CN108823417A - The method of useless power battery recycling non-ferrous metal removal of impurities - Google Patents

The method of useless power battery recycling non-ferrous metal removal of impurities Download PDF

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Publication number
CN108823417A
CN108823417A CN201810777692.9A CN201810777692A CN108823417A CN 108823417 A CN108823417 A CN 108823417A CN 201810777692 A CN201810777692 A CN 201810777692A CN 108823417 A CN108823417 A CN 108823417A
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China
Prior art keywords
impurities
ferrous metal
liquid
feed liquid
removal
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CN201810777692.9A
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Chinese (zh)
Inventor
孙东江
王志勇
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Individual
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Priority to CN201810777692.9A priority Critical patent/CN108823417A/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
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/0015—Obtaining aluminium by wet processes
    • C22B21/0023—Obtaining aluminium by wet processes from waste materials
    • 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
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • 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
    • C22B47/00—Obtaining manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C22B7/008—Wet processes by an alkaline or ammoniacal 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

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

Abstract

A kind of method of useless power battery recycling non-ferrous metal removal of impurities, prepare including slagging-off feed liquid, feed liquid cleans, alkali is leached except the several steps of precipitated aluminium hydroxide in aluminium, sodium aluminate, it is that have the characteristics that both sexes using aluminium, it is leached by aluminium hydroxide and non-ferrous metal mixing slag of the certain density sodium hydroxide solution to removal of impurities generation, so that aluminium hydroxide enters solution and non-ferrous metal hydroxide for precipitating reaches separation, slag phase is used without washing direct reuse to feed liquid removal of impurities or sour decomposition process after such separation of solid and liquid, NaAlO2Liquid can produce Al (OH) by coprecipitation mode3Product had not only reduced production link but also had improved nonferrous metals recycling rate, while producing Al (OH)3Product realizes no scorification.

Description

The method of useless power battery recycling non-ferrous metal removal of impurities
Technical field
The present invention relates to a kind of methods of useless power battery recycling non-ferrous metal removal of impurities.
Background technique
Current driving force battery is mainly lithium battery, and main Types have LiFePO4 series, cobalt acid lithium series, LiMn2O4 system Column, cobalt nickel ion doped series.Power battery includes shell and battery core two large divisions, is separated through physics dismantling rear casing with battery core, Battery core is after crushed for hydrometallurgical extraction purpose element.The battery core comminuting matter of cobalt acid lithium lithium battery, cobalt nickel ion doped battery Main component composition has cobalt, nickel, manganese, copper, aluminium, lithium, carbon dust and plastic diaphragms paper, and processing wet process is：Acid dissolution → copper Extraction → removal of impurities → P2O4Abstraction impurity removal → P5O7Separation of Cobalt and Nickel.In removal of impurities process, the removal of impurities of traditional handicraft and removal of impurities Slag treatment Primarily directed to the recycling of non-ferrous metal in element aluminum and hydroxide aluminium slag, main method is that pH=5 or so of adjustment feed liquid make aluminium It is removed in aluminum hydroxide precipitation, while being mingled with the non-ferrous metal sediment of part, point of non-ferrous metal and aluminum hydroxide precipitate It is realized from by multistage weak acid scrubbing, the aluminium of such part is returned in acidleach feed liquid, while the hydroxide aluminium slag abandoned In with a small amount of non-ferrous metal, process is many and diverse, and the rate of recovery has a certain impact.
Summary of the invention
Low, simple process that it is an object of the invention to provide a kind of production costs, can make aluminium hydroxide big with non-ferrous metal The method for being partially separated, and recycling the useless power battery recycling non-ferrous metal removal of impurities of a small amount of non-ferrous metal of discarding.
The method of useless power battery recycling non-ferrous metal removal of impurities of the invention, includes the following steps：
1, slagging-off feed liquid prepares：Slagging-off feed liquid is derived from copper feed liquid extracted, 500L, consisting of：CO 40g/l、Ni15 g/ L, Cu 2g/l, Mn 5g/l, Al 5g/l, system are sulfuric acid system, pH=1-1.5;
2, feed liquid cleans：Above-mentioned feed liquid is transferred in the pp material bucket with stirring, stirring is started, is uniformly added into solid sodium carbonate tune Then whole material liquid pH=3-3.5 is imported liquid sodium hydroxide tune pH=4.5-5.5 of concentration 5-10% by pipeline, passes through sheet frame Filters pressing, filtrate are transferred to extraction process separation non-ferrous metal, and filter residue is spare;
3, alkali, which leaches, removes aluminium：The filter residue that step 2 is generated is put into the pp material bucket with stirring, and 2 times of filter residue amount of water is added, Then 1.5 times of aluminum amount are added, the solid sodium hydroxide of weight ratio carries out alkali Leach reaction, is stirred to react half an hour or more, then It is filtered by sheet frame, filtrate is transferred to spare in liquid storing barrel, and filter residue is non-ferrous metal hydroxide and a small amount of sodium aluminate Mixture decomposes for acid and is used as alkali to use as raw material or removal of impurities；
4, precipitated aluminium hydroxide in sodium aluminate：Sodium aluminate solution in step 3 in liquid storing barrel is transferred to the pp material bucket with stirring In, it is slowly added to the dilute sulfuric acid of 30% concentration, pH value of solution=7 is adjusted under stirring conditions, then filters, filtrate abandons, filter residue As Al (OH)3Coarse products.
The method of useless power battery recycling non-ferrous metal removal of impurities of the invention, has the characteristics that both sexes using aluminium, passes through one The sodium hydroxide solution for determining concentration leaches the aluminium hydroxide and non-ferrous metal mixing slag of removal of impurities generation, so that aluminium hydroxide Into solution, non-ferrous metal hydroxide is that precipitating reaches separation, and reaction equation is：
Al(OH)3▪M(OH)n(Gu)+NaoH (liquid)=NaAlO2(liquid)+M (OH) n (Gu)+H2O ；
Slag phase is used without washing direct reuse to feed liquid removal of impurities or sour decomposition process after such separation of solid and liquid, NaAlO2Liquid Al (OH) can be produced by coprecipitation mode3Product had not only reduced production link but also had improved nonferrous metals recycling rate, generated simultaneously Al (OH)3Product realizes no scorification.
Specific embodiment
A kind of method of useless power battery recycling non-ferrous metal removal of impurities, includes the following steps：
1, slagging-off feed liquid prepares：Slagging-off feed liquid is derived from copper feed liquid extracted, 500L, consisting of：CO 40g/l、Ni15 g/ L, Cu 2g/l, Mn 5g/l, Al 5g/l, system are sulfuric acid system, pH=1-1.5;
2, feed liquid cleans：Above-mentioned feed liquid is transferred to 1 1m3In pp material bucket with stirring, stirring is started, solid carbon is uniformly added into Sour sodium adjusts material liquid pH=3.5, then by liquid sodium hydroxide tune pH=5 of pipeline importing concentration 10%, by plate compression, Filtrate is transferred to extraction process separation non-ferrous metal, and filter residue is spare;
3, alkali, which leaches, removes aluminium：The filter residue that step 2 is generated puts into a 1m3In pp material bucket with stirring, filter residue amount 2 is added Then water again is added 1.5 times of aluminum amount（Weight ratio）Solid sodium hydroxide carry out alkali Leach reaction, be stirred to react half an hour with On, it is then filtered by sheet frame, filtrate is transferred to spare in liquid storing barrel, and filter residue is non-ferrous metal hydroxide and a small amount of aluminium The mixture of sour sodium decomposes for acid and is used as alkali to use as raw material or removal of impurities；
4, precipitated aluminium hydroxide in sodium aluminate：Sodium aluminate solution in step 3 in liquid storing barrel is transferred to 1 1m3Pp with stirring In material bucket, it is slowly added to the dilute sulfuric acid of 30% concentration, pH value of solution=7 is adjusted under stirring conditions, then filters, filtrate is lost It abandons, filter residue is Al (OH)3Coarse products.

Claims (1)

1. a kind of method of useless power battery recycling non-ferrous metal removal of impurities, it is characterised in that：It includes the following steps：
（1）, slagging-off feed liquid prepare：Slagging-off feed liquid is derived from copper feed liquid extracted, 500L, consisting of：CO 40g/l、Ni15 g/ L, Cu 2g/l, Mn 5g/l, Al 5g/l, system are sulfuric acid system, pH=1-1.5;
（2）, feed liquid removal of impurities：Above-mentioned feed liquid is transferred to 1 1m3In pp material bucket with stirring, stirring is started, solid is uniformly added into Sodium carbonate adjusts material liquid pH=3-3.5, and liquid sodium hydroxide tune pH=4.5-5.5 of concentration 5-10% is then imported by pipeline, By plate compression, filtrate is transferred to extraction process separation non-ferrous metal, and filter residue is spare;
（3）, alkali leach remove aluminium：By step（2）The filter residue of generation puts into a 1m3In pp material bucket with stirring, filter residue is added Then the water of 2 times of amount is added 1.5 times of aluminum amount, the solid sodium hydroxide progress alkali Leach reaction of weight ratio, is stirred to react half an hour More than, it is then filtered by sheet frame, filtrate is transferred to spare in liquid storing barrel, and filter residue is non-ferrous metal hydroxide and a small amount of The mixture of sodium aluminate decomposes for acid and is used as alkali to use as raw material or removal of impurities；
（4）, precipitated aluminium hydroxide in sodium aluminate：By step（3）Sodium aluminate solution in middle liquid storing barrel is transferred to 1 1m3With stirring In pp material bucket, it is slowly added to the dilute sulfuric acid of 30% concentration, pH value of solution=7 is adjusted under stirring conditions, then filters, filtrate It abandons, filter residue is Al (OH)3Coarse products.
CN201810777692.9A 2018-07-16 2018-07-16 The method of useless power battery recycling non-ferrous metal removal of impurities Pending CN108823417A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113620482A (en) * 2021-07-12 2021-11-09 北京汉昌绿源环保工程有限公司 Process capable of circularly adjusting pH of liquid to be treated

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140286840A1 (en) * 2013-03-25 2014-09-25 Ping-Tao WU Method for recovering metals from waste aluminum catalyst
CN106319218A (en) * 2015-06-16 2017-01-11 有研稀土新材料股份有限公司 Method for recovering rare earth, aluminum and silicon from rare earth-containing aluminum and silicon wastes
CN105838881B (en) * 2016-06-12 2017-11-07 赣州稀土开采技术服务有限公司 Southern ion type rareearth ore leaching liquid impurity removal process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140286840A1 (en) * 2013-03-25 2014-09-25 Ping-Tao WU Method for recovering metals from waste aluminum catalyst
CN106319218A (en) * 2015-06-16 2017-01-11 有研稀土新材料股份有限公司 Method for recovering rare earth, aluminum and silicon from rare earth-containing aluminum and silicon wastes
CN105838881B (en) * 2016-06-12 2017-11-07 赣州稀土开采技术服务有限公司 Southern ion type rareearth ore leaching liquid impurity removal process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113620482A (en) * 2021-07-12 2021-11-09 北京汉昌绿源环保工程有限公司 Process capable of circularly adjusting pH of liquid to be treated

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Application publication date: 20181116