CN102181646A - Comprehensive recycle and utilization method based on selective oxidation/ reduction rare earth nickel-metal hydride battery waste - Google Patents
Comprehensive recycle and utilization method based on selective oxidation/ reduction rare earth nickel-metal hydride battery waste Download PDFInfo
- Publication number
- CN102181646A CN102181646A CN2011100935547A CN201110093554A CN102181646A CN 102181646 A CN102181646 A CN 102181646A CN 2011100935547 A CN2011100935547 A CN 2011100935547A CN 201110093554 A CN201110093554 A CN 201110093554A CN 102181646 A CN102181646 A CN 102181646A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- slag
- selective oxidation
- alloy
- reduction
- 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.)
- Pending
Links
Classifications
-
- 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
Abstract
The invention relates to a comprehensive recycle and utilization method based on selective oxidation/ reduction rare earth nickel-metal hydride battery waste. Rare earth hydrogen storage alloy smelting slag or abandoned rare earth nickel-metal hydride battery electrode powder serves as a raw material, and Ni-Co alloy and rare earth oxide slag are recovered with a selective oxidation/ reduction-slag metal melting and separating method. The raw material is subjected to oxidation/ reduction processing by mixed gas with oxidation reduction, active metallic elements in the raw material are selectively oxidized, and inert metallic elements are kept in the elementary substance state, or the compound of the inert metallic elements is reduced into the elementary substance state; and material subjected to the oxidation/ reduction processing is mixed into slag forming constituent for slag metal melting and separating to obtain Ni-Co alloy and rare earth oxide slag. The Ni-Co alloy can be used as a raw material for smelting rare earth hydrogen storage alloy or other alloys, but the rare earth oxide slag can be used as the raw material for smelting rare earth silicon iron alloy or the raw material for further extracting the rare earth, thereby comprehensively recycling the rare earth nickel-metal hydride battery waste.
Description
Technical field
The present invention relates to a kind of comprehensive reutilization method, belong to the rare earth metallurgy technical field, especially rare earth and Non-ferrous Metallurgy reclamation of waste materials aspect based on selective oxidation/reductive rare earth nickel metal hydride battery waste material.
Technical background
The application of rare earth nickel metal hydride battery is more and more wider, in all kinds of portable electronics, electromobile, Moped Scooter field very strong suitability is arranged.The nickel metal hydride battery development is rapid, but also is accompanied by the problem of waste material simultaneously.(1) in the smelting process of negative material alloy, owing to oxidation, scorification effect, formed a certain amount of waste residue, the waste residue rate accounts for about 2% of alloy mass.(2) nickel metal hydride battery is in long charge and discharge cycles process, can produce anodal and the negative pole powder that gives up because efflorescence and oxidation were lost efficacy gradually.The main component of rare earth nickel metal hydride battery waste residue, useless powder is Ni, Co and RE, is the noble metal element, and its comprehensive reutilization becomes the problem that must face.
The recycling of the useless powder of rare earth nickel metal hydride battery has patent and bibliographical information.Germany Patent document DE6110433 and Japanese documentation JP2639494, JP8157974 propose to adopt the chemical technology of complexity such as acid-alkali treatment, extraction and reextraction, each element of alloy is separated, the isolating product of art breading is the oxide compound of each element, as continue on for producing metal or alloy, must corresponding metallurgical technology.So complex process, the cost height.China Nankai University has reported the method that chemical treatment and smelting combine, after the acid of battery cathode powder is dissolved and is learned processing, and compressing tablet, melt back is 3～4 times in non-consumable arc furnace, and the zone of oxidation of removing melting ingot casting surface obtains alloy.Technical process is short, but only adopts simple acid pasting separating oxide, and the oxide compound separation rate is low, can only adopt the high arc temperature melting to separate a large amount of oxide compounds, and the cost height is difficult to industrialization.
The recycling report of hydrogen storage alloy waste residue is less.University Of Science and Technology of the Inner Mongol has reported the method for magnetic separation-melting slagging-off, and its shortcoming is: magnetic separation separating oxide weak effect influences follow-up melting deslagging process.Patent " the AB that the patented invention philtrum is asked
5The method that type lanthanon hydrogen storage alloy melting waste slag is recycled " (publication number CN101748279) then be only limited to the recovery melting waste slag, RE-M alloy (RE:La, Ce, Pr, the Nd of recovery; M:Ni, Co, Mn, Al etc.) component is many, and composition has fluctuation, is that raw material is smelted AB with the RE-M alloy that reclaims
5The type alloy, not too convenient during use.
Summary of the invention
The object of the present invention is to provide short, the efficient cheapness of a kind of technical process, less energy-consumption, oligosaprobic a kind of comprehensive reutilization method based on selective oxidation/reductive rare earth nickel metal hydride battery waste material.
Technical solution:
Nickel metal hydride battery waste material of the present invention adopts selective oxidation/reduction-molten point-score of slag gold to reclaim.
1. selective oxidation/reduction method
Waste material is made the following powder of 80 orders, and the powder nickel material boat of packing into is sent into the zone of constant temperature of High Temperature Furnaces Heating Apparatus, and High Temperature Furnaces Heating Apparatus is airtight, vacuumizes or feed argon gas earlier, discharges furnace air, feeds (H then
2+ H
2O) or (CO+CO
2) or (H
2+ CO+H
2O+CO
2) processing of carrying out property of mixed gas selective oxidation, 600～1200 ℃ of treatment temps, treatment time 〉=material reaches the constant weight time.After reaction finished, material cooled off under argon shield.Adopt (H
2+ H
2O) time, H
2O accounts for (H
2+ H
2O) volume percent is 20～80%; Adopt (CO+CO
2) time, CO
2Account for (CO+CO
2) volume percent be 20～80%; Adopt (H
2+ CO+H
2O+CO
2) time, (H
2+ CO) account for (H
2+ CO+H
2O+CO
2) volume percent be 20～80%.All gases is by the under meter accurate measurement.
H
2O or CO
2Be oxygenant, the active element of simple substance attitude and alloy attitude (rare earth, aluminium, manganese etc.) in the selective oxidation waste material.
H
2Or CO is reductive agent, inert metal (nickel, cobalt) oxide compound in the selective reduction expense material.
2. the slag gold melts point-score
The material that selective oxidation/reduction method is handled is allocated slag former into, adds in the crucible of electric furnace, and 1450～1650 ℃ of following meltings, realization slag gold melts and divides, and obtains Ni-Co alloy and rare earth oxide slag after the cooling.
Slag former is Al
2O
3, SiO
2, CaF
2, Na
2CO
3In one or more.Al
2O
3, SiO
2Add-on by the control of the basicity of slag.The basicity of slag is controlled between 0.5～1.5.The basicity of slag=alkaline oxygenated amount/acidic oxidation amount, rare earth oxide is basic oxide, Al
2O
3, SiO
2Be acidic oxide.CaF
2, Na
2CO
3Be the shoddye agent, add or do not add according to slag gold separation case.
Rare earth nickel metal hydride battery waste material refers to respectively: the waste residue that the rare earth nickel-hydrogen cell cathode alloy material produces when smelting; Discarded rare earth nickel-hydrogen battery electrode powder.The main component of rare earth nickel metal hydride battery waste material: category-A rare earth element (La, Ce, Pr, Nd), category-B element (Ni, Co, Mn, Al etc.), these elements are with simple substance attitude, alloy attitude (AB
x, x is 4.8～5.2), oxidation state exists.
The Ni-Co alloy can be used as smelts rare earth hydrogen storage alloy or other alloy materials, and the rare earth oxide slag then can be used as the smelting RE-Si alloy materials or further extracts the raw material of rare earth, has realized the comprehensive reutilization of rare-earth series nickel-hydrogen cell waste material.
Characteristics of the present invention are: utilize the chemical property of metallic element to determine the chemical state of element, promptly the active element selective oxidation is an oxide compound, and inert element is the simple substance attitude, and the high temperature sludge gold separates then.
The invention has the advantages that: whole process flow is short, and technology is simple, and energy consumption is low, and waste material obtains comprehensive reutilization.Ni-Co alloy purposes is wider.
Embodiment
Embodiment 1: the fragmentation of rare earth nickel metal hydride battery alloy smelting waste residue; sieve; make to the following powder of 80 orders, weighing waste residue powder 1000g puts into nickel material boat; send in the flat-temperature zone in the resistance furnace; be evacuated to below the 20Pa, charge into argon gas, heat up under the argon shield atmosphere; be warming up to 400 ℃, switch to (H
2+ H
2O), H
2O accounts for (H
2+ H
2O) volume percent is 25.0%, then is warming up to 950 ℃ of insulations 2.0 hours, carries out selective oxidation/reduction and handles.Insulation switches to argon gas after finishing, and is cooled to room temperature under the argon shield atmosphere.Get selective oxidation material handling 500.0g, with addition of SiO
2200.0g, CaF
220.0g, briquetting, the corundum crucible of packing into, 1600 ℃ of insulations 0.5 hour under the argon gas atmosphere in vacuum carbon tube furnace carry out that slag gold is molten to be divided.Obtain Ni-Co alloy 254.0g, rare earth slag 463.0g.The chemical ingredients of alloy and slag sees Table 1 respectively, table 2.
Embodiment 2: the fragmentation of rare earth nickel metal hydride battery alloy smelting waste residue; sieve; make to the following powder of 80 orders, weighing waste residue powder 1000g puts into nickel material boat; send in the flat-temperature zone in the resistance furnace; be evacuated to below the 20Pa, charge into argon gas, heat up under the argon shield atmosphere; be warming up to 400 ℃, switch to (CO+CO
2), CO
2Account for (CO+CO
2) volume percent be 50.0%, then be warming up to 900 ℃ of insulations 2.5 hours, carry out the processing of selective oxidation/reduction.Insulation switches to argon gas after finishing, and is cooled to room temperature under the argon shield atmosphere.Get selective oxidation material handling 500.0g, with addition of SiO
2200.0g, Na
2CO
320.0g, briquetting, the corundum crucible of packing into, 1550 ℃ of insulations 0.5 hour under the argon gas atmosphere in vacuum carbon tube furnace carry out that slag gold is molten to be divided.Obtain Ni-Co alloy 256.0g, rare earth slag 461.0g.
Embodiment 3: discarded rare earth nickel metal hydride battery; through Mechanical Crushing, washing, drying, screening; obtain 80 orders with the lower electrode powder, the weighing electrode powder 1000g that gives up puts into nickel material boat; send in the flat-temperature zone in the resistance furnace; be evacuated to below the 20Pa, charge into argon gas, heat up under the argon shield atmosphere; be warming up to 400 ℃, switch to (H
2+ H
2O), H
2O accounts for (H
2+ H
2O) volume percent is 30.0%, then is warming up to 1000 ℃ of insulations 1.5 hours, carries out selective oxidation/reduction and handles.Insulation switches to argon gas after finishing, and is cooled to room temperature under the argon shield atmosphere.Get selective oxidation material handling 500.0g, with addition of SiO
2100.0g, briquetting, the corundum crucible of packing into, 1580 ℃ of insulations 0.5 hour under the argon gas atmosphere in vacuum carbon tube furnace carry out that slag gold is molten to be divided.Obtain Ni-Co alloy 325.5g, rare earth slag 272.0g.
Embodiment 4: discarded rare earth nickel metal hydride battery; through Mechanical Crushing, washing, drying, screening; obtain 80 orders with the lower electrode powder, the weighing electrode powder 1000g that gives up puts into nickel material boat; send in the flat-temperature zone in the resistance furnace; be evacuated to below the 20Pa, charge into argon gas, heat up under the argon shield atmosphere; be warming up to 400 ℃, switch to (H
2+ CO+H
2O+CO
2), the percent by volume of all gases is: 35%H
2, 35%CO, 15%H
2O, 15%CO
2Then be warming up to 1050 ℃ of insulations 1.2 hours, carry out selective oxidation/reduction and handle.Insulation switches to argon gas after finishing, and is cooled to room temperature under the argon shield atmosphere.Get selective oxidation material handling 500.0g, with addition of SiO
2110.0g, briquetting, the corundum crucible of packing into, 1580 ℃ of insulations 0.5 hour under the argon gas atmosphere in vacuum carbon tube furnace carry out that slag gold is molten to be divided.Obtain Ni-Co alloy 324.3g, rare earth slag 283.2g.
The typical Ni-Co alloy mass index that reclaims of table 1
The typical rare earth slag chemical ingredients that reclaims of table 2
Claims (3)
1. based on the comprehensive reutilization method of selective oxidation/reductive rare earth nickel metal hydride battery waste material, it is characterized in that: waste material comprises rare earth hydrogen storage alloy melting waste slag and discarded rare earth nickel-hydrogen battery electrode powder, adopt the molten method that reclaims Ni-Co alloy and rare earth slag of dividing of selective oxidation/reduction-slag gold, recovery method is as follows: 1) waste material is made the following powder of 80 orders, carrying out selective oxidation/reduction by the mixed gas that has oxidation and reductibility simultaneously in High Temperature Furnaces Heating Apparatus handles, 600～1200 ℃ of treatment temps, treatment time 〉=material reaches the constant weight time; Handling the back material is metal simple-substance and hopcalite, 2) material of selective oxidation/reduction processing, carry out the molten divisional processing of slag gold, material is allocated slag former into, add in the electric furnace, 1450～1650 ℃ of following meltings realize the molten branch of slag gold, obtain Ni-Co alloy and rare earth oxide slag after the cooling, the add-on of slag former is controlled between 0.5～1.5 by the basicity of slag.
2. the comprehensive reutilization method based on selective oxidation/reductive rare earth nickel metal hydride battery waste material according to claim 1 is characterized in that, it is (H that the gas that has oxidation and reductibility when adopting is handled in selective oxidation/reduction
2+ H
2O) or (CO+CO
2) or (H
2+ CO+H
2O+CO
2) mixed gas, H
2O accounts for (H
2+ H
2O) or CO
2Account for (CO+CO
2) or (H
2+ CO) account for (H
2+ CO+H
2O+CO
2) volume percent be 20～80%.
3. the comprehensive reutilization method based on selective oxidation/reductive rare earth nickel metal hydride battery waste material according to claim 1 is characterized in that, the slag former that the molten divisional processing of slag gold is allocated into is Al
2O
3, SiO
2, CaF
2, Na
2CO
3In one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100935547A CN102181646A (en) | 2011-04-08 | 2011-04-08 | Comprehensive recycle and utilization method based on selective oxidation/ reduction rare earth nickel-metal hydride battery waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100935547A CN102181646A (en) | 2011-04-08 | 2011-04-08 | Comprehensive recycle and utilization method based on selective oxidation/ reduction rare earth nickel-metal hydride battery waste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102181646A true CN102181646A (en) | 2011-09-14 |
Family
ID=44567932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100935547A Pending CN102181646A (en) | 2011-04-08 | 2011-04-08 | Comprehensive recycle and utilization method based on selective oxidation/ reduction rare earth nickel-metal hydride battery waste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102181646A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876898A (en) * | 2012-09-27 | 2013-01-16 | 江西稀有稀土金属钨业集团有限公司 | Method and system for treatment of return scraps produced from rare-earth hydrogen storage alloy smelting process |
| CN104388684A (en) * | 2014-12-11 | 2015-03-04 | 内蒙古科技大学 | Method for preparing rare earth oxide slag from composite rare earth waste and method for leaching rare earth from slag |
| CN104611566A (en) * | 2014-12-29 | 2015-05-13 | 长沙矿冶研究院有限责任公司 | Method for recycling valuable metals in waste lithium ion batteries |
| CN106756042A (en) * | 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 | A kind of recovery processing technique of waste nickel hydrogen battery |
| CN110983043A (en) * | 2019-11-28 | 2020-04-10 | 武汉科技大学 | Method for preparing high-grade ferronickel from medium-low grade laterite-nickel ore |
| JP2021143394A (en) * | 2020-03-12 | 2021-09-24 | 株式会社神戸製鋼所 | Recovery method of valuable metal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1932054A (en) * | 2006-10-21 | 2007-03-21 | 内蒙古科技大学 | Process of extracting RE-Ni-Co alloy from waste hydrogen-storing RE alloy |
| CN101748279A (en) * | 2010-01-22 | 2010-06-23 | 内蒙古科技大学 | Method for recycling smelting slag of AB5 type rare earth-based hydrogen storage alloy |
-
2011
- 2011-04-08 CN CN2011100935547A patent/CN102181646A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1932054A (en) * | 2006-10-21 | 2007-03-21 | 内蒙古科技大学 | Process of extracting RE-Ni-Co alloy from waste hydrogen-storing RE alloy |
| CN101748279A (en) * | 2010-01-22 | 2010-06-23 | 内蒙古科技大学 | Method for recycling smelting slag of AB5 type rare earth-based hydrogen storage alloy |
Non-Patent Citations (3)
| Title |
|---|
| 《内蒙古科技大学学报》 20090930 高志平等 从废渣中提取的稀土镍钴合金储氢性能的研究 217-220 1-3 第28卷, 第3期 * |
| 《国外金属矿选矿》 20060630 H·海根 从废镍氢电池中再生回收镍、钴和稀土金属的闭路循环 第35页图2，1 废弃镍氢电池的机械处理，第36页2 火法冶金处理 1-3 , * |
| 《稀有金属》 20100131 吴巍等 废镍氢电池中镍、钴和稀土金属回收工艺研究 79-84 1-3 第34卷, 第1期 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876898A (en) * | 2012-09-27 | 2013-01-16 | 江西稀有稀土金属钨业集团有限公司 | Method and system for treatment of return scraps produced from rare-earth hydrogen storage alloy smelting process |
| CN104388684A (en) * | 2014-12-11 | 2015-03-04 | 内蒙古科技大学 | Method for preparing rare earth oxide slag from composite rare earth waste and method for leaching rare earth from slag |
| CN104611566A (en) * | 2014-12-29 | 2015-05-13 | 长沙矿冶研究院有限责任公司 | Method for recycling valuable metals in waste lithium ion batteries |
| CN106756042A (en) * | 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 | A kind of recovery processing technique of waste nickel hydrogen battery |
| CN110983043A (en) * | 2019-11-28 | 2020-04-10 | 武汉科技大学 | Method for preparing high-grade ferronickel from medium-low grade laterite-nickel ore |
| CN110983043B (en) * | 2019-11-28 | 2021-11-23 | 武汉科技大学 | Method for preparing high-grade ferronickel from medium-low grade laterite-nickel ore |
| JP2021143394A (en) * | 2020-03-12 | 2021-09-24 | 株式会社神戸製鋼所 | Recovery method of valuable metal |
| JP7378900B2 (en) | 2020-03-12 | 2023-11-14 | 株式会社神戸製鋼所 | How to recover valuable metals |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hu et al. | Recovery of Co, Ni, Mn, and Li from Li-ion batteries by smelting reduction-Part I: A laboratory-scale study | |
| CN102251097B (en) | Method for recovering metal from waste lithium battery | |
| CN101383440B (en) | Method for recycling and preparing superfine nickel powder from nickel-hydrogen cell | |
| KR100717389B1 (en) | A valuable material recovery method of a scrapped Lithium ion battery | |
| CN102181646A (en) | Comprehensive recycle and utilization method based on selective oxidation/ reduction rare earth nickel-metal hydride battery waste | |
| CN102251118B (en) | Method for recycling metals from waste nickel-hydrogen batteries | |
| CN103725897A (en) | Method for directly producing high-purity oxygen-free copper by pyrogenic process continuous refining of scrap copper | |
| CN103146943B (en) | Red impure copper refining agent and preparation method thereof | |
| CN103077796B (en) | Corrosion-resistant neodymium-iron-boron permanent magnet material and preparation method thereof | |
| WO2020151478A1 (en) | Method for recovering rare earth element from neodymium-iron-boron scrap by means of extraction with liquid metal bismuth | |
| CN101748279B (en) | Method for recycling smelting slag of AB5 type rare earth-based hydrogen storage alloy | |
| CN104451215A (en) | Method for preparing aluminum alloy by virtue of molten salt electrodeoxidation-ingot metallurgy | |
| CN102337408A (en) | Two-step reduction method for recycling stainless steel scales | |
| CN111187924A (en) | Device and method for continuously refining lithium from lithium-containing material | |
| WO2020215857A1 (en) | Method for extracting rare earth element from neodymium-iron-boron waste by means of metal lead liquid-liquid separation | |
| CN102206756B (en) | Method for comprehensively recycling rare earth nickel-metal hydride battery waste through direction reduction-slag-metal melting and separation | |
| Huang et al. | Hydrogen reduction of spent lithium-ion battery cathode material for metal recovery: Mechanism and kinetics | |
| CN112481499A (en) | Method for recycling and reusing silver graphite waste | |
| CN105514400B (en) | The method for battery cathode active material hydrogen bearing alloy is prepared using waste nickel hydrogen battery | |
| CN112111649B (en) | Method for recovering valuable metals in lithium ion battery | |
| CN211897068U (en) | Lithium-containing material continuous lithium smelting device | |
| Bian et al. | Recovery of rare earth elements from NdFeB magnet scraps by pyrometallurgical processes | |
| CN106636668A (en) | Waste electromagnetic wire copper refining agent and preparation method and application thereof | |
| JP3526983B2 (en) | Method for recovering active components from nickel-hydrogen storage alloy secondary batteries | |
| JP3614987B2 (en) | Method for reducing oxygen in hydrogen storage alloys |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110914 |