EP3365118A1 - Method and system for recovering rare earth elements from within an object - Google Patents
Method and system for recovering rare earth elements from within an objectInfo
- Publication number
- EP3365118A1 EP3365118A1 EP16781443.3A EP16781443A EP3365118A1 EP 3365118 A1 EP3365118 A1 EP 3365118A1 EP 16781443 A EP16781443 A EP 16781443A EP 3365118 A1 EP3365118 A1 EP 3365118A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- rare earth
- fluid
- mixture
- temperature
- metal
- 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
- 238000000034 method Methods 0.000 title claims abstract description 64
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 38
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 239000012530 fluid Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000011282 treatment Methods 0.000 claims abstract description 26
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 30
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 229910052779 Neodymium Inorganic materials 0.000 claims description 13
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 239000000470 constituent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910001004 magnetic alloy Inorganic materials 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- -1 salt sodium chloride Chemical class 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000005347 demagnetization Effects 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 claims description 2
- 235000006708 antioxidants Nutrition 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 description 13
- 229910001172 neodymium magnet Inorganic materials 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 239000011241 protective layer Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- RCYIWFITYHZCIW-UHFFFAOYSA-N 4-methoxybut-1-yne Chemical compound COCCC#C RCYIWFITYHZCIW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910001122 Mischmetal Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910000583 Nd alloy Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- ZBAQHMBLDSQPHC-UHFFFAOYSA-K neodymium(3+);trihydroxide Chemical class [OH-].[OH-].[OH-].[Nd+3] ZBAQHMBLDSQPHC-UHFFFAOYSA-K 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 206010011906 Death Diseases 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- KPLQYGBQNPPQGA-UHFFFAOYSA-N cobalt samarium Chemical compound [Co].[Sm] KPLQYGBQNPPQGA-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/41—Particle morphology extending in three dimensions octahedron-like
Definitions
- the invention particularly relates to a method and a system for the recovery of rare earths contained in permanent magnets for example. It applies more generally to the recovery of rare earths contained in an object composed of at least one rare earth part or a mixture of rare earths and at least one metallic element or a mixture of metal elements or a rare earth-metal alloy.
- Permanent magnets containing rare earths are currently considered to be the most powerful magnets and the market associated with them is constantly increasing.
- the materials concerned include Nd-Fe-B magnets directly from the dismantling of WEEE, computer hard drives, speakers, electric motors, etc. Since these magnets are very sensitive to corrosion, they are usually covered with one or more films in order to limit their exposure to air in electrical equipment and e. The nature of these films may be metallic and / or polymeric.
- the recycling of these magnets aims to overcome the steps of extraction of neodymium contained in the magnetic alloy, steps currently performed industrially using heavy chemical processes involving molten metal salts and organic solvents, for example .
- the magnets are magnetically attached to a wheel and the nickel magnetic film is removed by sand splashing.
- the liquid magnesium is used to form an Mg-Nd alloy and thus to separate the neodymium from the iron.
- the Mg-Nd alloy thus formed is then separated by vacuum distillation. All of these operations impose complex and specific equipment.
- US Patent 8734714 discloses a method for recovering rare earths contained in a material in which the assembly is exposed to hydrogen. This method of decrepitation by hydrogen, although presented as effective, has the main disadvantage of using dihydrogen explosive gas at high temperatures (up to 600 ° C), which generally implies very specific installations for its use and its reprocessing.
- Some methods for the extraction of neodymium involve molten metal salts or baths of strong acids. This can be a limit from an economic and environmental point of view. There is therefore a current need to provide a simple and inexpensive method for the recovery of rare earths contained in objects, the rare earth or rare earths occurring alone or in mixture with other elements.
- metal element will be used to designate a metal element or by extension a mixture of metal elements.
- the word component or constituent word will be used to designate a rare earth, a mixture of rare earths or a metallic element contained in the object to be treated.
- An object has several constituents.
- solvothermal treatment denotes a reaction carried out, for example in a sealed enclosure, in the presence of a solvent, a material to be treated and optionally one or more reagents.
- the invention relates to a method for recovering at least rare earths contained in an object "A" composed of at least a first rare earth part or a mixture of rare earths and a second metal part, characterized in that it comprises a solvothermal treatment step carried out in the presence of at least one solvent, bringing object A into contact with a fluid adapted to cause the oxidation of at least one rare earth part and / or mixture of rare earths and the metal part to separate them, the fluid or the mixture of fluids comprising one or more components of molar mass greater than 2g.
- the value of the reaction temperature Tr is chosen according to the nature of the object, with a maximum value lower than the melting temperature of the object and a minimum value greater than the evaporation temperature of the solvent, the reaction according to a scheme RM-R (X) x + M (X) y with R the rare earth or a rare earth mixture, M the transition metal, (X) a group depending on the fluid used.
- the method is for example applied to a magnetic object composed of at least one rare earth and a magnetic alloy, the fluid being a solvent adapted to separate the rare earths from the protective layer of antioxidant coating the magnet and then to separate the rare earth by oxidation.
- the reaction temperature Tr is chosen at least equal to the initiation temperature of an oxidation process of the constituent elements of the object which allows the diffusion of the oxidant within the object.
- a catalyst is used and the value of the reaction temperature Tr is chosen taking into account the catalyst.
- the operation is carried out by placing the fluid under supercritical conditions.
- the method can be used for an object comprising an Nd 2 Fe-i 4 B magnetic phase, an oxidizing solvent such as water being used as the fluid, separating the magnetic phase which dissociates, leading to the separation of neodymium and other elements in the form of crystals, according to the process
- Oxidizing salt of sodium chloride and / or oxides of sulfur can be used as the oxidizing fluid and the reaction is carried out at a temperature above 100 ° C.
- the object is, for example, a rare-earth alloy / metal electrode used within a battery or a rechargeable battery.
- the treatment time may be chosen depending on the subsequent treatment of the elements and / or crystals formed at the end of the process.
- the method may comprise a step of pretreatment of the object by grinding and / or demagnetization.
- the invention also relates to a system for recovering rare earths contained in an object A composed of at least a first rare earth part or a mixture of rare earths and a second metal part, characterized in that it comprises at least one less the following: An enclosure receiving the object A and a fluid having characteristics suitable for causing the oxidation of at least the first rare earth part and / or the second metal part,
- FIG. 1 a device making it possible to implement the method according to the invention
- FIGS. 3A to 3F the result showing the separation of the different elements obtained by the implementation of the steps of the method according to the invention.
- FIG. 1 schematizes an autoclave chamber made of Teflon 1, for example, in which an object to be treated will be positioned, an Nd-Fe-B magnet directly resulting from the dismantling of the WEEE, for example.
- the chamber 1 comprises an opening 2 for the introduction of the object "A" to be treated, and a lid 3 equipped for example with a seal 4 to ensure a tight seal.
- a first introduction conduit 5 equipped for example with a valve 6 which makes it possible to inject a fluid such as a solvent stored in a reservoir 7, the fluid having the particularity of causing the oxidation, at least of the rare earth component as well as the possible oxidation of a metal element (iron for example for Nd-Fe-B alloys) leading to the separation of these two rare earth components / metal element.
- a second exhaust duct 8 also equipped with a valve 9 makes it possible to evacuate the solvent, once the reaction has been completed, without having to open the enclosure.
- the enclosure 1 is also equipped with a heating means 10 making it possible to reach the temperature necessary to start the oxidation, ie, the reaction that will allow the separation.
- the heating means 10 is for example a heating resistor or any other suitable heating device.
- the chamber 1 is for example equipped with a temperature sensor Ct and a pressure sensor Cp to monitor the temperature and the pressure in the chamber.
- FIG. 2B shows a computer hard disk 30 comprising a nickel-coated Nd-Fe-B magnet 31 mounted on a support 32.
- the fluid is for example a solvent which is chosen according to the nature of the constituents of the object or element to be treated and the rare earths present in object A.
- the solvent will be chosen in particular to oxidize this protective sheet.
- the oxidation will initially cause cracking of the metal film, which allows the solvent to diffuse inside the constituents of the object.
- the swelling will complete dislocate the metal film.
- the fluid may comprise oxidizing salts.
- the component (s) of the fluid or mixture of fluids used will have a molar mass greater than 2 g. mol "1. We can also use a catalyst to promote this reaction.
- a mixed composition of rare earths and / or a rare earth will be obtained in the form of a crystalline phase separated from the other rare earth elements. . Separated rare earths or mixed compositions of rare earths will be treated, subsequently using, for example methods known to those skilled in the art.
- the solvent used is, for example, water, for reasons of simplicity and low cost.
- the temperature will be for example at least 375 ° C for reaction conditions in supercritical state, or at least 100 ° C for reaction conditions in gaseous state.
- the maximum treatment temperature T max will be chosen to be lower than the melting temperature T fu of the alloy and the minimum temperature T mir , always higher than the evaporation temperature T eva p of the solvent.
- the reaction will for example be carried out at a temperature above the boiling point of the solvent and lower for example at 650-700 ° C.
- the pressure value can be autogenous or imposed, but will always be greater than 1 bar.
- any solvent compatible with the conditions of temperature and pressure, and which does not react with the elements of the object, for example an alloy may be used.
- the following list of solvents is illustrative and in no way limiting: alcohols such as methanol, ethanol, isopropanol, butanol, esters, ketones, for example acetone, aromatic hydrocarbons and aliphatics, carbides for example methylene chloride, "alkylene glycol", for example ethyl glycol and diethyl glycol, a mixture of water and organic solvents.
- the solvent may be aqueous or non-aqueous, but will not consist mainly of acids or mineral bases.
- the object comprises an Nd 2 Fe-i 4 B magnetic phase
- water vapor is used for example, the dissociating magnetic phase is separated, leading to the separation of the neodymium and the other elements in the form of crystals.
- the treatment is carried out at high temperature, more precisely at a temperature Tr greater than 20 ° C., but preferably chosen between 200 ° C. and 400 ° C.
- the treatment temperature Tr is chosen according to the following parameters of the system and the knowledge of those skilled in the art: • Tr must be greater than a minimum value Tmin from which there is formation of the oxides of the constituent elements of the object , and which allows the diffusion of oxygen within the object. She will be chosen example greater than 100 ° C for the Nd-Fe-B alloys in the H 2 O-NaCl system:
- a catalyst can be added to accelerate the oxidation process. Any compound which makes it possible to reduce the reaction time, whether by promoting the ionic displacement of the species present in solution or by improving the oxidizing power of the solvent, can be used.
- the catalysts added belong to the family of oxidants conventionally used in industry.
- sulfur oxides such as sulfur dioxide, sodium sulphates and sulphites, sodium chloride, acids or acid mixtures such as hydrochloric, nitric acid, sodium hypochlorite, phosphoric acid, carbonic acid, chlorine dioxide, chlorinated hydrocarbons, sodium hydroxide, potassium and ammonium, iron chlorides.
- sodium chloride NaCl as well as sodium metabisulfite, used in smaller amounts but having a greater impact on the reaction time, can be used.
- an aqueous solution having an NaCl concentration of between 1 and 20 mmol.L -1 , and a Na 2 S 2 O 5 concentration of 0.5 mmol.L -1 .
- a surfactant which makes it possible to improve the extraction yields, the person skilled in the art will choose it according to the solvent and the conditions of the temperature and pressure.
- the pressure value is controlled by safety and to avoid possible degradation of the rare earths during adverse parallel reactions for example.
- the duration of the treatment is chosen in particular according to the chemical nature of the object A, its dimensions, its shape and the temperature at which the enclosure is worn. For example, it will be possible to choose a treatment duration of 12 to 24 hours in order to obtain the complete spraying of the material and therefore a powder.
- the duration of treatment generally depends on the treatment temperature and is shorter as the temperature is high. It can last between six hours when the first stages of dissociation are observed and twenty-four hours when the alloy is sprayed and dissociated.
- the crystallized component (s) may be cured, for example at about 50 ° to 200 ° C., at atmospheric or autogenous pressure, for 15 minutes to 48 hours.
- the curing treatment can be carried out in the presence of the fluid used during the process or in the presence of washing water. This ripening improves the crystallinity and / or increases the size of the crystallites.
- the choice of "ripening" treatment will be, for example, depending on the subsequent treatments envisaged for the mechanical separation of the various constituents obtained at the end of the process.
- the process according to the invention may comprise, for example, the steps described below, carried out in the same installation, with the same reaction fluid, without external intervention on an industrial scale, for example.
- the object for which the rare earths are to be recovered is brought into contact, at a chosen reaction temperature Tr, with a fluid whose physicochemical characteristics are adapted to separate the metal part of the rare earths which it contains by oxidation in temperature conditions selected to cause oxidation of at least the rare earth or rare earth mixtures and / or metal part by a separation mechanism RM-R (X) x + M (X) y
- R is the rare earth
- M represents the metal part, for example a transition metal
- (X) a group depending on the solvent used, for example the oxidizing salts used
- the temperature and the reaction pressure for example an oxygen element O, S sulfur, or OH hydroxide group.
- a sintered Neodymium-Iron-Bore magnet as received in a sorting center can take various forms. It can be coated with a protective layer, such as electrolytic nickel.
- the microstructure of a sintered Nd-Fe-B magnet consists of Nd 2 Fe-i 4 B crystallographic grains of micrometric dimensions, and an intergranular phase. This intergranular phase is composed mainly of neodymium, but also contains the different dopants that can be added by the industrialist (dysprosium, praseodymium ).
- the process will initially separate the protective layer from the protective layer.
- rare earth-metal complex by oxidation, for example degradation and fragmentation of the metal protective film.
- the solvent accesses the alloy and causes the separation of the metal part and rare earths.
- the residues of the protective layer can subsequently be removed by simple filtration after opening the enclosure. Indeed, after cooling of the chamber, the pieces of metal film remain of millimeter dimensions while the magnet powder is micrometric, the protective layer can be transmitted to a conventional processing step known to those skilled in the art.
- FIG. 3A microstructure of a Nd-Fe-B magnet: Nd 2 Fe-i 4 B grains, 41, and intergrain area 40
- the powder recovered at the end of the treatment is composed mainly of neodymium hydroxides Nd (OH) 3 and Fe 3 0 4 iron oxides. Indeed, during the same process, the Nd 2 Fe-i 4 B magnetic phase dissociates into Fe 3 O 4 (of octahedral form), 43, FIG. 3D, and Nd (OH) 3 (in the form of rods). , Figure 3E, leading to the separation of neodymium and other elements in the form of very distinct crystals. A complete dissociation of the Nd 2 Fe-i 4 B grains is observed, the octahedral magnetite 43 becoming detached from the grains, FIG. 3F.
- the treatment time chosen allows in particular the growth of the crystals formed during the metal / rare earth dissociation. Thus, depending on the separation treatments used after the "solvothermal" reaction, the treatment time will be chosen to vary the size of the recovered crystals.
- the neodymium hydroxides are separated from the iron oxides by the application of a weak magnetic field, for example, outside the enclosure.
- the Nd (OH) 3 neodymium hydroxide crystals are predominantly in the form of rods if they result from the dissociation of Nd 2 Fe-i 4 B grains.
- Neodymium hydroxide crystals can also have no apparent geometry when they come from the degradation of the phase (intergranular rich in Nd).
- the final separation of the compounds can be carried out using any type of known technique, for example by enrichment using physical techniques, grinding and flotation and / or gravity concentration on shaking tables and / or by magnetic separation and / or any other physical, physico-chemical or chemical technique.
- the method comprises a prior step during which the object is demagnetized. This step can also be carried out in the enclosure while maintaining a temperature higher than the Curie temperature of the magnetic alloy, for example 320 ° C which is the Curie temperature of Nd-Fe-B magnets.
- the method comprises a prior step during which the object is crushed, in order to promote and homogenize the diffusion of the fluid within the constituents of the object.
- the process steps described above can be applied to other families of magnets such as Samarium-Cobalt permanent magnets (Sm-Co). These magnets initially consist of SmCo 5 crystallographic grains, and after application of the process, the reaction products are Sm (OH) 3 and Co 8 S 9 .
- the oxidizing salt used in this example is Na 2 S 2 0 5 which explains the appearance of the compound Co 8 S 9 : cobalt was oxidized by sulfur.
- the reaction is longer in the case of Samarium-Cobalt magnets, because cobalt oxidizes more easily than iron, but is done according to an equivalent scheme: SmCo 5 -> Sm (OH) 3 + Co 8 S 9 .
- the enthalpy of formation of cobalt oxides being greater than that of neodymium oxides, the energy to be supplied is all the more important.
- the process may also comprise a grinding step of the powder resulting from the process making it possible to improve the magnetic separation efficiency and thus to enrich the fraction containing the rare earths.
- the link will be dissolved beforehand for example before introduction into the enclosure by techniques known to the man of the job.
- the process will comprise a preliminary step of dissolution treatment of the matrix, for example in a first reactor and its evacuation before starting the process steps of the invention. At the end of this step is recovered the neodymium-iron-boron powder contained in this type magnets. This powder is subsequently introduced into the chamber with a suitable solvent in order to separate the neodymium from the other elements.
- the method can also be used to recover rare earths present in rechargeable batteries and cells that have a rare-earth alloy / NdCo metal electrode, NiMH (nickel-metal hydride) cells / batteries, the most common having a Mischmetal composition. / Nickel with MnCl 5 stoichiometry. Mischmetal is an alloy of rare earths in varying proportions, typically: 45 to 50% cerium, 25% lanthanum, 15 to 20% neodymium and 5% praseodymium.
- the method can also be used to recover the neodymium present in Nd YAG laser crystals consisting of garnet, yttrium and aluminum doped with neodymium.
- the method according to the invention is inexpensive, it can operate in batch or continuous (industrial process) and does not require complex installation or specific safety system as for the hydrogen or molten salt treatments.
- the technique employed makes it possible to remove the protective antioxidant layer, in most cases an electrolytically deposited nickel metal film, and to dissociate the rare earth / metal unit in order to recover the rare earth, while limiting the environmental impact.
- the process is just as effective even if the rare earth / metal unit has been degraded beforehand, for example when it is used inside the appliances or during dismantling.
- the solvent can be reused to recycle new magnets.
- the reaction occurs in a closed environment, there is no evaporation in the atmosphere and has little impact on the environment.
- the same reaction bath can be used many times.
Abstract
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FR1559949A FR3042428B1 (en) | 2015-10-19 | 2015-10-19 | METHOD AND SYSTEM FOR RECOVERING RARE EARTH PRESENTED WITHIN AN OBJECT |
PCT/EP2016/074604 WO2017067844A1 (en) | 2015-10-19 | 2016-10-13 | Method and system for recovering rare earth elements from within an object |
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CN110538478A (en) * | 2018-10-29 | 2019-12-06 | 天津包钢稀土研究院有限责任公司 | High-quality anhydrous rare earth halide purification device |
KR102376951B1 (en) * | 2020-02-19 | 2022-03-22 | 순천향대학교 산학협력단 | Method of recovering rare earth metals from spent nuclear fuel and the apparatus thereof |
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WO1996000698A1 (en) * | 1994-06-28 | 1996-01-11 | Pure Etch Co. | Rare earth recovery process |
JP3145889B2 (en) * | 1995-02-16 | 2001-03-12 | 日本原子力研究所 | Sequential separation of uranium and rare earth elements using supercritical fluid as extraction medium |
CN100584967C (en) * | 2007-02-05 | 2010-01-27 | 扬州大学 | Method for separating highly-pure rare-earth oxide from rare earth mine for reinforced baking by sulfuric acid |
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JP5909125B2 (en) * | 2011-08-09 | 2016-04-26 | 大阪瓦斯株式会社 | Method for producing metal particles using solvothermal reaction |
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US9376736B2 (en) * | 2012-01-06 | 2016-06-28 | Hitachi Metals, Ltd. | Method for separating and recovering rare-earth elements |
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US10233516B2 (en) | 2013-01-28 | 2019-03-19 | Hitachi Metals, Ltd. | Method for recovering heavy rare earth element |
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US10316393B2 (en) * | 2014-03-28 | 2019-06-11 | Hitachi Metals, Ltd. | Method for recovering rare earth element |
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