和/或Mn；
(2)将上述准备的各种物料投入到熔炼炉中熔炼，熔炼产出含Co和/或Ni的合金、含Mn炉渣及烟尘；通过控制熔炼炉内的氧分压、熔炼温度和熔炼时间，使得熔炼产出的含Mn炉渣中Mn含量≥15wt.％、Fe含量≤5wt.％、Al2O3含量≤30wt.％；且0.2≤Mn/SiO2≤3.0。
作为进一步的改进，我们根据废旧电池种类及所含元素成分的不同，又将上述废旧电池的回收处理方法具体改进为以下两种。
第一种是含Co和/或Ni废旧电池的回收处理方法，包括以下步骤：
(1)准备含Co和/或Ni废旧电池(该废旧电池中几乎不含Mn，例如Mn含量在3wt.％以下，甚至1wt.％以下)，另外准备造渣剂，所述造渣剂中至少含10wt.％的Mn和Si；
(2)将上述准备的各种物料投入到熔炼炉中熔炼，熔炼产出含Co和/或Ni的合金、含Mn炉渣及烟尘；通过控制熔炼炉内的氧分压、熔炼温度和熔炼时间，将所述造渣剂中的高价态锰氧化物(如碳酸锰、MnO2等)转化成含Mn炉渣中易被硫酸浸出的低价态锰氧化物(如MnO)，熔炼产出的含Mn炉渣中Mn含量≥15wt.％、Fe含量≤5wt.％、Al2O3含量≤30wt.％；且0.2≤Mn/SiO2≤3.0；即所述炉渣为MnO-SiO2-Al2O3三元系冶炼渣型，且含Mn炉渣中的主要成分为MnO、SiO2和Al2O3；熔炼物料中所含有的绝大部分(90％以上)Fe进入所述含Co和/或Ni的合金中。
本发明的上述含Co和/或Ni废旧电池的回收处理方法主要基于以下思路：上述的含Co和/或Ni废旧电池的回收处理方法中，我们采用了MnO-SiO2-Al2O3三元系新的冶炼渣型；这相比现有常规采用的CaO-SiO2-Al2O3渣型或FeO-SiO2-Al2O3渣型，本发明对应的造渣剂物料中不必含有CaO，也不必含有Fe；更重要的是，本发明的炉渣组成中含有大量的Mn，而现有的冶炼渣型中几乎不含Mn或Mn含量很低(Mn含量≤10％，现有的炉渣一般仅能作建筑材料使用)。基于我们最新的研究成果，我们采用的这种新冶炼渣型中，炉渣的主要成分为MnO、SiO2和Al2O3，由于电池自身几乎无Mn和Si，因此添加的造渣剂有效造渣元素需含 有Mn和Si，并且，为了降低造渣剂的使用量，提高工艺的经济性，所述的添加的造渣剂中必须至少含10wt.％的Mn和Si；另外，熔炼产出的炉渣中MnO含量高，且Fe含量低，这有利于后续炉渣中Mn的回收再利用，达到炉渣的再次利用效果，提高了其价值，使工艺的经济性进一步提高。这种技术方案是将含Co和/或Ni废旧电池与含Mn和Si的造渣剂混合，可优选将少量冶金焦碳一同投入到熔炼炉(优选电炉)中熔炼；通过控制炉内合适的氧分压，使得混合物料中至少90％的Co和/或Ni及至少90％的Fe进入合金中，而几乎全部的Si和大部分的Mn以氧化物形式进入炉渣，并且将原料中的高价态锰氧化物(如MnO2)转化为低价态锰氧化物(如MnO)。炉内氧分压的控制是通过调整入炉物料中还原剂(冶金焦碳或电池中金属铝)和/或氧化剂(氧气或金属氧化物)的量来实现。通过分析熔炼产出合金及炉渣的成分，可以确定合适的氧分压。合适的氧分压可使得炉渣中Mn含量≥15wt.％、Fe含量≤5wt.％、Al2O3含量≤30wt.％；且0.2≤Mn/SiO2≤3.0。
上述的含Co和/或Ni废旧电池的回收处理方法中，所述含Co和/或Ni废旧电池包含废旧锂离子电池、废旧镍氢电池等废旧电池，但本发明中优选适用于废旧锂离子电池。该废旧锂离子电池指的是丢弃的或失效的锂离子电池、电池包装材料或其它电池产品，而不考虑其机械的或电能的完整性，其具体可以是含Cu、Co、Ni中一种或几种的废旧锂离子电池或锂离子电池生产制造中产生的废料。所述废旧锂离子电池优选包含废旧铝壳锂离子电池、废旧聚合物锂离子电池和废旧钢壳锂离子电池中的一种或几种。
在上述的含Co和/或Ni废旧电池的回收处理方法中，由于本发明仅添加含Mn和Si有效造渣元素的造渣剂，熔炼形成锰橄榄石为主要成分的含Mn炉渣，并且含Mn炉渣中Fe含量低，Fe含量≤5％。通过熔炼过程，一方面将造渣剂中不能被硫酸浸出的MnO2转化成炉渣中易被硫酸浸出的MnO；另一方面，熔炼物料中所含有的Fe 90％以上进入合金中，产出含Mn炉渣中Fe含量≤5％，有效降低炉渣的锰浸出液净化除铁负担，有利于后续炉渣中锰的回收；此外，当炉渣中Al2O3含量高达25％时，在熔炼温度超过1400℃条件下，炉渣的流动性依然非常好，这说明，本发明非常适合于处理铝含量高(例如Al含量≥5wt.％)的废旧锂离子电池，如废旧铝壳锂离子电池或Al含量在10％左右(例如8％～15％)的废旧聚合物锂离子电池，而且在处理这类铝含量高的废旧电池时，由于炉渣的Al2O3溶解能力高，可有效降低造渣剂的使用量，进而降低工艺的处理成本。
上述的含Co和/或Ni废旧电池的回收处理方法中，若造渣剂中仅添加含Si物料，一步熔炼难以产出Mn含量高(Mn含量≥25％)的富锰渣。但是，若造渣剂中同时含有Mn和Si，则可更容易熔炼产出Mn含量高的富锰渣。所以，所述造渣剂中的有效造渣元素同时包含Mn和Si。所述造渣剂中不额外添加Fe，但造渣剂一般不可避免的含有少量Fe，由于本发明的熔 炼工艺采用MnO-SiO2-Al2O3渣型，在炉渣还原性气氛的作用下，物料中的Fe氧化物将被还原至金属铁进入合金中，炉渣中Fe含量可控制在5％以下，这充分表明Fe不是炉渣的主体成分，不影响炉渣的主要性质。此外，提高造渣剂中有效造渣元素Si的含量，可显著降低造渣剂的用量，提高工艺的经济性。
上述的含Co和/或Ni废旧电池的回收处理方法中，更优选采用锰矿作为造渣剂，进一步优选的所述锰矿中Mn含量≥10％、Fe含量在5％以上。一般锰矿中，与Mn含量相比，Fe含量较高，大于5％以上，这种锰矿石难以经济有效地回收其中的锰。现有的锰矿冶炼技术均采用湿法冶金工艺，具体在硫酸体系下，将锰矿中的锰转化为硫酸锰溶液，然后经净化除杂，电解工艺回收锰。但是，由于锰矿中的高价态锰(如MnO2)不溶于硫酸，所以锰矿直接浸出回收率不高。为此，一般采用以下两种措施提高锰矿的浸出率：1)向硫酸体系加入还原剂，如黄铁矿、硫酸亚铁等，将其转化为低价态锰(Mn2+)，但是该方法锰浸出液中含有大量的Fe，后续浸出液除铁负担非常重；2)采用还原焙烧工艺，将高价锰氧化物预先还原至低价锰氧化物，再硫酸浸出，而该方法除需设备、能源外，工艺控制条件较复杂，如，焙烧矿需隔绝空气和快速冷却，以防止锰的二次氧化。然而，本发明中将这种锰矿作为本工艺的造渣剂，在熔炼过程中，一方面，锰矿中的高价锰氧化物(MnO2)被电池中的碳和金属铝还原至可被硫酸溶解的MnO；另一方面，电池中的金属铝被氧化为Al2O3；经转化形成的MnO和Al2O3，与造渣剂中的SiO2一起造渣，形成MnO-SiO2-Al2O3炉渣。此外，锰矿中至少90％Fe被还原，进入合金相中，使得熔炼产出炉渣中锰含量可显著提高，达到25％以上，并且Fe含量显著降低，低于3％，这种锰含量高、铁含量低的炉渣，在后续湿法冶金提取锰的工艺中，几乎无需除铁工序，因此，非常适合后续锰的回收。因此，这种工艺不仅回收了废旧电池中的有价金属Co、Ni、Cu，还回收了难选冶锰矿中的Mn，其综合经济与环境效益更加显著。虽然锰矿作为造渣剂，会带入较高含量的Fe，但是这与造渣剂中不额外添加Fe不冲突，因为，锰矿中的Fe几乎全部进入合金，产出炉渣Fe含量甚至可低于3％，这也再次表明Fe不作为造渣剂使用，不影响炉渣的主要性质。
上述的含Co和/或Ni废旧电池的回收处理方法，优选的：所述炉渣中Mn含量≥25wt.％(更优选大于35wt.％)、Fe含量≤3wt.％；且0.8≤Mn/SiO2≤2.5；且物料中的高价态锰氧化物均转化为低价态锰氧化物MnO。当控制炉渣中的物料成分含量达到此范围时，达到国家对富锰渣的质量要求，且Mn的存在形态易于湿法浸出回收锰，这便为后续锰的回收利用提供了有利条件，这使得该工艺的综合经济优势更加明显，即产出炉渣和合金均为富含有价金属的物料，两者经济价值均很高，且同时回收和利用了锰矿资源和废旧电池。
上述的含Co和/或Ni废旧电池的回收处理方法，优选的：所述造渣剂的添加量为含Co 和/或Ni废旧电池质量的0.25倍以上，甚至可在0.4倍以上。在保证熔炼过程顺利进行的前提下，尽可能降低造渣剂的添加量，有利于进一步提高工艺的经济效益。
上述的含Co和/或Ni废旧电池的回收处理方法中，造渣剂中含有一定量的CaO可以改善炉渣的起泡性能，有助于熔体的传质和传热，改善冶炼效果(即含Mn炉渣为MnO-SiO2-Al2O3-CaO四元系冶炼渣型)，但是过多的CaO会促进Mn的还原，使得渣中Mn的含量降低，不利于产出富锰渣，因此，炉渣中的CaO优选控制在合理的水平。根据我们的反复研究和实验，优选的，上述炉渣中CaO含量≤15％和/或CaO/SiO2≤0.8，更优选的，所述炉渣中，CaO含量≤10％和/或CaO/SiO2≤0.5。此时相当于是采用了MnO-SiO2-Al2O3-CaO四元系的冶炼渣型，但CaO含量较低。
第二种是含Mn废旧电池的回收处理方法，包括以下步骤：
(1)准备含Mn废旧电池，另外准备造渣剂，所述造渣剂中至少含10wt.％的Si；
(2)将上述准备的各种物料投入到熔炼炉中熔炼，熔炼产出含Co和/或Ni的合金、含Mn炉渣及烟尘；通过控制熔炼炉内的氧分压、熔炼温度和熔炼时间，使得熔炼产出的含Mn炉渣中Mn含量≥15wt.％、Fe含量≤5wt.％、Al2O3含量≤30wt.％；且0.2≤Mn/SiO2≤3.0；即所述炉渣为MnO-SiO2-Al2O3三元系冶炼渣型，且含Mn炉渣中的主要成分为MnO、SiO2和Al2O3。
本发明的上述含Mn废旧电池的回收处理方法主要基于以下思路：上述的含Mn废旧电池的回收处理方法中，我们采用了MnO-SiO2-Al2O3三元系新的冶炼渣型；这相比现有常规采用的CaO-SiO2-Al2O3渣型或FeO-SiO2-Al2O3渣型，本发明对应的造渣剂物料中不必含有CaO，也不必含有Fe；更重要的是，本发明的炉渣组成中含有大量的Mn，而现有的冶炼渣型中几乎不含Mn或Mn含量很低(Mn含量≤10％，现有的炉渣一般仅能作建筑材料使用)。基于我们最新的研究成果，我们采用的这种新冶炼渣型中，炉渣的主要成分为MnO、SiO2和Al2O3，由于电池自身几乎无Si，因此添加的造渣剂有效造渣元素需含有Si，并且，为了降低造渣剂的使用量，提高工艺的经济性，所述的添加的造渣剂中必须至少含10wt.％的Si；另外，熔炼产出的炉渣中MnO含量高，且Fe含量低，这有利于后续炉渣中Mn的回收再利用，达到炉渣的再次利用效果，提高了其价值，使工艺的经济性进一步提高。这种技术方案是将含Mn废旧电池与含Si的造渣剂混合，可优选将少量冶金焦碳一同投入到熔炼炉(优选电炉)中熔炼；通过控制炉内合适的氧分压，使得混合物料中至少90％的Co和/或Ni及至少90％的Fe进入合金中，而几乎全部的Si和大部分的Mn以氧化物形式进入炉渣。炉内氧分压的控制是通过调整入炉物料中还原剂(冶金焦碳或电池中金属铝)和/或氧化剂(氧气或金属氧化物)的量来实现。通过分析熔炼产出合金及炉渣的成分，可以确定合适的氧分压。合适的氧分压 可使得炉渣中Mn含量≥15wt.％、Fe含量≤5wt.％、Al2O3含量≤30wt.％；且0.2≤Mn/SiO2≤3.0。
上述的含Mn废旧电池的回收处理方法中，所述含Mn废旧电池包含废旧锂离子电池、废旧镍氢电池、含Mn干电池等废旧电池，但本发明中优选适用于废旧锂离子电池。该废旧锂离子电池指的是丢弃的或失效的锂离子电池、电池包装材料或其它电池产品，而不考虑其机械的或电能的完整性，其具体可以是含Cu、Co、Ni中一种或几种的废旧锂离子电池或锂离子电池生产制造中产生的废料。所述废旧锂离子电池优选包含废旧铝壳锂离子电池、废旧聚合物锂离子电池和废旧钢壳锂离子电池中的一种或几种。更优选的：所述含Mn废旧电池为Mn含量15wt.％以上(可以为20wt.％左右)的废旧锂离子电池、或者为前述废旧锂离子电池与Mn含量3wt.％以下的废旧锂离子电池的混合。
在上述的含Mn废旧电池的回收处理方法中，由于本发明仅添加含Si有效造渣元素的造渣剂，熔炼形成锰橄榄石为主要成分的含Mn炉渣，并且含Mn炉渣中Fe含量低，Fe含量≤5％。一方面，熔炼过程中，熔炼物料中所含有的Fe 90％以上进入合金中，产出含Mn炉渣中Fe含量≤5％，有利于后续炉渣中锰的回收；另一方面，当炉渣中Al2O3含量高达25％时，在熔炼温度超过1400℃条件下，炉渣的流动性依然非常好，这说明，本发明非常适合于处理铝含量高(例如Al含量≥5wt.％)的废旧锂离子电池，如废旧铝壳锂离子电池或Al含量在10％左右(例如8％～15％)的废旧聚合物锂离子电池，而且在处理这类铝含量高的废旧电池时，由于炉渣的Al2O3溶解能力高，可有效降低造渣剂的使用量，进而降低工艺的处理成本。
上述的含Mn废旧电池的回收处理方法中，基于我们最新的研究成果发现，所处理的含Mn废旧电池材料一般自身Mn/Al值较高，若造渣剂中仅添加含Si物料，一步熔炼难以产出Mn含量高(Mn含量≥35％)的富锰渣。但是，若造渣剂中同时含有Mn和Si，则可降低熔炼物料中总的Mn/Al值，进而能保证熔炼产出含Mn≥35％的富锰渣。所以，优选的：所述造渣剂中的有效造渣元素同时包含Mn和Si。所述造渣剂中不额外添加Fe，但造渣剂一般不可避免的含有少量Fe，由于本发明的熔炼工艺采用MnO-SiO2-Al2O3渣型，炉渣中Fe含量控制在5％以下，这充分表明Fe不是炉渣的主体成分，不影响炉渣的主要性质。此外，提高造渣剂中有效造渣元素Si的含量，可显著降低造渣剂的用量，提高工艺的经济性。
上述的含Mn废旧电池的回收处理方法中，更优选采用锰矿作为造渣剂，进一步优选的所述锰矿中Mn含量≥10％、Fe含量在5％以上。一般锰矿中，与Mn含量相比，Fe含量较高，大于5％以上，这种锰矿石难以经济有效地回收其中的锰。而将这种锰矿作为本工艺的造渣剂，在熔炼过程中，锰矿中至少90％Fe被还原，进入合金相中，使得熔炼产出炉渣中锰含量可显著提高，达到35％以上，并且Fe含量显著降低，低于3％，这种锰含量高、铁含量低 的炉渣，在后续湿法冶金提取锰的工艺中，几乎无需除铁工序，因此，非常适合后续锰的回收。因此，这种工艺不仅回收了废旧电池中的有价金属Co、Ni、Cu，还回收了电池中的Mn和难选冶锰矿中的Mn，其综合经济与环境效益更加显著。此外，值得一提的是，虽然锰矿作为造渣剂，会带入较高含量的Fe，但是，这与造渣剂中不额外添加Fe不冲突，因为，锰矿中的Fe几乎全部进入合金，产出炉渣Fe含量甚至可低于3％，这也表明Fe不作为造渣剂使用，不影响炉渣的主要性质。
上述的含Mn废旧电池的回收处理方法，优选的：所述炉渣中Mn含量≥25wt.％(更优选大于35wt.％)、Fe含量≤3wt.％；且0.8≤Mn/SiO2≤2.5。当控制炉渣中的物料成分含量达到此范围时，达到国家对富锰渣的质量要求，这便为后续锰的回收利用提供了有利条件，这使得该工艺的综合经济优势更加明显，即产出炉渣和合金均为富含有价金属的物料，两者经济价值均很高，且同时回收和利用了锰矿资源和废旧电池。
上述的含Mn废旧电池的回收处理方法，优选的：所述造渣剂的添加量为含Mn废旧电池质量的0.3倍以上，甚至可在0.5倍以上。在保证熔炼过程顺利进行的前提下，尽可能降低造渣剂的添加量，有利于进一步提高工艺的经济效益。
上述的含Mn废旧电池的回收处理方法中，造渣剂中含有一定量的CaO可以改善炉渣的起泡性能，有助于熔体的传质和传热，改善冶炼效果(即含Mn炉渣为MnO-SiO2-Al2O3-CaO四元系冶炼渣型)，但是过多的CaO会促进Mn的还原，使得渣中Mn的含量降低，不利于产出富锰渣，因此，炉渣中的CaO优选控制在合理的水平。根据我们的反复研究和实验，优选的，上述炉渣中CaO含量≤15％和/或CaO/SiO2≤0.8，更优选的，所述炉渣中，CaO含量≤10％和/或CaO/SiO2≤0.5。此时相当于是采用了MnO-SiO2-Al2O3-CaO四元系的冶炼渣型，但CaO含量较低。
与现有技术相比，本发明的优点在于：
(1)本发明的回收处理方法操作简单，工艺效率高，不仅非常适合于大规模处理含Co和/或Ni废旧电池及锰矿，而且也非常适合于Mn含量高的废旧电池的处理；
(2)本发明的回收处理方法不仅实现了废旧电池中高价值Co、Ni的回收再利用，还解决了电池中Mn的回收再利用问题，也解决了难选冶锰矿的回收再利用问题，大大提高了本发明在循环经济中的价值，具有显著的综合效益；
(3)本发明优选的回收处理方法中，通过搭配处理难选冶锰矿作为造渣剂，充分利用了电池自身还原性物料(金属铝和碳)过多的特点，将锰矿中的高价态锰氧化物还原至可被硫酸溶解的低价态MnO；也利用了造渣剂锰矿中Mn和SiO2含量较高的特点。采用锰氧化物调节了炉内的气氛；而采用SiO2调节了炉渣性质，使炉渣具有了合适的冶炼性能(低熔点、低 粘度、低Co、Ni等有价金属溶解度)，熔炼产出富锰渣(Mn含量≥25％甚至≥35％、Fe含量≤3％)，后续可经济有效地回收其中的Mn资源，即熔炼产出炉渣和合金均为有价物料、价值高，大大提高了本发明的经济效益。
综上所述，本发明充分利用了各原料的特点及互补性优势，达到了冶炼经济效益与社会效益的统一。
具体实施方式
为了便于理解本发明，下文将结合较佳的实施例对本发明作更全面、细致地描述，但本发明的保护范围并不限于以下具体的实施例。
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解的含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。
除非另有特别说明，本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。
实施例1：
一种本发明的含Co和/或Ni废旧电池的回收处理方法，包括以下步骤：
(1)备料
准备含Co和/或Ni废旧电池及含Mn和Si的造渣剂。本实施例中用到的含Co和/或Ni废旧电池为含Co和Ni的废旧铝壳锂离子电池(Cu 8wt.％，Co 16wt.％，Ni 2wt.％，Al 33wt.％，Fe 1wt.％，Mn 0.1wt.％，C 10wt.％)。本实施例中的造渣剂为软锰矿(Mn 33wt.％，Fe 7wt.％，SiO2 33wt.％，Al2O3 3.5wt.％，CaO 3.3wt.％；Mn以MnO2形态存在)，其有效造渣元素为Mn和Si，但软锰矿中不可避免地含有Fe。另外，造渣剂的用量为含Co和/或Ni废旧电池质量的3.0倍。
(2)熔炼
将上述准备的各种物料投入到电炉内熔炼，投入到熔炼炉中熔炼的各种物料还包括有另行添加的冶金焦炭，电炉内的氧分压的控制是通过调整入炉物料中还原剂和/或氧化剂的量来实现；通过控制电炉内的氧分压，控制熔炼温度1500℃，熔炼时间为15min，待炉渣与合金熔体完全分离，高温合金与炉渣分别从合金口和出渣口放出，得到含Cu、Co、Ni的合金、含Mn炉渣及烟尘。在产出的合金中，Co、Ni、Cu和Fe的回收率分别为96.8％、97.5％、95.8％和96.30％(90％以上的Fe进入含Co和/或Ni的合金中)；熔炼产出的炉渣组成为Co 0.41wt.％，Ni 0.02wt.％，Cu 0.38wt.％，Mn 34wt.％，Fe 2.3wt.％，SiO2 32.2wt.％，Al2O3 20.09wt.％，CaO 5.8wt.％，其中，Mn/SiO2＝1.05、CaO/SiO2＝0.18，且Mn以MnO形态存在。
在本实施例中，高铁含量的软锰矿(Fe含量7wt.％)转化为适于采用湿法冶金方法回收锰的原料-高锰渣(铁含量极低，仅为2.3wt.％)，并且渣中Mn以MnO形态存在，可直接被硫酸浸出，工艺的综合经济效益显著。
实施例2：
一种本发明的含Co和/或Ni废旧电池的回收处理方法，包括以下步骤：
(1)备料
准备含Co和/或Ni废旧电池及含Mn和Si的造渣剂。本实施例中用到的含Co和/或Ni废旧电池由废旧钢壳锂离子电池(Cu 8wt.％，Co 7wt.％，Ni 8wt.％，Al 5wt.％，Fe 35wt.％，Mn 0.1wt.％，C 10wt.％)与废旧铝壳锂离子电池(Cu 8wt.％，Co 16wt.％，Ni 2wt.％，Al 35wt.％，Fe 1wt.％，Mn 0.1wt.％，C 10wt.％)混合而成，其中，废旧铝壳锂离子电池占15％。本实施例中的造渣剂仅为软锰矿(Mn 38wt.％，Fe 7wt.％，SiO2 33wt.％，Al2O3 3.5wt.％，CaO 2.9wt.％；Mn以MnO2形态存在)，其有效造渣剂元素为Mn和Si，额外带入的Fe不是造渣元素，不影响后续炉渣性质。另外，造渣剂的用量为含Co和/或Ni废旧电池(或总电池物料)质量的0.55倍。
(2)熔炼：
将上述准备的各种物料投入到电炉内熔炼，电炉内的氧分压的控制是通过调整入炉物料中还原剂和/或氧化剂的量来实现；通过控制电炉内的氧分压，控制熔炼温度1450℃，熔炼时间为20min，待炉渣与合金熔体完全分离，高温合金与炉渣分别从合金口和出渣口放出，得到含Cu、Co、Ni的合金、含Mn炉渣及烟尘。在产出的合金中，Co、Ni、Cu和Fe的回收率分别为96.3％、96.8％、96.6％和98.01％(90％以上的Fe进入含Co和/或Ni的合金中)；熔炼产出的炉渣组成为Co 0.32wt.％，Ni 0.04wt.％，Cu 0.28wt.％，Mn 40.6％，Fe 0.6wt.％，SiO2 22wt.％，Al2O3 15.33wt.％，CaO 2.9wt.％，其中，Mn/SiO2＝1.84、CaO/SiO2＝0.13，Mn以MnO形态存在。
在本实施例中，熔炼产出炉渣Mn含量高，达到40.6％，且Fe含量低于3％，达到国家对富锰渣的质量要求，即炉渣与合金均为有价物料，价值高，综合经济效益显著提高。
实施例3：
一种本发明的含Co和/或Ni废旧电池的回收处理方法，包括以下步骤：
(1)备料
准备含Co和/或Ni废旧电池及含Mn和Si的造渣剂。本实施例中用到的含Co和/或Ni废旧电池由废旧聚合物锂离子电池(Cu 9wt.％，Co 16wt.％，Ni 0.1wt.％，Al 15wt.％，Fe 1wt.％，Mn 0.1wt.％，C 29wt.％)与废旧铝壳锂离子电池(Cu 8wt.％，Co 16wt.％，Ni 2wt.％， Al 35wt.％，Fe 1wt.％，Mn 0.1wt.％，C 10wt.％)混合而成，其中，废旧聚合物锂离子电池占50％。本实施例中的造渣剂为高铁锰矿(Mn 31wt.％，Fe 27wt.％，SiO2 35wt.％，Al2O3 4.5wt.％，CaO 8.3wt.％)、贫锰矿(Mn 16wt.％，Fe 11wt.％，SiO2 18wt.％，Al2O3 3.6wt.％，CaO 5.6wt.％；Mn以MnCO3和MnO2形态存在)和硅石(SiO2 98wt.％)的混合物，其中高铁锰矿占55％、贫锰矿占35％、硅石占10％，其有效造渣剂元素为Mn和Si，但额外带入的Fe不是造渣元素，不影响后续炉渣性质。另外，造渣剂的用量为含Co和/或Ni废旧电池(或总电池物料)质量的2.6倍。
(2)熔炼：
将上述准备的各种物料投入到电炉内熔炼，电炉内的氧分压的控制是通过调整入炉物料中还原剂和/或氧化剂的量来实现；通过控制电炉内的氧分压，控制熔炼温度1425℃，熔炼时间为30min，待炉渣与合金熔体完全分离，高温合金与炉渣分别从合金口和出渣口放出，得到含Cu、Co、Ni的合金、含Mn炉渣及烟尘。在产出的合金中，Co、Ni、Cu和Fe的回收率分别为96.9％、97.5％、97.2％和98.02％(90％以上的Fe进入含Co和/或Ni的合金中)；熔炼产出的炉渣组成为Co 0.23wt.％，Ni 0.03wt.％，Cu 0.31wt.％，Mn 32.15％，Fe 1.45wt.％，SiO2 36.82wt.％，Al2O3 22.53wt.％，CaO 12.9wt.％，其中，Mn/SiO2＝0.87、CaO/SiO2＝0.35、Mn以MnO形态存在。
在本实施例中，熔炼产出炉渣Mn含量高，达到32.15％，且Fe含量低于3％，达到国家对富锰渣的质量要求，即炉渣与合金均为有价物料，价值高，综合经济效益显著提高。
实施例4：
一种本发明的含Mn废旧电池的回收处理方法，包括以下步骤：
(1)备料
准备含Mn废旧电池及含Si的造渣剂。本实施例中用到的含Mn废旧电池由含Mn废旧聚合物锂离子电池(Cu 9wt.％，Co 5wt.％，Ni 1wt.％，Al 15wt.％，Fe 1wt.％，Mn 22wt.％，C 19wt.％)与几乎不含Mn废旧钢壳锂离子电池(Cu 8wt.％，Co 15wt.％，Ni 2wt.％，Al 5wt.％，Fe 30wt.％，Mn 0.2wt.％，C 11wt.％)混合而成，其中，含Mn废旧聚合物锂离子电池占70％。本实施例中的造渣剂由铜冶炼渣(Cu 0.8wt.％，Fe 36.9wt.％，SiO2 34.5wt.％，Al2O3 4.5wt.％，CaO 8.5wt.％)和硅石(SiO2 98wt.％)混合而成，其中铜渣占57％、硅石占43％，其有效造渣元素仅为Si，但铜冶炼渣中不可避免地含有Fe。另外，造渣剂的用量为含Mn废旧电池(或总电池物料)质量的0.4倍。
(2)熔炼
将上述准备的各种物料投入到电炉内熔炼，投入到熔炼炉中熔炼的各种物料还包括有另 行添加的冶金焦炭，电炉内的氧分压的控制是通过调整入炉物料中还原剂和/或氧化剂的量来实现；通过控制电炉内的氧分压，控制熔炼温度1500℃，熔炼时间为15min，待炉渣与合金熔体完全分离，高温合金与炉渣分别从合金口和出渣口放出，得到含Cu、Co、Ni的合金、含Mn炉渣及烟尘。在产出的合金中，Co、Ni、Cu和Fe的回收率分别为97.5％、97.9％、95.5％和95.60％；熔炼产出的炉渣组成为Co 0.45wt.％，Ni 0.02wt.％，Cu 0.50wt.％，Mn 17.98wt.％，Fe 2.8wt.％，SiO2 33.51wt.％，Al2O3 21.54wt.％，CaO 12.6wt.％，其中，Mn/SiO2＝0.54、CaO/SiO2＝0.38。
在本实施例中，造渣剂用量仅为含Mn废旧电池质量的0.4倍，远低于现有技术中的造渣剂消耗量；炉渣中Cu含量仅为0.50％，同时回收了电池和铜冶炼渣中的铜，经济效益显著。
实施例5：
一种本发明的含Mn废旧电池的回收处理方法，包括以下步骤：
(1)备料
准备含Mn废旧电池及含Si的造渣剂。本实施例中用到的含Mn废旧电池由含Mn废旧聚合物锂离子电池(Cu 9wt.％，Co 5wt.％，Ni 1wt.％，Al 15wt.％，Fe 1wt.％，Mn 22wt.％，C 19wt.％)与几乎不含Mn的废旧铝壳锂离子电池(Cu 8wt.％，Co 16wt.％，Ni 2wt.％，Al 35wt.％，Fe 1wt.％，Mn 0.1wt.％，C 10wt.％)混合而成，其中，含Mn废旧聚合物锂离子电池占50％。本实施例中的造渣剂仅为锰矿(Mn 33wt.％，Fe 7wt.％，SiO2 33wt.％，Al2O3 3.5wt.％，CaO 2.9wt.％)，其有效造渣剂元素为Mn和Si，但额外带入的Fe不是造渣元素，不影响后续炉渣性质。另外，造渣剂的用量为含Mn废旧电池(或总电池物料)质量的2倍。
(2)熔炼：
将上述准备的各种物料投入到电炉内熔炼，电炉内的氧分压的控制是通过调整入炉物料中还原剂和/或氧化剂的量来实现；通过控制电炉内的氧分压，控制熔炼温度1450℃，熔炼时间为20min，待炉渣与合金熔体完全分离，高温合金与炉渣分别从合金口和出渣口放出，得到含Cu、Co、Ni的合金、含Mn炉渣及烟尘。在产出的合金中，Co、Ni、Cu和Fe的回收率分别为96.5％、97.8％、95.1％和96.08％；熔炼产出的炉渣组成为Co 0.35wt.％，Ni 0.04wt.％，Cu 0.33wt.％，Mn 39.2％，Fe 1.09wt.％，SiO2 20wt.％，Al2O3 17.91wt.％，CaO 3.3wt.％，其中，Mn/SiO2＝1.95、CaO/SiO2＝0.17。
在本实施例中，熔炼产出炉渣Mn含量高，达到39.2％，且Fe含量低于3％，达到国家对富锰渣的质量要求，即炉渣与合金均为有价物料，价值高，综合经济效益显著提高。
实施例6：
一种本发明的含Mn废旧电池的回收处理方法，包括以下步骤：
(1)备料
准备含Mn废旧电池及含Si的造渣剂。本实施例中用到的含Mn废旧电池由含Mn废旧聚合物锂离子电池(Cu 9wt.％，Co 5wt.％，Ni 1wt.％，Al 15wt.％，Fe 1wt.％，Mn 22wt.％，C 19wt.％)与几乎不含Mn的废旧铝壳锂离子电池(Cu 8wt.％，Co 16wt.％，Ni 2wt.％，Al 35wt.％，Fe 1wt.％，Mn 0.1wt.％，C 10wt.％)混合而成，其中，含Mn废旧聚合物锂离子电池材料占50％。本实施例中的造渣剂为软锰矿(Mn 33wt.％，Fe 7wt.％，SiO2 33wt.％，Al2O3 3.5wt.％，CaO 3.3wt.％)、贫锰矿(Mn 16wt.％，Fe 11wt.％，SiO2 18wt.％，Al2O3 3.6wt.％，CaO 5.6wt.％)和硅石(SiO2 98wt.％)的混合物，其中软锰矿占55％、贫锰矿占35％、硅石占10％，其有效造渣剂元素为Mn和Si，但额外带入的Fe不是造渣元素，不影响后续炉渣性质。另外，造渣剂的用量为含Mn废旧电池(或总电池物料)质量的2.6倍。
(2)熔炼：
将上述准备的各种物料投入到电炉内熔炼，电炉内的氧分压的控制是通过调整入炉物料中还原剂和/或氧化剂的量来实现；通过控制电炉内的氧分压，控制熔炼温度1425℃，熔炼时间为30min，待炉渣与合金熔体完全分离，高温合金与炉渣分别从合金口和出渣口放出，得到含Cu、Co、Ni的合金、含Mn炉渣及烟尘。在产出的合金中，Co、Ni、Cu和Fe的回收率分别为97.3％、98.3％、96.2％和96.68％；熔炼产出的炉渣组成为Co 0.15wt.％，Ni 0.03wt.％，Cu 0.28wt.％，Mn 38.25％，Fe 0.35wt.％，SiO2 33.01wt.％，Al2O3 21.82wt.％，CaO 7.2wt.％，其中，Mn/SiO2＝1.15、CaO/SiO2＝0.22。
在本实施例中，熔炼产出炉渣Mn含量高，达到38.25％，且Fe含量低于3％，达到国家对富锰渣的质量要求，即炉渣与合金均为有价物料，价值高，综合经济效益显著提高。

Claims (18)

  1. 一种废旧电池的回收处理方法，包括以下步骤：
    (1)准备废旧电池，另外准备造渣剂，所述造渣剂中至少含10wt.％的Si和/或Mn；
    (2)将上述准备的各种物料投入到熔炼炉中熔炼，熔炼产出含Co和/或Ni的合金、含Mn炉渣及烟尘；通过控制熔炼炉内的氧分压、熔炼温度和熔炼时间，使得熔炼产出的含Mn炉渣中Mn含量≥15wt.％、Fe含量≤5wt.％、Al2O3含量≤30wt.％；且0.2≤Mn/SiO2≤3.0。
  2. 根据权利要求1所述的废旧电池的回收处理方法，其特征在于，所述废旧电池为含有Mn元素的含Mn废旧电池。
  3. 根据权利要求2所述的废旧电池的回收处理方法，其特征在于，所述含Mn废旧电池为Mn含量15wt.％以上的废旧锂离子电池、或者为前述废旧锂离子电池与Mn含量3wt.％以下的废旧锂离子电池的混合。
  4. 根据权利要求3所述的废旧电池的回收处理方法，其特征在于，所述的废旧锂离子电池为废旧铝壳锂离子电池和/或Al含量在8％～15％的废旧聚合物锂离子电池。
  5. 根据权利要求1所述的废旧电池的回收处理方法，其特征在于，所述废旧电池为几乎不含锰元素的含Co和/或Ni废旧电池，且所述造渣剂中至少含10wt.％的Mn和Si；熔炼时将所述造渣剂中的高价态锰氧化物转化成含Mn炉渣中易被硫酸浸出的低价态锰氧化物，且熔炼物料中所含有的绝大部分Fe进入所述含Co和/或Ni的合金中。
  6. 根据权利要求5所述的废旧电池的回收处理方法，其特征在于，所述含Co和/或Ni废旧电池为废旧锂离子电池。
  7. 根据权利要求6所述的废旧电池的回收处理方法，其特征在于，所述的废旧锂离子电池为废旧铝壳锂离子电池和/或Al含量在8％～15％的废旧聚合物锂离子电池。
  8. 根据权利要求1-7中任一项所述的废旧电池的回收处理方法，其特征在于，所述造渣剂中的有效造渣元素包含Mn和Si，且不额外添加Fe作为造渣剂，并尽量提高造渣剂中的Si含量。
  9. 根据权利要求8所述的废旧电池的回收处理方法，其特征在于，所述造渣剂为锰矿，所述锰矿中Mn含量≥10％、Fe含量在5％以上。
  10. 根据权利要求1-7中任一项所述的废旧电池的回收处理方法，其特征在于，所述含Mn炉渣中Mn含量≥25wt.％、Fe含量≤3wt.％；且0.8≤Mn/SiO2≤2.5。
  11. 根据权利要求10所述的废旧电池的回收处理方法，其特征在于，所述物料中的高价态锰氧化物均转化为低价态锰氧化物MnO。
  12. 根据权利要求1-7中任一项所述的废旧电池的回收处理方法，其特征在于，所述造渣剂的添加量为所述废旧电池质量的0.25倍以上。
  13. 根据权利要求12所述的废旧电池的回收处理方法，其特征在于，所述造渣剂的添加量为所述废旧电池质量的0.3倍以上。
  14. 根据权利要求1-7中任一项所述的废旧电池的回收处理方法，其特征在于，所述含Mn炉渣为MnO-SiO2-Al2O3-CaO四元系冶炼渣型，且含Mn炉渣中的主要成分为MnO、SiO2、Al2O3和CaO，所述含Mn炉渣中CaO含量≤15％和/或CaO/SiO2≤0.8。
  15. 根据权利要求1-7中任一项所述的废旧电池的回收处理方法，其特征在于，所述熔炼温度控制在1350℃～1600℃，所述熔炼时间不低于10min。
  16. 根据权利要求1-7中任一项所述的废旧电池的回收处理方法，其特征在于，所述投入到熔炼炉中熔炼的各种物料还包括有另行添加的冶金焦炭。
  17. 根据权利要求1-7中任一项所述的废旧电池的回收处理方法，其特征在于，所述熔炼炉内的氧分压的控制是通过调整入炉物料中还原剂和/或氧化剂的量来实现。
  18. 根据权利要求17所述的废旧电池的回收处理方法，其特征在于，所述还原剂包括冶金焦碳或废旧电池中的铝。
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