CN106086418B - A kind of method that waste and old device performance of sintered NdFeB recovers - Google Patents
A kind of method that waste and old device performance of sintered NdFeB recovers Download PDFInfo
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- CN106086418B CN106086418B CN201610504099.8A CN201610504099A CN106086418B CN 106086418 B CN106086418 B CN 106086418B CN 201610504099 A CN201610504099 A CN 201610504099A CN 106086418 B CN106086418 B CN 106086418B
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- waste
- slag
- iron boron
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- neodymium iron
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- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000002699 waste material Substances 0.000 title claims abstract description 35
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002893 slag Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 238000011084 recovery Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 230000007797 corrosion Effects 0.000 claims abstract description 16
- 238000005260 corrosion Methods 0.000 claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000470 constituent Substances 0.000 claims abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 9
- 230000005347 demagnetization Effects 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000004566 building material Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 23
- 238000010792 warming Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000013461 design Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000005275 alloying Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- 239000012224 working solution Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 239000010953 base metal Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 230000007423 decrease Effects 0.000 claims 1
- 230000003628 erosive effect Effects 0.000 claims 1
- 238000007499 fusion processing Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims 1
- 235000010234 sodium benzoate Nutrition 0.000 claims 1
- 239000004299 sodium benzoate Substances 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 claims 1
- 229910052692 Dysprosium Inorganic materials 0.000 abstract description 4
- 229910052771 Terbium Inorganic materials 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 229910052733 gallium Inorganic materials 0.000 abstract description 2
- 229910052758 niobium Inorganic materials 0.000 abstract description 2
- 230000002829 reductive effect Effects 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract 2
- 229910017061 Fe Co Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 230000005389 magnetism Effects 0.000 description 7
- 229910052779 Neodymium Inorganic materials 0.000 description 6
- -1 cobalt Rare earth Chemical class 0.000 description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- PXAWCNYZAWMWIC-UHFFFAOYSA-N [Fe].[Nd] Chemical compound [Fe].[Nd] PXAWCNYZAWMWIC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- GEZAXHSNIQTPMM-UHFFFAOYSA-N dysprosium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Dy+3].[Dy+3] GEZAXHSNIQTPMM-UHFFFAOYSA-N 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
-
- 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
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a kind of method for recovering the waste and old device performance of sintered NdFeB.The waste and old device of sintered NdFeB removes water demagnetization removal of impurities through oil removing and goes the processes such as corrosion-resistant coating cleaning-drying vacuum melting to obtain (Nd, R)x(Fe, M)yBz(R refers to substitution Nd heavy rare earth metal Dy, Tb etc. to alloy；M refers to substitution Fe Co, Nb, Ga, Cu, Al etc.).Alloy produces sintered NdFeB device, realizes performance recovery " from the old to the new " with 1~10% new raw material dispensing.The advantage of the invention is that：Technological process is short, and metal recovery rate is high, and energy consumption is low；Equipment is simple, reduced investment, and obtained alloy can be directly used for producing neodymium iron boron, and added value is high；Whole process does not produce waste water, and tail gas is free of nuisance, and after slag recovery valuable constituent, finishing slag is harmless, available for doing building materials.Whole method integrated cost is low, green, can create huge economic and social benefit.
Description
Technical field:
The present invention relates to the waste and old device renovation process of sintered NdFeB, especially a kind of waste and old device performance of sintered NdFeB
The method of recovery, belong to vacuum metallurgy field.
Background technology：
Nineteen eighty-two, the researcher of SUMITOMO CHEMICAL particulate metal company help river true man (Masato Sagawa) and are found that one
New rare earth permanent-magnetic material-neodymium iron boron the Nd of kind2Fe14B, sintered NdFeB rare-earth permanent magnetism (the rear abbreviation using the material as matrix phase
Neodymium iron boron) device has excellent comprehensive magnetic energy, it is widely used in electronics, electric machinery, Medical Instruments, packaging, hardware machine
The fields such as tool, computer, Aero-Space, ocean engineering and Chemical Engineering.
It is with the same iron of neodymium metal, boron and other alloys, metal (praseodymium, dysprosium, terbium, niobium, aluminium, gallium, cobalt, copper etc.) to produce neodymium iron boron
Carry out composition design, dispensing, melting, Cast Strip, powder processed, shaping, sintering, heat treatment, cutting polishing processing, preservative treatment, magnetize,
The series of processes such as inspection and packaging, which is made, meets that user requires the process of product/device.The normal use temperature of neodymium iron boron device
Spend for ± 40~80 DEG C, normal service life is 20~30 years, the temperature of workplace, the time, electromagnetic field, machinery (vibration with
Impact), ray, chemical action etc. can all influence service life, in adverse circumstances such as Aero-Space, ocean engineering, Chemical Engineerings
Lower service life is shorter.Neodymium iron boron industrialization is passed by 30 years, and early production production technology is immature, has been reached and has been scrapped the time limit, many
The waste and old device amount of neodymium iron boron that more scholars think to scrap in recent years will increase severely, and these waste and old devices contain (Nd, R) 20~33%, contained
(Fe, M) 50~69%, containing B 0.7~1.3%, recovery value is high, along with the increasingly rare of non-renewable mineral resources,
Controlling ecological environment, the waste and old device performance of progress neodymium iron boron recover energetically for country, recycle the strategic resources such as rare earth, meaning weight
Greatly, have a extensive future.
People begin to pay close attention to scrap loop Utilizing question at the beginning of neodymium iron boron industry is risen, and the research of domestic this aspect is very
It is more, the research of external correlation is not found.The country, Lin Hecheng is using neodymium iron boron waste material as raw material, using sulfuric acid dissolution, sodium sulfate double salt
Precipitation, oxalic acid conversion, the technique of drying calcining, the neodymia that purity is more than 95% is made, the rate of recovery is more than 85%, processing one
Ton waste material can make a profit profit 0.55~0.60 ten thousand yuan；It is real that Chen Yufeng etc. carries out sulfuric acid dissolution, calcium phosphate precipitation neodymium to neodymium iron boron waste material
Existing neodymium iron separation, change molten acid, ammonium carbonate precipitation through alkali, calcine to obtain neodymia, purity is more than 99%, and the rate of recovery is more than 90%；
Zhang Wanyan etc. is aoxidized respectively using sour decomposition, purification and impurity removal, the precipitation PROCESS FOR TREATMENT neodymium iron boron waste material such as rare-earth separating and cobalt
Rare earth and cobalt oxide powder, cobalt oxide powder have reached Y1 class product requirements, the rare earth oxide rate of recovery 95.2%, the cobalt rate of recovery
82.2%；Each clear wait of Liu carries out the masters such as oxidizing roasting, the molten removal of impurities of acid, extract and separate, ignition of precipitate by raw material of neodymium iron boron waste material
Process is wanted, has obtained the rare earth oxide that purity is more than 99%, the rate of recovery of rare earth oxide is more than 95%.Chinese patent
200410020840.0 disclose a kind of new technology of the recovering rare earth from neodymium iron boron waste material, have obtained purer neodymia, oxygen
Change terbium and dysprosia；Chinese patent 201210164586.6 discloses a kind of side of the recovering rare earth from waste and old NdFeB material
Method, the method eliminate conventional technique to carry out purification by liquid extraction and use the trouble of middle calcination and secondary dissolving, Ke Yizhi
Connect for purification by liquid extraction, improve the rate of recovery, simplify production process, reduce production cost；Chinese patent 201410073670.6 is public
A kind of separation Application way of neodymium iron boron waste material is opened, the method rate of recovery and purity are high, environment friendly and pollution-free, cost recovery is low.
These methods, as raw material, it is waste and old not to be suitable for neodymium iron boron to manufacture waste material caused by neodymium iron boron device process
The performance recovery of device；Technological process is grown, and process conditions are harsh, and equipment corrosion resistance requires high, and investment is big, high energy consumption, cost
It is high；Product is generally rare earth oxide, single rare earth oxide, it is impossible to is directly used in production neodymium iron boron, added value is relatively low；To ring
Border pollution is larger, and " three wastes " are not administered effectively；Majority is also in laboratory stage, and the road also very long from industrialization will
Walk.
In view of the waste and old device performance of neodymium iron boron recovers technique and still belongs to blank at present, the present invention proposes that a kind of flow is short, production
High, the green technique for recovering the waste and old device performance of neodymium iron boron of product added value, can fill up this blank.
The content of the invention：
A kind of method recovered it is an object of the invention to disclose a kind of waste and old device performance of neodymium iron boron, it is proposed that flow
The method that the waste and old device performance of neodymium iron boron short, that added value of product is high, green recovers.As shown in Figure 1, key step is such as
Under：
1. the waste and old device of neodymium iron boron is placed in vacuum resistance baking oven, it is evacuated to pressure in case and is down to 20~10-1Pa, start
Heating systems, 150~400 DEG C are warming up to 1~10 DEG C/min heating rate, is incubated 10~60min oil removings, water removal, demagnetization,
It is cooled to room temperature and takes out material.Collected after oil volatilization in accumulator tank, with the purified emptying of flue gas after water volatilization；
2. material crosses 2~10 mesh sieves, mud, dirt, metal powder/bits, oxide skin etc. are screened out, is cleaned with 35~50 DEG C of water, mud,
Dirt, metal powder/bits, oxide skin etc. reclaim valuable constituent；
3. material, which immerses, removes corrosion-resistant coating groove, start supersonic generator, 20~30kHz of frequency, each soak time is not
More than 40s, repeatedly immersion, corrosion-resistant coating is removed completely, with 35~50 DEG C of water cleaning, drying；Corrosion removal layer liquid works one section
After valuable constituent, purification are reclaimed after time, return to match somebody with somebody and remove corrosion-resistant coating liquid working solution；
4. material is added in vacuum medium frequency induction furnace, active metal is deoxidier, and calcium oxide and silica are slag former,
It is evacuated to furnace pressure and is down to below 10Pa, starts heating system, 450 are warming up to 5~15 DEG C/min heating rate~
650 DEG C, 10~40min is incubated, then 1350~1500 DEG C are warming up to 5~15 DEG C/min heating rate.Temperature-rise period treats stove
Interior pressure is down to below 1Pa, starts high vacuum system, and furnace pressure is down to 10-2~10-3Below Pa.Treat that material is completely melt to add
Enter deoxidier and slag former, tune up intermediate frequency power supply frequency to 1500~2500Hz, 10~40min of melting, melting and terminate to topple over earthenware
Crucible, alloy molten solution is injected into mold, be cooled to room temperature, blow-on, take out alloy, smelting slag recovery valuable constituent, finishing slag is harmless, can
For doing building materials；
5. according to alloying component, related grade neodymium-iron-boron composition design is carried out, a small amount of virgin material dispensing is added, neodymium iron boron device is made
Part.
Advantages of the present invention：
1. a technique recovers its performance using the waste and old device of neodymium iron boron as raw material, without the separation of thulium, system
Composition and alloy similar in product are obtained, after adding the simply adjustment of 1~10% new raw material, neodymium iron boron production is can be directly used for, avoids class
Like traditional waste recovery technique with after chemical method one by one separating rare-earth metal, " detour " for preparing neodymium iron boron device is reconfigured,
Technological process is short, and the rate of recovery is high, and cost can be greatly reduced；
2. the killing vacuum melting control oxygen technology of autonomous innovation, deoxidier dosage is few, and deaerating effect is good, avoids similar
Traditional waste recovery technique deep oxidation-oxide-reduction-metal, " idle work " that " oxidationreduction " is done, can significantly drop
Low energy consumption；
3. whole technical process do not produce waste water, waste gas it is pollution-free it is purified after can directly empty, slag etc. recovery it is valuable
After composition, finishing slag amount is few pollution-free, and for doing building materials, whole technical process is green.
4. equipment is simple, corrosion resistance is saved without particular/special requirement, construction investment, scale is changeable, and promotion prospect is good.
Brief description of the drawings
Fig. 1 is the process chart of the present invention
Embodiment：
The present invention is further illustrated in conjunction with the embodiments, without limiting the present invention
Embodiment 1
Operated according to technological process described in Fig. 1：The waste and old device 10000g of neodymium iron boron is taken to be placed in vacuum electric as raw material
Hinder in baking oven, vacuumize when pressure is down to 3Pa in case, start heating system, 300 are warming up to 10 DEG C/min heating rate
DEG C, insulation 20min oil removings, water removal, demagnetization, cooling, material is taken out, cross 4 mesh sieves, screen out mud, dirt, metal powder/bits, oxide skin
Deng after being cleaned with 40 DEG C of water, immersion is gone in corrosion-resistant coating groove, soaks 20s every time, totally 4 times, 50 DEG C of water cleaning, drying, is obtained clean
Expect 9589g.It will totally expect to add in intermediate frequency vaccum sensitive stove, 200g calcium metals are deoxidier, 280g calcium oxide and 224g dioxies
SiClx is slag former, is vacuumized when furnace pressure is down to 8Pa, starts heating system, high vacuum system is preheated, with 10 DEG C/min
Heating rate be warming up to 500 DEG C of insulation 20min, then be warming up to 1410 DEG C with 10 DEG C/min heating rate, temperature-rise period, treat
Furnace pressure is down to below 1Pa, starts high vacuum system.Temperature rises to 1410 DEG C, material rapid melting, adds deoxidier, makes
Slag agent, tuning up intermediate frequency power supply frequency to 2000Hz, melting 22min, melting and terminate to topple over crucible, alloy molten solution is injected in mold,
Cooling, furnace temperature are down to room temperature, take out alloy 9493g.By alloy and the boron of 15g neodymium metals, 467g straight iron powders and 25g boracics 20%
Ferroalloy, by (Nd, Dy)30.84%(Fe、Cu)68.11%B1.05%(mass fraction) carries out partition design, dispensing 10000g, entrusts neodymium
20mm × 5mm × 30mm neodymium iron boron device example is made in Tie Peng device productions producer, and to the remanent magnetism B of sampler, magnetic induction rectifys
Stupid power Hcb, HCJ Hcj, maximum magnetic energy product (BH)maxIt is tested etc. main magnetic property, as a result sees below expression：
The main magnetism testing result of table neodymium iron boron device example
It is 048011 (NdFeB380/107) that the main magnetic property of device example, which meets the M classes trade mark in GB/T1560-2009,
Performance requirement.
Embodiment 2
Operated according to technological process described in Fig. 1：The waste and old device 10000g of neodymium iron boron is taken to be placed in vacuum electric as raw material
Hinder in baking oven, vacuumize when pressure is down to 5Pa in case, start heating system, 320 are warming up to 10 DEG C/min heating rate
DEG C, insulation 30min oil removings, water removal, demagnetization, cooling, material is taken out, cross 4 mesh sieves, screen out mud, dirt, metal powder/bits, oxide skin etc.
Afterwards, cleaned with 45 DEG C of water, immersion is gone in corrosion-resistant coating groove, soaks 15s every time, totally 4 times, and 50 DEG C of water are cleaned, dried, and is obtained clean
Expect 9243g.It will totally expect to add in intermediate frequency vaccum sensitive stove, 313g calcium metals are deoxidier, 438g calcium oxide and 500g dioxies
SiClx is slag former, is vacuumized when furnace pressure is down to 10Pa, start heating system, preheat high vacuum system, with 15 DEG C/
Min heating rate is warming up to 500 DEG C of insulation 20min, then is warming up to 1400 DEG C with 10 DEG C/min heating rate, heats up
Journey, when furnace pressure is down to below 1Pa, start high vacuum system.Temperature rises to 1400 DEG C, material rapid melting, adds de-
Oxygen agent, slag former, tune up intermediate frequency power supply frequency to 2200Hz, melting 25min, melting and terminate to topple over crucible, alloy molten solution injection
In mold, cooling, furnace temperature is down to room temperature, takes out alloy 9123g.By alloy with 369g neodymiums, 258g straight iron powders, by (Nd,
Dy)31.56%Fe67.40%B1.04%(mass fraction) carries out partition design, dispensing 9750g, and commission neodymium iron boron device production producer is made
20mm × 5mm × 30mm neodymium iron boron device example, and to the remanent magnetism B of sampler, magnetic induction coercivity Hcb, HCJ Hcj、
Maximum magnetic energy product (BH)maxIt is tested etc. main magnetic property, as a result sees below expression：
The main magnetism testing result of table neodymium iron boron device example
It is 048021 (NdFeB365/127) that the main magnetic property of device example, which meets the H classes trade mark in GB/T1560-2009,
Performance requirement.
Embodiment 3
Operated according to technological process described in Fig. 1：The waste and old device 10000g of neodymium iron boron is taken to be placed in vacuum electric as raw material
Hinder in baking oven, vacuumize when pressure is down to 10Pa in case, start heating system, be warming up to 10 DEG C/min heating rate
350 DEG C, insulation 15min oil removings, water removal, demagnetization, cooling, material is taken out, cross 4 mesh sieves, screen out mud, dirt, metal powder/bits, oxidation
After skin etc., cleaned with 45 DEG C of water, immersion is gone in corrosion-resistant coating groove, is soaked 12s every time, totally 4 times, 50 DEG C of water cleaning, drying, is obtained dry
Net material 9460g.It will totally expect to add in intermediate frequency vaccum sensitive stove, 210g calcium metals are deoxidier, 294g calcium oxide and 336g bis-
Silica is slag former, when being evacuated to furnace pressure and being down to 8Pa, starts heating system, preheats high vacuum system, with 5 DEG C/
Min heating rate is warming up to 500 DEG C of insulation 20min, then is warming up to 1430 DEG C with 5 DEG C/min heating rate, temperature-rise period,
When furnace pressure is down to below 1Pa, start high vacuum system.Temperature rises to 1430 DEG C, material rapid melting, adds deoxidation
Agent, slag former, tune up intermediate frequency power supply frequency to 2400HZ, melting 30min, melting and terminate to topple over crucible, alloy molten solution injection casting
In mould, cooling, furnace temperature is down to room temperature, takes out alloy 9372g.Alloy is pressed into Nd with 150g neodymiums, 28g straight iron powders31.14(Fe,
Co)67.84B1.02Partition design is carried out, 20mm × 5mm × 30mm neodymium is made in dispensing 9550g commission neodymium iron boron device productions producer
Iron boron device example, and to the remanent magnetism B of the sampler, magnetic induction coercivity Hcb, HCJ Hcj, maximum magnetic energy product (BH)max
It is tested etc. main magnetic property, as a result sees below expression：
The main magnetism testing result of the neodymium iron boron device example of table 1
It is 048001 (NdFeB380/80's) that the main magnetic property of device example, which meets the N classes trade mark in GB/T1560-2009,
Performance requirement.
Claims (6)
1. a kind of method that waste and old device performance of sintered NdFeB recovers, its feature include：
Step 1, the waste and old device of sintered NdFeB are placed in vacuum resistance baking oven, are evacuated to pressure in case and are down to 20~10-1Pa,
Start heating system, 150~400 DEG C be warming up to 1~10 DEG C/min heating rate, 10~60min of insulation oil removings, water removal,
Demagnetization, material is taken out after cooling, is collected after oil volatilization in accumulator tank, with the purified emptying of flue gas after water volatilization；
Step 2, the material obtained in step 1 cross 2~10 mesh sieves, screen out mud, dirt, metal powder/bits, oxide skin, then with 35~
50 DEG C of water is cleaned, mud, dirt, metal powder/bits, oxide skin recovery valuable constituent；
Step 3, the material obtained in step 2, which immerses, removes corrosion-resistant coating groove, starts supersonic generator, 20~30kHz of frequency,
Each soak time is no more than 40s, repeatedly immersion, and corrosion-resistant coating removes completely, with 35~50 DEG C of water cleaning, drying, goes corruption
Erosion layer reclaims valuable constituent after liquid work a period of time, after purification, returns to match somebody with somebody and removes corrosion-resistant coating liquid working solution；
Step 4, the material obtained in step 3 are added in vacuum medium frequency induction furnace, and active metal is deoxidier, calcium oxide and two
Silica is slag former, is evacuated to furnace pressure and is down to below 10Pa, starts heating system, with 5~15 DEG C/min heating
Speed is warming up to 450~650 DEG C, is incubated 10~40min, then be warming up to 1350~1500 with 5~15 DEG C/min heating rate
DEG C, temperature-rise period treats that furnace pressure is down to below 1Pa, starts high vacuum system, it is quick that temperature rises to 1350~1500 DEG C of materials
Fusing, deoxidier, slag former are added, intermediate frequency power supply frequency to 1500~2500Hz, 10~60min of melting, melting is tuned up and terminates
Topple over crucible, alloy molten solution injection is put into the steel mold in burner hearth in advance, starts to be naturally cooling to room temperature, blow-on, takes out and close
Gold, smelting slag recovering rare earth valuable constituent, finishing slag is harmless, for doing building materials；
Step 5, according to alloying component, neodymium iron boron composition design is carried out, 1~10% new raw material dispensing is added, neodymium iron boron device is made
Part.
2. according to the method for claim 1, it is characterised in that：The waste and old device of sintered NdFeB in step 1 refers to exceed
Service life, magnetic property decline, machinery, the waste and old device that mechanical property is insufficient or other reasons can not be continuing with, containing Nd 20
~33%, containing Fe 50~69%, containing B 0.7~1.3%, remaining 1~10% is that oil, mud, metal powder/bits, oxide skin etc. are miscellaneous
There is corrosion-resistant coating on matter, surface, have certain magnetic, and because magneticaction is easily reunited, accumulator tank is the pass for forming oil collecting system
Key member, oil herein collect by condensation.
3. according to the method for claim 1, it is characterised in that：Mud, dirt, metal powder/bits, oxide skin are impure in step 2
It is more, it is corroded serious, not influence subsequent step, sieving is sorted out, and after reclaiming valuable constituent, finishing slag is harmless, for doing building materials.
4. according to the method for claim 1, it is characterised in that：Step 3 removes the nitric acid that corrosion-resistant coating liquid contains 2~10%,
To avoid base metal from dissolving, add 0.5~1.5% sodium benzoate, 0.3~0.9% triethanol ammonium as additive, delay
Agent is lost, valuable constituent is rich in after going corrosion-resistant coating liquid work a period of time, reclaims valuable constituent, is returned after purification and prepares work
Liquid, recycle.
5. according to the method for claim 1, it is characterised in that：Step 4 deoxidier is strong with the adhesion of oxygen, fusion process
Capture the formation oxide of the oxygen in material and enter slag, effectively reduce the oxygen content of material, slag density is less than liquation, after layering
Float on crucible top, slag is separated with liquation, and the addition of deoxidier is pressed using the analysis result of clean material oxygen content as foundation
The theoretical amount of equation 1 adds,
XMe (deoxidier)+yO=MexOy‥‥‥‥‥‥‥‥1。
6. according to the method for claim 1, it is characterised in that：Step (5) neodymium iron boron composition design should close to alloying component,
Less plus new raw material.
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| CN110055433B (en) * | 2019-01-21 | 2021-05-18 | 中国科学院金属研究所 | Method for extracting and recycling rare earth elements in neodymium iron boron waste material by using liquid metal bismuth |
| CN111933373A (en) * | 2020-06-12 | 2020-11-13 | 宁波源盛磁业有限公司 | Method for preparing regenerated neodymium-iron-boron magnet by using sintered neodymium-iron-boron slag |
| CN112188765B (en) * | 2020-10-12 | 2022-05-17 | 深圳市格仕乐科技有限公司 | 5G case base production forming process |
| CN114597044B (en) * | 2022-02-23 | 2023-10-24 | 赣州市华新金属材料有限公司 | Method for preparing sintered NdFeB permanent magnet by taking rare earth oxide as raw material |
| CN116313351B (en) * | 2023-03-10 | 2023-10-20 | 山西汇镪磁性材料制作有限公司 | Method for preparing low-cost neodymium iron boron by composite deoxidization process |
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