EP2885436A1 - Recovery of rare earth metals - Google Patents
Recovery of rare earth metalsInfo
- Publication number
- EP2885436A1 EP2885436A1 EP13879584.4A EP13879584A EP2885436A1 EP 2885436 A1 EP2885436 A1 EP 2885436A1 EP 13879584 A EP13879584 A EP 13879584A EP 2885436 A1 EP2885436 A1 EP 2885436A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- salt
- melt
- chloride
- rem
- aluminium
- 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.)
- Withdrawn
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 67
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 62
- 238000011084 recovery Methods 0.000 title claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 30
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 22
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 17
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 17
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 17
- 150000003841 chloride salts Chemical class 0.000 claims abstract description 16
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 15
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 15
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 15
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 15
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 15
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 15
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 14
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 14
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 14
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 14
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims description 96
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 42
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 30
- 239000011780 sodium chloride Substances 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 229910052782 aluminium Chemical group 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 16
- 150000002739 metals Chemical class 0.000 claims description 16
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 14
- 239000004411 aluminium Chemical group 0.000 claims description 14
- 239000001110 calcium chloride Substances 0.000 claims description 14
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 14
- 239000000274 aluminium melt Substances 0.000 claims description 13
- 229910001510 metal chloride Inorganic materials 0.000 claims description 11
- -1 rare earth metal chloride Chemical class 0.000 claims description 11
- 230000004907 flux Effects 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 150000001805 chlorine compounds Chemical class 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 7
- 229910001172 neodymium magnet Inorganic materials 0.000 claims description 7
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010952 in-situ formation Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Chemical group 0.000 claims description 4
- 239000011833 salt mixture Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- 238000009435 building construction Methods 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Chemical group 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 229910052730 francium Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052705 radium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 238000009834 vaporization Methods 0.000 abstract description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 20
- 239000001103 potassium chloride Substances 0.000 description 10
- 235000011164 potassium chloride Nutrition 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 229910017544 NdCl3 Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- 229910016644 EuCl3 Inorganic materials 0.000 description 1
- 229910003317 GdCl3 Inorganic materials 0.000 description 1
- 229910002249 LaCl3 Inorganic materials 0.000 description 1
- 229910019328 PrCl3 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- BOXVSFHSLKQLNZ-UHFFFAOYSA-K dysprosium(iii) chloride Chemical compound Cl[Dy](Cl)Cl BOXVSFHSLKQLNZ-UHFFFAOYSA-K 0.000 description 1
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 1
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- AEDROEGYZIARPU-UHFFFAOYSA-K lutetium(iii) chloride Chemical compound Cl[Lu](Cl)Cl AEDROEGYZIARPU-UHFFFAOYSA-K 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 description 1
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- 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
- the invention relates to a process for recovering at least one rare earth metals (REM) from the group of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
- REM rare earth metals
- Rare earth metals i.e. Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
- Nd containing magnets such as NdFeB -magnets
- batteries such as battery cathodes containing AB5, where A is lanthanum, cerium, neodymium and/or praseodymium, and B is nickel, cobalt, manganese and/or aluminium, thin films, lightings and displays, ores, rare earth concentrates from ores.
- the rare metals can be present in metallic form but commonly as oxides, e.g. La 2 0 3 , Ce0 2 , Pr 6 On, Nd 2 0 3 , Sm 2 0 3 , Eu 2 0 3 , Gd 2 0 3 , Tb 4 0 7 , Dy 2 0 3 , Ho 2 0 3 , Er 2 0 3 , Tm 2 0 3 , Yb 2 0 3 , Lu 2 0 3 , and Y 2 0 3 .
- oxides e.g. La 2 0 3 , Ce0 2 , Pr 6 On, Nd 2 0 3 , Sm 2 0 3 , Eu 2 0 3 , Gd 2 0 3 , Tb 4 0 7 , Dy 2 0 3 , Ho 2 0 3 , Er 2 0 3 , Tm 2 0 3 , Yb 2 0 3 , Lu 2 0 3 , and Y 2 0 3 .
- the object of the invention is to provide a process for recovering at least one rare earth metal from the group of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu from a resource containing at least one of these metals.
- Another object of the invention is to recover Nd and/or Dy from Nd/Dy containing magnets.
- At least one of the objects mentioned above is met by a process for recovering at least one rare earth metals (REM) from the group of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, said process including the steps of: a) providing a crucible for supporting a salt melt; b) providing a salt melt consisting of (in weight %):
- a chloride salt composition consisting of at least two metal chlorides selected from the group consisting of chlorides of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, and Ra, - optionally 0-10 of halides, additional chlorides, sulphides and/or oxides; c) providing at least one REM containing resource to the crucible before or after heating to form the salt melt, said REM containing resource including at least one rare earth metal from the group of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; d) reacting the aluminium chloride as a chloride donor with at least one rare earth metal of the REM containing resource to form at least one rare earth metal chloride dissolved in the salt melt; e) optionally maintaining AICI3 levels by adding AICI3 stepwise or continuously as it is consumed or by in situ formation of A1C13 in
- At least one rare earth metal from the group of: Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu can be recovered.
- the salt melt is preferably heated under protective atmosphere, suitably argon.
- the atmosphere may also be nitrogen.
- chlorine gas may be admixed to the nitrogen or argon atmosphere.
- the contents of the salts are within 10 % by weight from the lowest eutectic point of the salt combination, more preferably within 5% by weight , most preferably within 1 % by weight.
- other contents may be used as long as the liquidus temperature of the salt combination is at least 50°C lower than the operating temperature during electrolyzing; preferably 100 °C lower than the operating temperature.
- the salt composition comprises at least two of the salts selected from the group: NaCl, KCl, LiCl, and CaCl 2 , preferably at least three of the salts selected from the group: NaCl, KCl, LiCl, and CaC12.
- the at least one chloride salt composition includes by weight % of the at least one chloride salt, 3-20 NaCl, 30-70 KCl, 20-60 LiCl, preferably 5-15 NaCl, 40-60 KCl, 30-50 LiCl, more preferably 7-12 NaCl, 45-55 KCl, 35-45 LiCl.
- the at least one chloride salt composition includes by weight % of the at least one chloride salt, 10-50 NaCl, 2-20 KCl, 50-80 CaCl 2 preferably 25-35 NaCl, 3-10 KCl, 60-75 CaCl 2 .
- the at least one chloride salt composition includes by weight % of the at least one chloride salt, 5-20 NaCl, 20-40 LiCl, 40-70 CaCl 2 preferably 7-15 NaCl, 25-35 LiCl, 50-60 CaCl 2 .
- the at least one chloride salt composition includes by weight % of the salt composition, 35-65 KCl, 20-50 LiCl, 5-20 CaC12 preferably 45-55 KCl, 30-40 LiCl, 10-15 CaCl 2 .
- the flux is A1C1 3 .
- the flux can be added before or after forming the salt melt. It may also be added stepwise as it is consumed. In one embodiment at least a fraction up to all of the AICI3 is generated in situ by reacting chloride ions in the salt melt with an aluminium anode, preferably the aluminum anode is an aluminum melt at the bottom of the crucible.
- the REM containing resource may be crushed and/or ground and/or milled before being provided to the crucible.
- the crushed and/or ground and/or milled may be pelletized before being provided to the crucible.
- the REM containing resource may e.g. be: - permanent magnets, in particular Nd and/or Dy containing magnets, preferably
- NdFeB -magnets where Nd may be partially replaced by Dy.
- the magnets may be coated with metallic zinc, nickel, nickel+nickel, copper+nickel,
- the magnets may also include other metals such as Nb and Co. These metals may be selectively electrodeposited during electrolysis.
- batteries preferably cathodes containing AB5, where A is lanthanum, cerium, neodymium and/or praseodymium, and B is nickel, cobalt, manganese and/or aluminium;
- Rare earth oxides are particularly suitable, for instance rare earth oxides from the group of: La 2 0 3 , Ce0 2 , Pr 6 On, Nd 2 0 3 , Sm 2 0 3 , Eu 2 0 3 , Gd 2 0 3 , Tb 4 0 7 , Dy 2 0 3 , Ho 2 0 3 , Er 2 0 3 , Tm 2 0 3 , Yb 2 0 3 , Lu 2 0 3 , and Y 2 0 3 .
- Resources of particular interest are those containing at least one of Dy, Nd, Pm, Sm, Ho, Er, Tm, Yb and Lu. At present the most interesting elements to recover are Dy and Nd since these elements may be present in high contents in permanent magnets.
- the ocean floor nodule ore is excluded as a REM containing resource because said raw material normally has a very low content of rare earth oxides and since they contain high amounts of base metals such as Mn, Fe and Ni.
- the flux A1C1 3 acts as a chloride donor dissolving rare earth metal oxides and/or rare earth metals to rare earth metal chlorides in the salt melt.
- the following chlorides can be formed depending on which are earth oxides or metals that are present in the resource to be dissolved: LaCl 3 , CeCl 3 , PrCl 3 , NdCl 3 , SmCl 3 , EuCl 3 , GdCl 3 , TbCl 3 , DyCl 3 , HoCl 3 , ErCl 3 , TmCl 3 , YbCl 3 , LuCl 3 , and YC1 3 .
- A1C1 3 dissolves rare earth metal oxides, aluminium will form A1 2 0 3 .
- A1C1 3 dissolves rare earth metals, Al metal is released which will is highly reactive and is hence likely to react with other reducible chlorides in the salt melt.
- the dissolving step d) is performed before the recovering step d). However they may in different embodiments partly or fully overlap as will be described below, in particular in relation to the use of a liquid aluminium anode.
- the salt melt is kept at high temperature usually for a time between about 2 and about 10 hours, preferably 3-8 hours, more preferably 4-8 hours.
- the amount of REM-containing resource is preferably such that a weight ratio
- “flux'V'REM in the resource” is between 0.1-3, preferably 0.2-2.0, more preferably 0.3- 1.0, most preferably 0.4-0.6.
- the temperature should be lower than 1000 °C, more preferably lower than 900 °C.
- the temperature is preferably in the range of 550-700 °C during the dissolution, more preferably 580-650 °C.
- the temperature of the salt melt is preferably at least 50 °C above the liquidus temperature of the salt melt, more preferably at least 100°C above the liquidus temperature of the salt melt.
- Nd+ A1C1 3 Al+ NdCl 3
- Neodymium can be recovered from neodymium chloride by electrolysis and/or vaporization.
- the salt melt used for extraction may optionally be recycled.
- the at least one rare earth metal and other metals can be selectively electro-deposited from the salt melt.
- the process can be designed to be continuous by combining the two steps. Residues after processing, such as A1 2 0 3 , may be used for landfill, building construction or as a raw material for the refractory industry.
- the salts can be recovered and reused.
- the REM is recovered by electrolysis by having at least one anode and at least one cathode are connected to the salt melt.
- the recovering includes the step of electrolyzing the salt melt to form at least one rare earth metal at the cathode.
- at least one REM from the group Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu is selectively electrodeposited on the at least one cathode.
- the electrolysis is done using conventional anode/s and cathode/s which is further described under "Electrolysis using conventional anode/s and cathode/s".
- the electrolysis includes an aluminium anode which facilitates an in situ formation of an aluminium chloride. This is further described under "Dissolving and electrolysis using aluminium anode”.
- a conventional anode and cathode configuration is used, e.g. at least one cathode and at least one anode submerged in the salt melt.
- two electrodes e.g. of graphite
- a DC source e.g. a DC source.
- the theoretical decomposition voltage for MC1 3 , where M is a rare earth metal is around 2.5-3 V.
- a voltage in the range of 2.5-5 V is used for the electrolysis, more preferably 3-4 V. If A1C1 3 remains in the salt melt it may be selectively electrodeposited or co-deposited with the rare earth metal on the cathode.
- the flux can be added in a single batch or in several batches as the aluminium chloride is consumed, preferably 5-30% by weight of the salt mixture when added in a single batch, more preferably 5-20 % by weight of the mixture, most preferably 7-15 wt%. Since the flux is difficult to recover after the extraction process, it is desirable that there is no excessive addition of aluminium chloride.
- the amount of AICI 3 is maintained at a sufficient level. This may be done by adding AICI 3 stepwise or continuously as it is consumed and/or by in situ formation of AICI 3 in the salt melt. In situ formation of AICI 3 is discussed under "Dissolving and electrolysis using aluminium anode".
- the content of aluminium chloride in the salt melt is dependent on the material to be treated.
- the AlC ⁇ /Nd-ratio is 2/1 considering the reaction set out above.
- the amount of AICI 3 is controlled within ⁇ 7 %, preferably within ⁇ 5 % or within ⁇ 3%.
- the electrolysis preferably is carried out in the crucible that holds the salt melt with the dissolved REM containing resource containing at least one rare earth metal from the group of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
- the temperature of the salt melt is preferably lower than 1000 °C, more preferably lower than 900 °C.
- the temperature is preferably in the range of 550-700 °C, more preferably 580-650 °C.
- the temperature of the salt melt is preferably at least 50 °C above the liquidus temperature of the salt melt, more preferably at least 100°C above the liquidus temperature of the salt melt.
- the dissolving step and the electrolysis step may be performed separately or they may fully or partly overlap.
- the at least rare earth metal of the group Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and optionally other dissolved metals can selectively be electrodeposited on the cathode. After depositing one metal the cathode can be removed and the metal deposited on the cathode can be extracted. To avoid interrupts of the electrolysis, another "clean" electrode can be submerged.
- the salt melt may have a plurality of electrodes which one after the other is activated as a cathode while the former is deactivated. Thereby, the metals can be selectively deposited at individual electrodes.
- the chloride salts of the salt melt may be recycled.
- the residue after processing contains A1 2 0 3 and for instance other stable oxides such as Si0 2 , depending on the contents of the REM containing resource.
- the residues may for instance be used for landfill, building construction or as a raw material for the refractory industry.
- the at least one anode includes aluminium, preferably in the form of an aluminium melt provided at the bottom of the crucible.
- the aluminium melt form the anode or a part of the anode, for instance by immersing an electrode, e.g. a graphite electrode, in the aluminium melt and connecting it to positive polarity during electrolysis.
- the crucible is at least partly made in a conductive material being in contact with the aluminium melt, and connecting the crucible positive polarity during the electrolysis. Thereby, the crucible and the molten aluminium operate as an anode.
- at least one cathode is still required during electrolysis, e.g.
- the salt melt and the aluminium are heated to a temperature where both are in liquid phase.
- the temperature of the salt melt is preferably at least 50 °C above the liquidus temperature of the salt melt, more preferably at least 100°C above the liquidus temperature of the salt melt.
- the temperature should be at least 660 °C and not more than 1000 °C, preferably the temperature is in the range of 700-900 °C.
- the initiating chloride donor is provided to start the reactions in the salt melt.
- the initiating chloride donor may be aluminium chloride and/or at least one metal chloride that can be electrolyzed, i.e. so that chloride ions forms AICI 3 at the contact surface between the salt melt and the aluminium melt.
- the initiating chloride donor includes a metal chloride of the same type as provided in the chloride salt composition, e.g. at least one metal chloride selected from the group consisting of chlorides of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, and Ra.
- a metal chloride of the same type as provided in the chloride salt composition e.g. at least one metal chloride selected from the group consisting of chlorides of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, and Ra.
- the initiating chloride donor includes aluminium chloride added to the mixture before heating it or to the salt melt, said aluminium chloride being added up to 20 % by weight of the salt mixture, preferably 1-15 % by weight, more preferably 5-10% by weight.
- aluminium melt as the anode or part of the anode the steps dissolving and recovering by electrolysis are expedited simultaneously, preferably for at least 2 hours.
- additional REM containing resource can be stepwise or continuously added to the salt melt.
- the electrolysis and dissolving operation can for instance be performed for 2-8 hours; where after metals deposited at the cathode/s is collected, and the electrolysis can be restarted.
- another "clean" electrode can be submerged.
- the salt melt may have a plurality of electrodes which one after the other is activated as a cathode and while the former is deactivated. Thereby the metals can be selectively deposited at individual electrodes.
- the voltage is suitably within the range of 2.5-5V, preferably 3-4 V.
- the rare earth metal may be co-deposited with aluminum or they may be selectively electrodeposited.
- the residue after processing may contain A1 2 0 3 and for instance other stable oxides such as Si0 2 , depending on the contents of the REM containing resource; in particular if the REM containing resource contains REM oxides A1 2 0 3 may form when chlorinating the REM oxides.
- the residues may for instance be used for landfill, building
- Al CI 3 /neodymium ratio was 2/1 and the AlC13/salt ratio was 20 wt%.
- the whole mixture was weighted before each experiment.
- the masses of the each material are shown in the table 1.
- the powders were poured in an alumina crucible and the crucible was put in the vertical furnace.
- the time to reach the target temperature which was 850 °C was about 6 hours. Then the graphite electrodes were dipped into the salt bath and the electrolysis was started. The voltage was first set on 4 but due to the high current it was decreased to 3.2 in order to avoid constant current condition. The saturation current of the equipment which was used in this experiment was 5. By fixing the voltage on 4 the current increased to 4.99 (saturation current). Hence the voltage was decreased to 3.2 V. The electrolysis was done during 5 hours.
- the deposited layer contained over 40 % by weight of Nd and over 20 % by weight of Al.
- the amount of Fe was below 5 % by weight. It should be noted that the essentially all Fe remained in the salt melt although the theoretical decomposition voltage of FeCl 3 is below 1 V. From the experiment it can be concluded that Nd can be recovered from the salt melt by electrolysis.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE1250932 | 2012-08-17 | ||
PCT/SE2013/050970 WO2014027950A1 (en) | 2012-08-17 | 2013-08-14 | Recovery of rare earth metals |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2885436A1 true EP2885436A1 (en) | 2015-06-24 |
EP2885436A4 EP2885436A4 (en) | 2015-08-19 |
Family
ID=50685665
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13879584.4A Withdrawn EP2885436A4 (en) | 2012-08-17 | 2013-08-14 | Recovery of rare earth metals |
Country Status (8)
Country | Link |
---|---|
US (1) | US20150203979A1 (en) |
EP (1) | EP2885436A4 (en) |
JP (1) | JP2015531827A (en) |
CN (1) | CN104685078A (en) |
AU (1) | AU2013303264A1 (en) |
CA (1) | CA2881811A1 (en) |
RU (1) | RU2015105027A (en) |
WO (1) | WO2014027950A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111440947A (en) * | 2020-04-17 | 2020-07-24 | 包头稀土研究院 | Method for preparing metal ytterbium by adopting high-chlorine-content ytterbium oxide raw material through reduction distillation |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6444058B2 (en) * | 2014-05-20 | 2018-12-26 | 国立大学法人秋田大学 | Recovery method of dysprosium by molten salt electrolysis using lithium halide |
JP6502621B2 (en) * | 2014-06-03 | 2019-04-17 | 株式会社東芝 | Complex oxide separation method |
CN104120288B (en) * | 2014-07-21 | 2016-01-20 | 东北大学 | A kind of method of direct thermal reduction continuous production samarium metal |
CN104498723B (en) * | 2014-12-16 | 2016-07-06 | 湖南稀土金属材料研究院 | The method extracting Scia from titanium slag chlorized abraum salt |
CN108505069B (en) * | 2018-03-30 | 2021-04-20 | 西安瑞鑫科金属材料有限责任公司 | Method for recovering iridium and rhodium from iridium-rhodium alloy waste |
CN109161934B (en) * | 2018-11-13 | 2019-12-31 | 内蒙古科技大学 | Method for separating rare earth elements in neodymium iron boron alloy waste and directly preparing rare earth metals |
CN110611136B (en) * | 2019-09-09 | 2022-10-21 | 华北理工大学 | Method for recovering and preparing cobalt elementary substance from waste lithium battery by molten salt method |
WO2021133106A1 (en) * | 2019-12-27 | 2021-07-01 | 한국생산기술연구원 | Method for recovering rare earth metal |
KR102303795B1 (en) * | 2019-12-27 | 2021-09-23 | 한국생산기술연구원 | Method for converting rare earth metal |
CN111411235A (en) * | 2020-04-16 | 2020-07-14 | 管玲飞 | Method for recycling rare earth elements of lanthanum, cerium, neodymium, iron and boron waste materials without ammonia nitrogen |
BR112022026942A2 (en) * | 2020-07-01 | 2023-01-24 | Yeda Res & Dev | RECOVERY OF RARE EARTH METALS FROM FERROMAGNETIC ALLOYS |
CN114657397B (en) * | 2022-04-01 | 2023-06-02 | 南昌航空大学 | Method for preparing 6N-level samarium chloride by extraction separation |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN85100812A (en) * | 1984-10-05 | 1986-09-03 | 通用汽车公司 | Use metallothermic reduction of rare earth oxides with calcium metal |
CN1004427B (en) * | 1984-10-05 | 1989-06-07 | 通用汽车公司 | Metallothermic reduction of rare earth oxides |
CN1013323B (en) * | 1986-03-04 | 1991-07-24 | 住友特殊金属株式会社 | Method for producing rare earth alloy |
US4680055A (en) * | 1986-03-18 | 1987-07-14 | General Motors Corporation | Metallothermic reduction of rare earth chlorides |
SE532674C2 (en) * | 2008-05-13 | 2010-03-16 | Salt Extraction Ab | Process for chlorination of ores, slag, filament, scrap, powder and other assets containing recoverable metals |
US8282703B2 (en) * | 2010-12-20 | 2012-10-09 | General Electric Company | Rare earth recovery from phosphor material and associated method |
-
2013
- 2013-08-14 RU RU2015105027A patent/RU2015105027A/en not_active Application Discontinuation
- 2013-08-14 US US14/421,445 patent/US20150203979A1/en not_active Abandoned
- 2013-08-14 CN CN201380051127.XA patent/CN104685078A/en active Pending
- 2013-08-14 JP JP2015527425A patent/JP2015531827A/en active Pending
- 2013-08-14 EP EP13879584.4A patent/EP2885436A4/en not_active Withdrawn
- 2013-08-14 CA CA 2881811 patent/CA2881811A1/en not_active Abandoned
- 2013-08-14 WO PCT/SE2013/050970 patent/WO2014027950A1/en active Application Filing
- 2013-08-14 AU AU2013303264A patent/AU2013303264A1/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111440947A (en) * | 2020-04-17 | 2020-07-24 | 包头稀土研究院 | Method for preparing metal ytterbium by adopting high-chlorine-content ytterbium oxide raw material through reduction distillation |
Also Published As
Publication number | Publication date |
---|---|
CA2881811A1 (en) | 2014-02-20 |
JP2015531827A (en) | 2015-11-05 |
WO2014027950A1 (en) | 2014-02-20 |
EP2885436A4 (en) | 2015-08-19 |
AU2013303264A1 (en) | 2015-03-05 |
CN104685078A (en) | 2015-06-03 |
RU2015105027A (en) | 2016-10-10 |
US20150203979A1 (en) | 2015-07-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2885436A1 (en) | Recovery of rare earth metals | |
Meshram et al. | Perspective of availability and sustainable recycling prospects of metals in rechargeable batteries–a resource overview | |
CN106573792B (en) | For extracting and the method for separation of rare earth elements | |
CN103261457B (en) | Autofluorescence body salvage material rare earth and methods involving | |
JP5504515B2 (en) | Rare earth metal recovery method | |
US9150973B2 (en) | Process for recovering metals and an electrolytic apparatus for performing the process | |
CN108138343B (en) | Metal refining method using electrolytic reduction and electrolytic refining process | |
WO2022237514A1 (en) | Method for preparing rare earth alloy | |
JP2014529681A (en) | Recovery of lead and indium from glass, mainly electronic waste materials | |
Mishra et al. | Extraction and recovery of rare-earth metals: challenges in processing | |
JP2012214855A (en) | Method and apparatus for recovering rare earth metal | |
WO2011092516A1 (en) | Novel method for steel production | |
CN108018465A (en) | A kind of method that aluminothermic reduction ilmenite prepares Al-Ti-Fe alloys in ice crystal ground mass fused salt | |
AU2018312365B2 (en) | Electrolytic production of reactive metals | |
JP2013117063A (en) | Method of producing metal by molten salt electrolysis | |
EP2143827A1 (en) | Process for the production of copper from sulphide compounds | |
Makaseev et al. | Production of Nd-Fe foundry alloy by electrolysis in molten salts | |
Shamsuddin et al. | Role of electrochemical processes in the extraction of metals and alloys–a review | |
JP2002080988A (en) | Method of recovering mixed rare earth metal from scrap | |
JP2022168438A (en) | Manganese recovery method | |
CN103132108A (en) | Method for preparing heat resistance magnesia-alumina-neodymium alloy through electrolysis in fused salt system | |
KR20190035329A (en) | Recovering method of rare earth metal from rare earth compound and apparatus for recovering the same | |
KR20220096742A (en) | Process for recovering neodymium and apparatus for recovering neodymium | |
CN102373490A (en) | Method for separating Gd and Eu through fused salt electrolysis | |
CN116288531A (en) | Method for producing ferroniobium alloy by utilizing fused salt electrolysis of co-associated ores containing niobium, titanium and iron rare earth |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20150316 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
RA4 | Supplementary search report drawn up and despatched (corrected) |
Effective date: 20150722 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C25C 3/34 20060101ALI20150716BHEP Ipc: C22B 59/00 20060101AFI20150716BHEP Ipc: C22B 7/00 20060101ALI20150716BHEP |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20160616 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20161027 |