WO2023031932A1 - Electrolytic atomic hydrogen decrepitation of rare-earth-containing materials - Google Patents
Electrolytic atomic hydrogen decrepitation of rare-earth-containing materials Download PDFInfo
- Publication number
- WO2023031932A1 WO2023031932A1 PCT/IL2022/050955 IL2022050955W WO2023031932A1 WO 2023031932 A1 WO2023031932 A1 WO 2023031932A1 IL 2022050955 W IL2022050955 W IL 2022050955W WO 2023031932 A1 WO2023031932 A1 WO 2023031932A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cathode
- rare
- earth
- atomic hydrogen
- electrolytic
- Prior art date
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- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 119
- 150000002910 rare earth metals Chemical class 0.000 title claims description 83
- 239000000463 material Substances 0.000 title claims description 57
- 238000000034 method Methods 0.000 claims abstract description 91
- 229910045601 alloy Inorganic materials 0.000 claims description 101
- 239000000956 alloy Substances 0.000 claims description 101
- 230000005294 ferromagnetic effect Effects 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 76
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 70
- 238000005868 electrolysis reaction Methods 0.000 claims description 58
- 229910052742 iron Inorganic materials 0.000 claims description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 35
- 239000012634 fragment Substances 0.000 claims description 31
- 239000003792 electrolyte Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910052779 Neodymium Inorganic materials 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000010959 steel Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 12
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052689 Holmium Inorganic materials 0.000 claims description 5
- 229910052765 Lutetium Inorganic materials 0.000 claims description 5
- 229910052773 Promethium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 229910052775 Thulium Inorganic materials 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 5
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 5
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 5
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 5
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 5
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 5
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 5
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims description 5
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910000859 α-Fe Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 description 72
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 30
- 239000001257 hydrogen Substances 0.000 description 29
- 229910052739 hydrogen Inorganic materials 0.000 description 29
- -1 rare earth metal chloride Chemical class 0.000 description 27
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 26
- 230000005291 magnetic effect Effects 0.000 description 22
- 239000000047 product Substances 0.000 description 22
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- 238000005660 chlorination reaction Methods 0.000 description 16
- 239000000460 chlorine Substances 0.000 description 15
- 229910052801 chlorine Inorganic materials 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 229910001172 neodymium magnet Inorganic materials 0.000 description 14
- 238000002203 pretreatment Methods 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 13
- 150000002431 hydrogen Chemical class 0.000 description 12
- 238000011084 recovery Methods 0.000 description 12
- 238000004364 calculation method Methods 0.000 description 10
- 150000004678 hydrides Chemical class 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
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- 239000002184 metal Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 7
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- 230000005347 demagnetization Effects 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 241000238366 Cephalopoda Species 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
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- 238000010521 absorption reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 1
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
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- 229910000182 britholite Inorganic materials 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910000175 cerite Inorganic materials 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
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- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005293 ferrimagnetic effect Effects 0.000 description 1
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- 239000010436 fluorite Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910000199 gadolinite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
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- 150000004687 hexahydrates Chemical class 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- AFEXUNWJRCURNJ-UHFFFAOYSA-M iron(3+);oxygen(2-);chloride Chemical compound [O-2].[Cl-].[Fe+3] AFEXUNWJRCURNJ-UHFFFAOYSA-M 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
- 229910001710 laterite Inorganic materials 0.000 description 1
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- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 238000005065 mining Methods 0.000 description 1
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- 231100001228 moderately toxic Toxicity 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-N phosphoric acid;yttrium(3+) Chemical compound [Y+3].OP(O)(O)=O UXBZSSBXGPYSIL-UHFFFAOYSA-N 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical class Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 230000002588 toxic effect Effects 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- C22B59/00—Obtaining rare earth metals
-
- 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
Definitions
- Rare earth magnets based upon neodymium-iron-boron are employed in many clean energy and high-tech applications, including hard disk drives (HDDs), motors in electric vehicles and electric generators in wind turbines.
- HDDs hard disk drives
- the supply of rare earth metals has come under considerable strain. This resulted in dramatic price fluctuations for the rare earth metals, in particular, neodymium, praseodymium and dysprosium, the rare earth constituents of NdFeB magnets.
- rare earth metals are classified as at greatest risk of supply shortages compared to those of all other materials used for clean energy technologies.
- Recycling of magnet scrap from waste products consists of multiple steps, including preliminary steps; separation of the magnets from the waste product, demagnetization through heat treatment at 300-350°C, decarbonization (for removal of resin) by combustion at 700-1000°C under air or oxygen flow, and deoxidization by hydrogen reduction.
- the main process (separation of rare earth metals and iron) begins after these preliminary stages.
- Several wet processes acid dissolution, solvent extraction, and the oxalate method are also used for the recovery of neodymium. These wet chemical methods have poor yield from the acid dissolution and effluent treatment steps, which requires a multi-step process resulting in high cost. It is important that the recovery process for the rare earth metals from magnet scraps has as low cost and as few steps as possible, because recovery of magnetic material from the product is itself a multi-step process.
- the presently disclosed subject matter provides an electrolysis apparatus for atomic hydrogen decrepitation of at least one rare-earth containing material, the apparatus comprises: a cathode where the at least one rare-earth material is the cathode itself; an anode; an electrolyte in a bath; and wherein the electrolysis apparatus is configured to carry out an electrolytic reaction to decrepitate said at least one rare-earth-containing material.
- the at least one rare-earth-containing material comprises a ferromagnetic alloy or rare-earth magnet.
- the rare-earth magnet is selected from a list comprising: Nd2Fei4B, SmCOs, Sm(Co,Fe,Cu,Zr)7, Sr-ferrite, iron bar-magnets or combinations thereof.
- iron-containing materials undergo further treatment processes to separate rare-earth materials from iron-containing ones, as detailed herein.
- further pre-treatment processes can include milling, grinding, crushing, pulverizing ferromagnetic alloys, before the electrolytic atomic hydrogen decrepitation processes.
- the cathode of the apparatus further comprises copper, nickel, steel, titanium or any combination thereof.
- the electrolyte of the apparatus is a hydroxide.
- the electrolyte is KOH or NaOH aqueous solution.
- the cathode further comprises at least one grid adapted to allow decrepitated fragments to pass through it.
- the grid has holes with a size ranging from 1 to 100 pm in diameter.
- the at least one grid is comprised of copper, nickel, steel, titanium, ferromagnetic alloy or any combination thereof.
- the apparatus further comprises at least one additional cathode.
- the presently disclosed subject matter provides a method for electrolytic atomic hydrogen decrepitation of at least one rare-earth-containing materials, the method comprising: providing an electrolysis apparatus comprising an anode, cathode and electrolyte, configured to carry out an electrolytic reaction to decrepitate said at least one rare-earth- containing material; disposing said at least one rare-earth-containing materials onto said cathode; and carrying out an electrolytic reaction by providing an applied potential between said anode and said cathode, producing atomic hydrogen at said cathode.
- the cathode and the ferromagnetic alloy are different materials. In some embodiments of the method the cathode and the ferromagnetic alloy comprise the same material. In one embodiment of the method the cathode and the ferromagnetic alloy are the same material. In one embodiment of the method the electrolytic reaction is carried out at room temperature. In one embodiment of the method the electrolytic reaction is carried out at an elevated temperature. In one embodiment of the method the applied potential is between 4 to 10V. In one embodiment of the method atomic hydrogen is released from the cathode by a reduction reaction of 2 H + ( g) + 2e“ — 2H(g).
- the H+ is a result of electrolysis of the water (H2O) within the cell.
- the electrolyte comprises hydroxide.
- the electrolyte comprises KOH or NaOH aqueous solution.
- the cathode further comprises at least one grid adapted to allow decrepitated fragments through it.
- the at least one grid is comprised of copper, nickel, steel, titanium, ferromagnetic alloy or any combination thereof.
- Figure 1 shows a ferromagnetic alloy before atomic hydrogen decrepitation.
- Figure 2 shows a ferromagnetic alloy after atomic hydrogen decrepitation.
- Figures 4A and 4B show X-ray diffraction (XRD) of the ferromagnetic alloy (initial magnet) before atomic hydrogen decrepitation -
- Figure 4A sample 1
- Figure 4B sample 2.
- the contents of samples 1 and 2 are provided in Example 3, Table 3 ).
- Figures 5A-5D represent characterization of initial magnet characterized by energy dispersive X-ray fluorescence spectroscopy providing SEM image of the initial magnet, Sample 1, ( Figure 5A); SEM image of the initial magnet, Sample 2, ( Figure 5B); EDS spectrum of the initial magnet - Sample 1 ( Figure 5C); and EDS spectrum of the initial magnet - Sample 2 ( Figure 5D).
- Figure 6A shows the laboratory setup for the atomic hydrogen decrepitation.
- 4.7V DC, 13-15A was applied for 2 hrs under ambient conditions.
- Figure 6B shows a photograph of a ferromagnetic alloy as the cathode itself.
- Figure 7 shows powder X-ray diffraction (XRD) pattern of the magnet powder after atomic hydrogen decrepitation.
- XRD powder X-ray diffraction
- Figures 10A and 10B show characterization of the composition of the material after chlorine gas treatment by energy dispersive X-ray fluorescence spectroscopy (EDS, LEO Supra) of Sample 1 ( Figure 10A) and Sample 2 ( Figure 10B).
- EDS energy dispersive X-ray fluorescence spectroscopy
- Figure 11A shows a powder X-ray diffraction (XRD) pattern of the sublimations from neodymium magnet samples following temperature treatment (400°C) with chlorine gas. “1” refers to Fe2O3 and “2” refers to FeOCl.
- Figure 11B shows quantitative phase analysis of the sublimations as obtained from the XRD pattern in Figure 11A.
- Figures 12A-12B represent fine grain powder obtained following electrolytic hydrogen decrepitation of cm-size, Nd-magnet fragments during 2 hrs under ambient conditions:
- the carbon peak in panel (marked ** on the left side of the spectrum) is not due to the powder, but rather to the thin carbon support foil, rare earth elements indicates (REE) overlap XRF peaks of the rare earth elements.
- Figure 13 represents a powder X-ray diffraction (XRD) pattern of the fine grain, decrepitated magnet powder obtained following 2 hrs of room temperature electrolysis in IM KOH solution is compared with that of the Nd2Fei4BHi,86 standard powder pattern (ICSD #80973).
- the XRD pattern of the HD (hydrogen decrepitated) powder was unchanged after 4 months storage in air under ambient conditions.
- Figures 14A-14C represent SQUID magnetometer VSM measurements of the magnetic properties of the HD powder at 300K as a function of applied magnetic field, poH [T]: Figures 14A and 14B present Magnetic polarization J[T]; Figure 14C presents magnetic energy density
- the presently disclosed subject matter provides an electrolysis apparatus and method for atomic hydrogen decrepitation of ferromagnetic alloys by electrolysis.
- the method of atomic hydrogen decrepitation can further include pre-treatment steps.
- the electrolysis apparatus comprises a cathode, anode and electrolyte wherein at least one rare-earth containing material is disposed on the cathode.
- the terms “ferromagnetic alloy”, “rare-earth-containing material” and “rare-earth magnets” are used interchangeably.
- any rare-earth containing material that can be coupled to an electrode for electrolysis can be used for this invention.
- Rare-earth containing materials can include any material that comprises any number of rare-earth elements and/or other materials e.g., a mineral, an alloy or a magnet.
- the ferromagnetic alloy is attached to the cathode in the electrolysis apparatus. In some embodiments the ferromagnetic alloy is disposed on the cathode wherein the ferromagnetic alloy and the cathode are electronically coupled. In some embodiments the electrolysis apparatus can comprise at least one additional cathode.
- the electrolysis apparatus further comprises a grid, containing holes, beneath the ferromagnetic alloy/pieces.
- the hole size in the grid can be any appropriate size configured to allows ferromagnetic pieces/fragments to pass through it, to achieve a powder of a desired grain size at the base of the electrolysis tank, following electrolytic decrepitation.
- the hole size of the grid ranges between 1 to 100 pm in diameter. In some embodiments the hole size of the grid ranges between 1 to 1000 pm in diameter. In some embodiments the hole size of the grid ranges between 1 to 50 pm in diameter. In some embodiments the hole size of the grid ranges between 50 to 100 pm in diameter. In some embodiments the hole size of the grid ranges between 100 to 500 pm in diameter. In some embodiments the hole size of the grid ranges between 500 to 1000 pm in diameter. In some embodiments the hole size of the grid ranges between 1mm to 5 mm in diameter. [0038] In some embodiments more than one grid, connected to the cathode, is used. With multiple grids, larger pieces may pass through the upper grid, but not through the lower grid.
- Ferromagnetic alloy fragments get smaller as they decrepitate and pass through subsequent grids with progressively smaller hole sizes.
- Multiple grids can facilitate a greater surface area of exposure between the ferromagnetic alloy and the electrolyte, as the ferromagnetic alloy is decrepitating.
- any grid configuration that allows for a higher surface area of exposure between the ferromagnetic alloy and the electrolyte is within the scope of the invention.
- the ferromagnetic alloy, rare-earth-containing material or rare-earth magnet itself is the cathode, that is, atomic hydrogen is released directly on the surface of the ferromagnetic alloy cathode.
- Figure 6B shows a ferromagnetic alloy integrated as the cathode itself.
- the cathode itself can comprise the ferromagnetic alloy and rare earth magnets.
- the cathode itself comprises rare-earth containing materials.
- the cathode itself comprises any of the following: cerium (Ce), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), holmium (Ho), lanthanum (La), lutetium (Lu), neodymium (Nd), praseodymium (Pr), promethium (Pm), samarium (Sm), scandium (Sc), terbium (Tb), thulium (Tm), ytterbium (Yb) and yttrium (Y). In some embodiments there is more than one cathode.
- the electrolysis apparatus further comprises a grid, connected to the cathode, configured to allow decrepitated fragments to pass through it.
- This invention further provides a method for electrolytic atomic decrepitation of at least one rare-earth-containing material.
- “Atomic hydrogen decrepitation” generally refers to a process using atomic hydrogen to break down rare-earth-containing materials into smaller pieces, generally small fragments or powders.
- “Electrolytic atomic hydrogen decrepitation” refers to the decrepitation process carried out, at least, by electrolysis.
- “atomic hydrogen decrepitation” and “electrolytic atomic hydrogen decrepitation” or just “decrepitation” are used interchangeably. As such, terms like “decrepitated” and “decrepitated fragments” are understood in view of the definitions herein.
- no pre-treatment step is required before placing ferromagnetic alloys into the electrolysis apparatus.
- pre-treatment stages to the atomic hydrogen decrepitation can be included, as will be detailed below.
- ferromagnetic alloy pieces are placed immediately in an electrolysis apparatus to perform electrolytic atomic hydrogen decrepitation forming an alloy powder.
- Such an alloy power can be separated by any number of additional methods to recover different materials. For example, chlorination treatment to separate iron and rare-earth metals, as described herein.
- a method of electrolytic atomic hydrogen decrepitation of rare earth metals comprises: providing any one of the electrolysis apparatuses disclosed herein, generally comprising an anode, cathode, electrolyte and bath; disposing at least one rare-earth-containing material onto the cathode; and carrying out an electrolytic reaction by providing an applied potential between the cathode and anode, producing atomic hydrogen at the cathode.
- the method comprises a cathode which is itself made of ferromagnetic alloy fragments, pieces or material.
- the method is carried out at room temperature. In some embodiments the method is carried out in ambient conditions. In some embodiments the electrolysis is carried out at an elevated temperature. In some embodiments the elevated temperature is between 20 - 30 °C. In some embodiments the elevated temperature is between 20 - 40 °C. In some embodiments the elevated temperature is between 20 - 50 °C. In some embodiments the elevated temperature is between 30 - 40 °C. In some embodiments the elevated temperature is between 40 -
- the electrolyte is a hydroxide. In some embodiments the electrolyte is KOH or NaOH aqueous solution. In some embodiment the method further comprises the filtering of decrepitated ferromagnetic fragments through a grid. In some embodiments there is more than one grid.
- One advantage of the present invention is in not requiring pre-treatment or a chlorination step. However, some embodiments may use these as additional steps in methods of decrepitation.
- This invention further provides a method for atomic hydrogen decrepitation of at least one rare earth metal from a ferromagnetic alloy, further comprising a chlorination step, the method comprises:
- Figure 3 shows one embodiment for rare earth metal recovery which involves a chlorination step.
- the chlorination step is required to separate iron from the ferromagnetic alloy. In other embodiments no chlorination step is required.
- the atomic hydrogen decrepitation is carried out by electrolysis as described herein.
- this invention provides a method for recovery of at least one rare earth metal from ferromagnetic alloys, the method comprises:
- the atomic hydrogen decrepitation is performed at room temperature. In other embodiments, the atomic hydrogen decrepitation is performed using electrolysis. In other embodiments, the electrolysis is performed using a first electrode (cathode) of copper, nickel, steel, titanium, or combination thereof; and a second electrode (anode) of lead, nickel, steel or combination thereof. In other embodiments, the ferromagnetic alloy is attached to said first electrode (cathode).
- this invention also provides a method for recovery of spent neodymium magnets by chlorine treatment that does not require pre-treatment of magnets.
- magnets that were used without demagnetization, crushing and milling. After treatment at 400°C, a clinker consisting of rare earth metal chlorides, sublimates consisting of iron oxide and iron chlorides were obtained. The resulting rare earth metals chlorides are then processed by electrolysis of the molten salts for rare earth metals production.
- pre-treatment refers to any process or processes that occur before another process.
- pre-treatment may refer to physical processes such as milling and grinding, but may also refer to non-electrolytic atomic hydrogen decrepitation.
- Other examples of pre-treatment may include, but is not limited to: magnetic separation, demagnetization, heating, chemical processes, etc.
- ferromagnetic used interchangeably with ‘ferrimagnetic’
- any type of source (including spent) of permanent magnet made of a combination of metals that creates its own permanent magnetic field.
- metals include, but are not limited to the elements iron, nickel and cobalt, rare-earth metals, naturally occurring minerals (such as lodestone) and any combination thereof.
- the ferromagnetic alloy is Nb2Fei4B, (Nb,Pr)Fei4B with Dy20a additions.
- the present invention provides for the recovery and/or extraction of rare earth metals from any naturally occurring mineral.
- the present invention provides for the recovery and/or extraction of rare earth metals from naturally occurring sources of rare earth elements such as, but not limited to: rare earth minerals, aeschynite-(Y or Ce), allanite, apatite, bastnasite, britholite, brockite, cerite, Dollaseite-(Ce), euxenite, fluocerite, fluorite, gadolinite, laterite clays, loparite, monazite, parisite-(Ce or La), stillwellite, synchysite, titanite, wakefieldite, xenotime, zircon or combinations thereof.
- said at least one rare earth metal is selected from cerium (Ce), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), holmium (Ho), lanthanum (La), lutetium (Lu), neodymium (Nd), praseodymium (Pr), promethium (Pm), samarium (Sm), scandium (Sc), terbium (Tb), thulium (Tm), ytterbium (Yb), and yttrium (Y).
- Neodymium magnets absorb gaseous hydrogen.
- Ndi5Fe77Bs alloys absorb hydrogen readily at room temperature (provided that the surface is not heavily oxidized), with consequent decrepitation (pulverization) of the bulk material into a friable powder. Friability, being the tendency of a solid substance to break into smaller pieces under duress or contact, especially by rubbing.
- Absorption of hydrogen is carried out in two stages: hydrogen is first absorbed by the Nd-rich grain boundary material and then by the matrix Nd-Fe-B phase. Due to a large electronegativity difference, the insertion of hydrogen is favored in the vicinity of the rare earth elements (REE). Inter-grain failure may produce single crystal particles; however, these particles are nevertheless brittle and amenable to further reduction in size by ball milling.
- REE rare earth elements
- This invention is directed to a method of decrepitation of a ferromagnetic alloy using atomic hydrogen (via electrolysis), as opposed to gaseous hydrogen.
- electrolytic atomic hydrogen compared to gaseous hydrogen is in its use of mild conditions, wherein the reaction is conducted at room temperature and eliminates the need of pure hydrogen at high pressure.
- the atomic hydrogen further forms a gaseous hydrogen (H2) [2H (g) — H2 (g)] in the water electrolytic bath.
- Atomic hydrogen forms on the metal surface at the cathode and reacts with the ferromagnetic alloy. Its remainder goes into the water solution and forms molecular hydrogen.
- the cathode comprises copper, nickel, steel, titanium or any combination thereof.
- the anode comprises lead, nickel, steel or combination thereof.
- the atomic hydrogen decrepitation comprises an electrolytic reaction, wherein the electrolyte is a KOH or NaOH aqueous solution.
- the atomic hydrogen decrepitation comprises an electrolytic reaction, wherein the electrolytic reaction is conducted at room temperature. In another embodiment, the electrolytic reaction is carried out at a temperature of between 20 to 40°C degrees. In another embodiment, the electrolytic reaction is carried out between 20 to 30°C degrees. In another embodiment, the electrolytic reaction is carried out between 20 to 35°C deg.
- this process eliminates the need for high temperature equipment or for a pure hydrogen atmosphere at high pressure.
- the fine grain NdFeB hydride powder may be processed further to form new magnetic materials or to facilitate separation of valuable rare earth metals from the iron-containing components of the magnet
- the ferromagnetic alloy powder obtained by the atomic hydrogen decrepitation method of this invention comprises grains of size ⁇ 50 pm. In other embodiments, the ferromagnetic alloy powder obtained by the atomic hydrogen decrepitation method of this invention comprises grains of between 1 pm to 50 pm in size. In other embodiments, the ferromagnetic alloy powder obtained by the atomic hydrogen decrepitation method of this invention comprises grains of between 10 pm to 50 pm in size. In other embodiments, the ferromagnetic alloy powder obtained by the atomic hydrogen decrepitation method of this invention comprises grains of between 30 pm to 50 pm in size.
- the ferromagnetic alloy powder obtained by the atomic hydrogen decrepitation method of this invention comprises grains of between 10 pm to 40 pm in size. In other embodiments, the ferromagnetic alloy powder obtained by the atomic hydrogen decrepitation method of this invention comprises grains of between 10 pm to 30 pm in size. In some embodiments the obtained ferromagnetic alloy powder comprises grains shaped as any of the followings: globular, spherical, cylindrical, non-uniform, cuboidal or combinations thereof. In some embodiments the grains are smooth and in others the grains are rough.
- methods for recovery of at least one rare earth metal from ferromagnetic alloys comprise a reaction with at least one chlorine-containing gas.
- the reaction is performed at a temperature of between 400°C and 450°C.
- the at least one chlorine-containing gas which is used in the methods of this invention is present in an amount of 0.5 - 2.0 kg of the chlorine per 1 kg of the ferromagnetic alloy (or powder alloy).
- the chloride product is a highly pure chloride (both purity and yield
- the methods for recovery of at least one rare earth metal from ferromagnetic alloys comprise a step of electrolyzing the cooled non-volatile at least one rare earth metal chloride.
- the electrolysis is performed using graphite electrodes (cathode, anode).
- the electrolysis is performed at a temperature range of between about 500 to 1500°C.
- said electrolysis is performed using a potential of between 10 to 15 V.
- this invention provides at least one rare earth metal composition prepared by the methods of this invention.
- the following non-limiting examples are presented in order to more fully illustrate certain embodiments of the invention. They should in no way, however, be construed as limiting the broad scope of the invention.
- One skilled in the art can readily devise many variations and modifications of the principles disclosed herein without departing from the scope of the invention.
- EXAMPLE 1 - Magnets Treatment with Atomic Hydrogen - Decrepitation [0077] The decrepitation of the ferromagnetic alloy was carried out in aqueous IM sodium hydroxide solution at room temperature. Electrolysis was carried out with cathode copper electrode and lead anode electrode. Current density was 0.1A/cm 2 . Uncrushed ferromagnetic alloy was attached to the cathode electrode. The atomic hydrogen that is released at the cathode passes through a pieces of ferromagnetic alloy and reacted with it. The pieces of ferromagnetic alloy were scattered by the atomic hydrogen reaction with ferromagnetic alloy powder production. Figures 1, 2 and 8 show the ferromagnetic alloy before and after atomic hydrogen decrepitation.
- Dy20a does not react with molecular hydrogen (reactions 8, 9). Iron from a magnet practically does not participate in reactions with hydrogen under the experimental conditions (reactions 3, 8).
- Group 3 includes hydrolysis reactions of the neodymium, praseodymium, and dysprosium hydrides in the water. Under the experimental conditions, the Gibbs energy of the hydrolysis reactions (11- 16) in Group 3 for rare metals is strongly negative (- 350-530 kJ/mole). Thermodynamic calculations predict that the hydrolysis reactions of the neodymium, praseodymium, and dysprosium hydrides can result in the formation of Nd, Pr, and Dy hydroxides or oxides within a wide temperature range, including the range of interest 273-373 K.
- a process for rare-earth extraction did not require pre-treatment of magnets.
- the magnets that were used did not include demagnetization, crushing and milling pretreatments.
- This example relates to rare-earth metal extraction from pieces of magnets whereas example 4 relates to rare-earth metal extraction from powders, using electrolytic atomic hydrogen decrepitation.
- a clinker consisting of rare earth metals chlorides and sublimates consisting of iron oxide and iron chlorides were obtained. It is noted that the rate of chlorination and the completeness of chlorination (where chlorination is required to separate iron from rare-earth metals) is higher for processes that include pre-treatment with electrolytic hydrogen decrepitation.
- Dy2C>3 were formed of the solid powder clinker (Melting point of the NdCh is 758°C, melting point of the P1CI3 is 786°C, melting point of the Dy2Oa is 2408°C). Air was added 6 to the top part of the reactor for iron chloride oxidation in accordance with reaction (7):
- Chlorine was obtained by reaction (7) and could have returned to the Pilot or industrial unit to the chlorination stage, therefore a circulation of chlorine gas can be achieved.
- X-ray diffraction (XRD) of the as-received magnet fragments was performed on a TTRAX III theta-theta diffractometer while the patterns of the HD (hydrogen decrepitated) powder were measured on an Ultima III theta-theta diffractometer (both diffractometers are products of the Rigaku Corporation, Japan).
- Phase identification was accomplished using Jade_Pro (MDI, CAL.) software and the Inorganic Crystal Structure Database (ICSD).
- Cu K a X-radiation, Bragg-Brentano protocol, diffracted beam monochromator and variable divergence slit widths constituted our standard operating procedure on both diffractometers.
- Element content of the magnet fragments and HD powders was characterized by energy dispersive (X-ray fluorescence) spectroscopy (EDS) on a LEO Supra scanning electron microscope (SEM). Mass% metal content was quantified by inductively coupled plasma mass spectroscopy (ICP-MS, Agilent 7700s) following dissolution of the magnet or HD powder in aqua regia. 0.65 grams of the as-received magnet fragments were dissolved in 100 ml aqua regia at room temperature with continuous stirring during 24 hours. This solution was diluted to 1000 ml with deionized water to prepare stock solution. 2 ml of stock solution were subsequently diluted to 100 ml with deionized water.
- ICP-MS inductively coupled plasma mass spectroscopy
- FIG. 6A Details of the laboratory-scale electrolysis cell are shown in Figure 6A.
- a glass vessel containing 700ml of IM/liter KOH solution served as the electrolytic bath.
- a homemade titanium metal cathode, dimensions [3.5x3.5] cm 2 , and a nickel, plate-shaped anode, dimensions [4.0x4.0] cm 2 served as the electrodes.
- An 18 mesh titanium grid was in electrical contact with the cathode.
- An electrical potential of 4.7 V and a current of 13-15A, were provided by a Kepco power supply KLP- 20-120-1200.
- the cathode current density was 0.8-0.9 A/cm 2 , where the total area included the Ti grid.
- a SQUID magnetometer (MPMS3, L.O.T. -Quantum Design, Inc.) was used in the vibrating (VSM) mode with peak amplitude 2mm, frequency 13 Hz and averaging time 10s.
- the magnetic moment (M, [10' 3 Am 2 ]) of each sample was measured at ambient temperature (300 K) with field strengths I p. o H I ⁇ 6T.
- Nd-magnet fragments appear irregularly shaped, 20-30mm dimensions and with a partially corroded surface.
- the CuK a radiation was only able to probe - 10 micron thick layer at the magnet surface, due to the strong absorption of the RE (rare earth) metals and iron at 8 KeV.
- a SEM image of the surface and an EDS spectrum are shown in Figures 5A-5D. Here again, only a thin layer (l-2pm) at the fragment surface is probed.
- the magnet contained Dy (Dysprosium) as an additive, in addition to Pr (Praseodymium).
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