CN103682509A - Method for recycling mixed rare earth from waste nickel-hydrogen battery - Google Patents
Method for recycling mixed rare earth from waste nickel-hydrogen battery Download PDFInfo
- Publication number
- CN103682509A CN103682509A CN201210360827.4A CN201210360827A CN103682509A CN 103682509 A CN103682509 A CN 103682509A CN 201210360827 A CN201210360827 A CN 201210360827A CN 103682509 A CN103682509 A CN 103682509A
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- Prior art keywords
- rare earth
- hydrogen battery
- recycling
- waste nickel
- waste
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- 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
-
- 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
- C22B59/00—Obtaining rare earth metals
-
- 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
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- 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)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of recycling of nickel-hydrogen batteries and provides a method for recycling mixed rare earth from a waste nickel-hydrogen battery. The method for recycling the mixed rare earth from the waste nickel-hydrogen battery comprises the following steps: mechanically stripping the waste nickel-hydrogen battery to separate a negative electrode material and a positive electrode material; carrying out ultrasonic treatment on the negative electrode material to separate a base body from negative electrode powder; then adding the negative electrode powder into a leaching solution containing hydrochloric acid and nitric acid; raising the temperature to 40-60 DEG C and immersing for 2-3 hours; filtering and adjusting the PH (Potential of Hydrogen) value of a filtering solution to 3-6; adding water-soluble carbonate to precipitate rare earth elements; and finally, separating, washing and drying obtained sediments and calcining under the protection of inert gas to obtain the mixed rare earth. According to the method for recycling mixed rare earth from the waste nickel-hydrogen battery, the rare earth elements can be effectively recycled; energy sources consumed in the recycling process are few and the route of a recycling process is short; the recycling benefits are good; the pollution to the environment by rare-earth waste residues in the nickel-hydrogen battery is greatly reduced.
Description
Technical field
The present invention relates to the recovery of waste nickel hydrogen battery, relate in particular to a kind of method that reclaims mishmetal from waste nickel hydrogen battery.
Background technology
Along with electronic industry fast development, waste battery has become important pollutant sources.In waste and old nickel-hydrogen chargeable cell, contain a large amount of nickel, cobalt, iron, rare earth (La, Ce, Pr, Nd) composition, and rare earth metal composition is at occurring in nature or scarce resource, to the research of waste and old nickel radical battery recycling, is very valuable.Nickel-hydrogen waste battery reclaims and adopts traditional dressing and smelting process to reclaim nickel at present, for other materials such as rare earth in battery, take to fill up processing, such one is to environment, the 2nd, waste rare earth resources, press content of rare earth 12% and calculate (Ni-MH battery Rare-Earth Content 10%～15%), mishmetal price is calculated by 250,000/ton, its Huge value.This old Ni-MH battery recovery process is difficult to meet waste nickel hydrogen battery resource recycling and utilizes the basic demand at economy, ecological property, high efficiency, the aspect such as comprehensive.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the method that reclaims mishmetal from waste nickel hydrogen battery is provided.
For realizing above object, the technical solution used in the present invention is:
From waste nickel hydrogen battery, reclaim a method for mishmetal, comprise the steps:, by waste nickel hydrogen battery process mechanical stripping, to isolate negative material, positive electrode, negative material is processed through ultrasonic wave, and matrix is separated with negative pole powder; Negative pole powder is dropped in the leachate that contains hydrochloric acid and nitric acid, rising temperature to 40～60 ℃, soak 2～3 hours again; Then filter, regulating the pH value of filtrate is 3～6, adds water soluble carbonate, precipitation rare earth element wherein; Last separation, washing, dry gained precipitation, and it is calcined and obtain mishmetal under inert gas shielding.
Every kilogram of negative pole powder joins in 1～5L leachate.
In described leachate, concentration of hydrochloric acid is 0.5～1mol/L, and concentration of nitric acid is 2～4mol/L.
The amount of the water soluble carbonate that precipitating rare earth is used is 2～3 times of the required theoretical amount of precipitating rare earth element.
Beneficial effect of the present invention: recovering rare earth element effectively, in removal process, consume the energy few, recovery process route is short, reclaims profitablely, greatly reduces in Ni-MH battery containing the pollution of rare earth waste to environment.
Embodiment
Below by an embodiment, be described further.
Embodiment 1
1) by waste nickel hydrogen battery process mechanical stripping, isolate negative material, positive electrode;
2) negative material is processed through ultrasonic wave, and matrix is separated with negative pole powder;
3) preparation leachate, contains hydrochloric acid and nitric acid in leachate, and concentration of hydrochloric acid is that 0.5mol/L concentration of nitric acid is 2mol/L;
4) every kilogram of negative pole powder is put in 3L leachate, rising temperature to 40 ℃, leaches 2 hours;
5) filter, then to regulate the pH value of filtrate (can add NaOH solution to regulate) be 3, add Na
2cO
3, precipitation rare earth element wherein;
6) separation, washing, dry rare earth carbonate;
7) rare earth carbonate is calcined under inert gas shielding.
Wherein, the amount of precipitating rare earth water soluble carbonate used is 2 times of the required theoretical amount of precipitating rare earth element.
The rare earth element rate of recovery: 98.5%.
Rare earth yield account form is: the rare earth of recovery/negative pole powder/negative pole powder middle rare earth theoretical content * 100%, negative pole powder middle rare earth theoretical content is 33%.
Embodiment 2
1) by waste nickel hydrogen battery process mechanical stripping, isolate negative material, positive electrode;
2) negative material is processed through ultrasonic wave, and matrix is separated with negative pole powder;
3) preparation leachate, contains hydrochloric acid and nitric acid in leachate, and concentration of hydrochloric acid is that 1mol/L concentration of nitric acid is 4mol/L;
4) every kilogram of negative pole powder is put in 3L leachate, rising temperature to 60 ℃, leaches 3 hours;
5) filter, regulate the pH value 3 of (can add NaOH solution to regulate) filtrate, add Na
2cO
3, precipitation rare earth element wherein;
6) separation, washing, dry rare earth carbonate;
7) rare earth carbonate is calcined under inert gas shielding.
Wherein, the amount of precipitating rare earth water soluble carbonate used is 3 times of the required theoretical amount of precipitating rare earth element.
The rare earth element rate of recovery: 99.2%.
The rare earth of rare earth yield account form=recovery/negative pole powder/negative pole powder middle rare earth theoretical content * 100%, negative pole powder middle rare earth theoretical content is 33%.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, make concrete change or change and all belong to protection scope of the present invention.
Claims (4)
1. a method that reclaims mishmetal from waste nickel hydrogen battery, it is characterized in that comprising the steps: by waste nickel hydrogen battery through mechanical stripping, isolate negative material, positive electrode, negative material is processed through ultrasonic wave, and matrix is separated with negative pole powder; Negative pole powder is dropped in the leachate that contains hydrochloric acid and nitric acid, rising temperature to 40～60 ℃, soak 2～3 hours again; Then filter, regulating the pH value of filtrate is 3～6, adds water soluble carbonate, precipitation rare earth element wherein; Last separation, washing, dry gained precipitation, and it is calcined and obtain mishmetal under inert gas shielding.
2. the method that reclaims mishmetal from waste nickel hydrogen battery according to claim 1, is characterized in that: every kilogram of negative pole powder joins in 1～5L leachate.
3. the method that reclaims mishmetal from waste nickel hydrogen battery according to claim 1, is characterized in that: in described leachate, concentration of hydrochloric acid is 0.5～1mol/L, and concentration of nitric acid is 2～4mol/L.
4. the method that reclaims mishmetal from waste nickel hydrogen battery according to claim 1, is characterized in that: the amount of the water soluble carbonate that precipitating rare earth is used is 2～3 times of the required theoretical amount of precipitating rare earth element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210360827.4A CN103682509A (en) | 2012-09-25 | 2012-09-25 | Method for recycling mixed rare earth from waste nickel-hydrogen battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210360827.4A CN103682509A (en) | 2012-09-25 | 2012-09-25 | Method for recycling mixed rare earth from waste nickel-hydrogen battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103682509A true CN103682509A (en) | 2014-03-26 |
Family
ID=50319303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210360827.4A Pending CN103682509A (en) | 2012-09-25 | 2012-09-25 | Method for recycling mixed rare earth from waste nickel-hydrogen battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103682509A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106222456A (en) * | 2016-08-23 | 2016-12-14 | 金川集团股份有限公司 | A kind of recovering rare earth method of making the transition from waste nickel hydrogen battery |
| CN107955879A (en) * | 2017-12-05 | 2018-04-24 | 广东省稀有金属研究所 | A kind of method of valuable element in recycling waste lithium ion battery electrode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171170A (en) * | 1994-12-20 | 1998-01-21 | 瓦尔达电池股份公司 | Process for recovery of metals from used nickel-metal hydride accumulators |
| CN1070536C (en) * | 1996-02-13 | 2001-09-05 | 三德金属工业株式会社 | Method for recovering reusable elements from rare earth-nickel alloy |
| CN102304620A (en) * | 2011-09-23 | 2012-01-04 | 先进储能材料国家工程研究中心有限责任公司 | Comprehensive recovery and treatment method of waste nickel-hydrogen battery |
-
2012
- 2012-09-25 CN CN201210360827.4A patent/CN103682509A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171170A (en) * | 1994-12-20 | 1998-01-21 | 瓦尔达电池股份公司 | Process for recovery of metals from used nickel-metal hydride accumulators |
| CN1070536C (en) * | 1996-02-13 | 2001-09-05 | 三德金属工业株式会社 | Method for recovering reusable elements from rare earth-nickel alloy |
| CN102304620A (en) * | 2011-09-23 | 2012-01-04 | 先进储能材料国家工程研究中心有限责任公司 | Comprehensive recovery and treatment method of waste nickel-hydrogen battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106222456A (en) * | 2016-08-23 | 2016-12-14 | 金川集团股份有限公司 | A kind of recovering rare earth method of making the transition from waste nickel hydrogen battery |
| CN107955879A (en) * | 2017-12-05 | 2018-04-24 | 广东省稀有金属研究所 | A kind of method of valuable element in recycling waste lithium ion battery electrode material |
| CN107955879B (en) * | 2017-12-05 | 2019-08-30 | 广东省稀有金属研究所 | A kind of method of valuable element in recycling waste lithium ion battery electrode material |
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Application publication date: 20140326 |