AU601270B2 - Process for separation of rare earths - Google Patents
Process for separation of rare earths Download PDFInfo
- Publication number
- AU601270B2 AU601270B2 AU13387/88A AU1338788A AU601270B2 AU 601270 B2 AU601270 B2 AU 601270B2 AU 13387/88 A AU13387/88 A AU 13387/88A AU 1338788 A AU1338788 A AU 1338788A AU 601270 B2 AU601270 B2 AU 601270B2
- Authority
- AU
- Australia
- Prior art keywords
- accordance
- fact
- organic phase
- aqueous solution
- concentration
- 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.)
- Ceased
Links
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000000926 separation method Methods 0.000 title claims description 28
- -1 rare-earth nitrates Chemical class 0.000 claims abstract description 57
- 238000000605 extraction Methods 0.000 claims abstract description 56
- 239000012074 organic phase Substances 0.000 claims abstract description 42
- 239000007864 aqueous solution Substances 0.000 claims abstract description 33
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000008346 aqueous phase Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 15
- 238000000622 liquid--liquid extraction Methods 0.000 claims abstract description 10
- 238000000638 solvent extraction Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 23
- 229910052727 yttrium Inorganic materials 0.000 claims description 18
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 229910002651 NO3 Inorganic materials 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 9
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229910021398 atomic carbon Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 13
- 150000003254 radicals Chemical class 0.000 description 12
- 229910052747 lanthanoid Inorganic materials 0.000 description 5
- 150000002602 lanthanoids Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 101000634404 Datura stramonium Tropinone reductase 1 Proteins 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 101000848007 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) Thioredoxin-1 Proteins 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 101100031674 Arabidopsis thaliana NPF8.3 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 101100235787 Schizosaccharomyces pombe (strain 972 / ATCC 24843) pim1 gene Proteins 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical class CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- SWMBQMGPRYJSCI-UHFFFAOYSA-N octylphosphane Chemical compound CCCCCCCCP SWMBQMGPRYJSCI-UHFFFAOYSA-N 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NYBYXXFMCVWVHH-UHFFFAOYSA-N phosphanyloxyphosphane Chemical compound POP NYBYXXFMCVWVHH-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003003 phosphines Chemical class 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
- 101150114015 ptr-2 gene Proteins 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 208000027653 severe early-childhood-onset retinal dystrophy Diseases 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium (III) oxide Inorganic materials [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 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
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/382—Phosphine chalcogenides, e.g. compounds of the formula R3P=X with X = O, S, Se or Te
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
-
- 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
- C01F17/10—Preparation or treatment, e.g. separation or purification
- C01F17/17—Preparation or treatment, e.g. separation or purification involving a liquid-liquid extraction
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/387—Cyclic or polycyclic compounds
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/408—Mixtures using a mixture of phosphorus-based acid derivatives of different types
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Extraction Or Liquid Replacement (AREA)
- Ultra Sonic Daignosis Equipment (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Rare-earth elements present in aqueous solutions are separated using a solvent by a process which consists in performing a liquid- liquid extraction between an aqueous phase containing the rare-earth nitrates and an organic phase, characterised in that a mixture of organophosphorus compounds is used as extraction agent. <IMAGE>
Description
r_ rIIrrarrrl~sz ~c-l d"E4THE A7,STaIA VV Ub t L I" V FORM PATENTS ACT 1952 COMPLETE SPECIFICATION FOR OFFICE USE: Class Int.Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority: Related Art: I1, Name of Applicant: Address of Applicant: Actual Inventor: RHONE-POULENC CHIMIE 25,quai Paul Doumer 92408, Courbevoie, France Thierry Delloye and Jean-Louis Sabot Address for Service: SHELSTON WATERS, 55 Clarence Street, Sydney Complete Specification for the Invention entitled: "PROCESS FOR SEPARATION OF RARE EARTHS" The following statement is a full description of this invention, including the best method of performing if- known to me/us:- 1 EROCESS FOR SEPARATION OF FARE EARTHS This invention deals with a process for the separation of rare earth elements contained in aqueous solutions, using a solvent.
The invention relates, more precisely, to a process of separation by liquid-liquid extraction of rare earths in aqueous solutions of nitrates of these elements.
The term "rare earths" used in accordance with the invention includes rare earth elements by the name of lanthanides oolO which have atomic numbers from 57 to 71 inclusive and yttrium a 00 o with atomic number 39.
SIn the description of this invention which follows, 00 00 o 0 we indicate by "ceric rare earths" the lighter elements of rare earths, starting with lanthane, through to neodyme, in accordance with the atomic numbers and by "yttric rare earths" we designate the heaviestelements of rare earths, starting with samarium and ending with lutecium and including yttrium.
0 ou It is a well known fact that rare earths are difficult S to separate because the differences in the properties of one rare earth in relation to those next to it are extremely slight.
o. Methods for the separation of these very similar elements have been developed which have taken on particular importance in the separation of rare earths, i.e. liquid-liquid extraction methods. They are based on the selective extraction S of one of the rare earths using the solution in which they are contained aided by an extracting solvent which is immiscible with the solution.
As an extracting solvent, certain organophosphorus compounds are already used in solution with an organic diluent to separate rare earths from one another. The use of tri n-octylphosphine oxide by the name of TOPO is particularly well known. However, TOPO is in a solid form at ambient temperature and because of the reduced solubility in the usual diluents 47 3/ of the kerosene type, it's use is not recommended for certain applications, particularly for the separation of rare earths in a nitrate medium and in concentrated solutions.
Furthermore, certain separations, for example that of yttrium from other yttric rare earths are difficult to carry out because of the great similarity of their properties and also because, under industrial conditions of attack on the rare earth ore, yttrium is present in relatively large quantities of yttric rare earths, these quantities are, of course, in correlation with the composition of the rare earth ore.
The applicant has found that the extraction agents defined hereafter obviate the drawbacks previously mentioned and provide a very good selectivity in relation to the rare earths in general.
The invention deals with a method of separation of rare earths in an aqueous solution containing at least two of these rare earths by liquid-liquid extraction between a 0 20 an aqueous phase containing the rare earth nitrates to be separated and an organic phase containing an extraction agent composed of an organophosphorus compound characterised by this extraction agent being made up of an organophosptaorus compound answering to the formula
R
1 R 2 P 0 (1) 3 in which: V 7P 2a
R
1 R2' R 3 represent a hydrogen atom or a radical which can possibly be substituted and which can be a linear or ramified hydrocarbon containing radirnal, saturated or unsaturated or a cyclic hydrocarbon containing radical, saturated or unsaturated: the total number of carbon atoms of the radicals R1,
R
2
R
3 being at least 12 carbon atoms: at least two of the radicals R 1
R
2
R
3 are different.
10 It should be noted that the radicals R 1
R
2
R
3 S, o f f 0 4 t 446 1 444/ 44* 4 004*4/ 4 4 I- -L1-~
R
3 can carry replacement groups, such as hydroxy or nitro groups: halogen atoms, in particular chlorine and fluorine lower alkoxy radicals with a low carbon condensation, for example, 1 to 4 atoms cyano groups, etc...
The radicals R 1
R
2
R
3 have a number of carbon atoms which generally vary between 1 and 18 carbon atoms and preferably between 2 and 8 carbon atoms.
They are selected so that the total number of carbon atoms of the radicals R R 2 t R 3 give a total of at least 12 carbon atoms and preferably more than 18.
For preference, at least two of the radical R 1 R2, R 3 represent linear or ramified alkyl radicals with at least 6 carbon atoms or cycloakyl radicals, having at least 6 carbon S atoms.
I
e 0 o o b 0 <f 44 ts As an example of the radicals R 1
R
2
R
3 we mention S methyl, ethyl, n-propyle, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, methyl-1 butyl, isopentyl, tert-pentyl, neo-pentyl, the normal alkyl radicals which follow n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, as well as the ramified alkyl radicals which 6o correspond and the cycloalkyl radicals in particular the Scyclohexyl radical.
Organophosphorus compounds which answer to foramia(tC) are particularly suited for use in this invention in which R1 R2 R 3 are different linear alkyl radicals, .444, meaning at least two of the radicalsRI, R 2 R3 are S' different, notably as far as the carbon condensation is concerned,
R
1
R
2
R
3 are different ramified alkyl radicals, meaning that at least two of the radicals Rl, R2, R 3 are different,
R
1
R
2
R
3 are linear or ramified alkyl radicals meaning that at least one linear alkyl radical and at least one ramified alkyl radical are present.
We quote the following as examples of the phosphines i-which are preferred for the invention, ethylphosphine bioxide I (ethyl-2 hexyl) (DEHEPO) and the n-octylphosphine bioxide (trimethyl-2,4,4 pentyl).
The extraction agents mentioned in the invention are usually liquid at the ambient temperature and miscible with the normal diluent in all proportions.
The applicant has found that these extraction agents have a very good selectivity in relation to all rare earths and particularly to yttrium and yttric rare earths, notably gadolinium, to lutecium, contrary to the more usual neutral orqanosphophorus extraction agents such, for example as tribytyl phosphate.
os A well adapted method of application of the invention Q 0 is a method of separating yttrium from other yttric rare earths 0 S° yttrium can represent from 5 to 80% of the total weight of yttric S rare earths the percentage being expressed by weight of yttrium oxide in relation to the weight of yttric rare earth oxides, yttrium included.
Another advantage of these extration agents is that they can be used with an aqueous phase highly concentrated in rare earth nitrates (more than 300 g/l) and highly concentrated organic o phases can be obtained, more than 50 g up to 100 g/l and more of rare earths expressed in oxides.
In accordance with the method used in the invention, S the aqueous phase which is placed in contact with the extraction agent can be composed of an aqueous solution provided by the redissolution by nitric acid, of the hydroxides obtained following the sodic attack of the ores containing the rare earths such as monazite, bastnasite, and xenotime. Any other solution of rare earth salts can be used after changing the anion present into a nitrate anion.
The method used in this invonticLa applies to solutions as they are or after being .previously concentrated.
Usually, the liquid-liquid extraction process is carried out on aqueous solutions of rare earth nitrates which have a concentration, expressed in rare earth oxides which vary between g/1 and 500 g/1 the limits which are given are not in any way critical. For preference, they have a concentration between 100 g/l and 500 g/l.
A
-I They usually have an acidity which varies between 0.01 N and 3.0 N.
In accordance with the method used in this invention, the organic phase may contain, as well as the extraction agent, an organic diluent. As diluents which may be used are those usually employed for liquid-liquid extraction. Among theseccan be mentioned, aliphatic or cycloaliphatic hydrocarbons such for example as hexane, heptane, dodecane, cyclohexane, isoparafine the aromatic hydrocarbons such, for example, as benzene, toluene, ethylbenzene, xylene, petroleum cuttings made up of a mixture of alkylbenzene, in particulat cuttings of the SOLVESSO type (trade mark of EXXON) and halogenated hydrocarbons such as chloroform, carbon tetrachbride, dichloro-1,2, ethylene, monochloro~enzene.
A mixture of these diluents can also be used.
For preference, an aliphatic hydrocarbon is selected.
The extractive strength of the organic solution to the rare earths increases as the concentration of the organophosphorus compound in the organic phase is increased however the separation factor of the element between them is not notably modified by the concentration of organophosphorus compound.
Thus the concentration of organophosphorus compound in the organic phase is not a critical factor of this invention and can vary within wide limits. It can vary from 5% of the volume of the organic phase when the extraction agent is in solution in a diluent up to approximately 100% when the extraction agent is used neat.
For preference, the concentration is selected between and 100 of the volume of the organic phase.
The organic phase, in accordance with the method used in this invention can also contain various modifying agents one of the essential aims of which is to improve the hydrodynamic properties of the system without altering the extracting properties of the organophosphorus compound. Among the compounds which are well suited are the compounds with an alcohol function and, in particular, heavy alcohols with the number of carbon atoms between 4 and 15 and the heavy phenols as well as various other compounds such as certain posphoric esters such as tri- V% E c a 1 6 butylphosphates. A proportion between 3 and 20 of the volume in relation to the organic phase is usually favourable.
When establishing the conditions under which the extraction is to be carried out, the concentration of nitrate ions is important as it can facilitate the extraction of the one or several rare earths to be extracted in the organic phase.
The ion nitrate concentration can vary between 1 and 10 moles/ litre and is preferably selected between 2 and 9 moles/litre.
If required, the concentration of nitrate ions can be increased by adding these, for example, by an aqueous solution of nitric acid, an aqueous solution of a salt in the form of a nitrate such as ammonium nitrate.
During the extraction phase, the organic and the aqueous phase are placed in contact at a temperature which is in no way crik\ al it is usually selected between 10 0 C and 80C and more oftqi between 3Q°C and The output ratio of the organic phase and aqueous phase is in correlation with the concentration of the extraction agent and is selected in accordance with the concentration of rare earths to be extracted in the aqueous phase and according to the equipment usually employed for a liquid-liquid extraction operation.
When certain rare earths have been extracted in the organic phase in small quantities when they should have remained in the aqueous phase, it is sometime necessary to include a washing stage after that of extraction.
At the washing stage, the organic phase is washed with water, preferably de-ionised water or in an aqueous solution containing nitrate ions such as an aqueous solution of diluted nitric acid or an aqueous solution or rare earth nitrates of the same nature as the rare earths to be extracted and Which may be present in the part of the aqueous phase obtained in the following regeneration operation of the extraction solvent.
When the washing is carried out with a nitric acid solution, the concentration is selected at less than 1N and is preferably between 10- 3 and 10-1 N. When an aqueous solution of rare earth nitrates is used, the concentration expressed in rare earth oxides can be between 5 and 500 g/l, preferably ifi_
I
I k between 100 and 500 g/l.
After the extraction and washing, followed by the separation of the aqueous phase and the organic phase, the extraction agent goes through a regenerating stage.
The, or the several rare earths are extracted from the organic phase by placing it in contact with water, preferably de-ionised or with an acid aqueous solution, such, for example as a nitric acid aqueous solution, sulphuric acid, hydrochloric agid, perchloric acid solution. Nitric acid is usea for preference.
S 10 The concentration of the acid solution is preferably less than 1N and is preferably between 10 3 and 10-1 N.
The or the several rare earths are recovered in the aqueous phase while the extraction solvent can be recycled at the extracting stage. This recycling is not essential to the-.
invention but is desirable for economic reasons.
A plan follows which allows for the separation in accordance with the method, as previously described in this inventionlof a minimum of at least two and up to n rare earths.
In the case of the separation of two rare earths symbolized by TR 1 and TR 2 the factor of separation between these rare earths is defined as being the relation between the coefficie-h of distribution of TR 1 and TR 2
PTRI
F PTR2 The co-efficient of distribution is equal to the ratio between the concentration of TR 1 (or TR 2 in the organic phase and the concentration of TR 1 (or TR 2 in the aqueous phase.
So that the separation between TRI and TR 2 may be possible, F must be different by 1.
If TR 1 is the rare earth which has the higher coefficient of distribution, F in this case is greater than 1.
In accordance with the invention at least two rare earths, TR 1 and TR 2 are separated by liqud-liquid extraction between on aqueous phase containing at least the nitrates of these rare earths and an organic phase containing the aforesaid organophosyhorus coumpound by proceeding as follows 1 ',1 8 in the first stage, the separation of TR I and TR 2 is done by extracting TR I in the organic phase TR 2 remaining essentially in the aqueous phase at the secord stage, selective washing of the organic phase containing TR I and a- small quantity of TR 2 is carried out using an aqueous solution containing nitrate ions which allows b e elimination of TR 2 from the organic phase by passing into the aqueous phase the organic phase and aqueous phase are then separated at the third stage, the extraction solvent is regenerated by placing the organic phase in contact with water or an acid aqueous solution.
The method of operation of each stage has been previously described.
In accordance with the invention, a mixture of n rare earths can be separated into two sub-groups by assimilating each sub-group to TR I and TR 2 If a mixture of n rare earths are to be individually separated, the sequence of three stages previously described are repeated, (n 1) times in order to sep4 rate all the rare earths from one another.
The practical application of the invention can be carried out using the usual counter-current technique such as described here put also using co-current and cross-current techniques well known to the experts.
The various contact stages can be effected in the usual liquid-liquid extraction equipment which operatE counter-current.
Such equipment usually includes several tiers of mixers-decanters or columns lined, and/or agitated, intended for extraction, selective wdshing and the recovery of the elements of rare earths in an aqueous phase and the regeneration of the extraction agent.
The following example5 are given only as indicatiom and cannot be considered as limitinig the areas or the concepts of the invention.
11.~aw -,^l*rAll^l*.*l t -rf1f ri_.Tl-lT- 1.
In the following examples, the percentages given are expressed in weight unless otherwise specified.
EXAMPLE 1 The factor of separation of yttrium in relation to a lanthanide in a nitrate medium using a liquid phosphine oxide in an aromatic hydrocarbon (SOLVESSO 150).
The mixture of rare earths is a solution of rare earth nitrates with a concentration expressed in rare earth oxides of 500 g/l distributed as follows ceric rare earths La 2 0 3 23.0 Ce02 46.5 Pr 6 0 1 1 51 3 18.4 yttric rare earths Sm2 0 3 2.3 Eu 2 0 3 0.07% Gd 2 0 3 1.7 Tb 4 0 7 0,16% D2 0 3 0,52% Ho 2 0 3 0.09% Er 2 0 3 0.13% 3 0.013% Yb 2 0 3 0.061%
LU
2 0 3 0.006% Y203 2.0 As the extraction agent bi oxide ethylphosphine (ethyl- 2 hexyl) is used (DEHEPO).
This extraction agent is placed in solution in an aromatic hydrocarbon, petroleum cutting SOLVESSO 150, composed of a mixture of alkylbenzene, in particular dimethylbenzene :atd tetramethylbenzene at the rate of 1 mole/litre and the mixture obtained is the extraction solvent.
The aqueous phase composed of the rare earth nitrate solution and the organic phase composed by the extraction agent are placed in contact the ratio of the volume of the phases being equal to the unit.
l!~j [1 The extraction Is carried out at the ambient temperature.
TPhis permits the factorsof .5epaiation of VL n/s' for the lanthanide (Ln/yttrium) pair to be determined as shown in the following table I Ln x :rac La Ce Pr Nd Sm Eu Qd Tb Dy H3 Er Tm Yb b~u Lon igent
U
VE{EPO 10.25 0.75 1,12 1.25 1.75 2,00 1.50 1.87 1.75 1.62 1.62 2,25 1,50 1,37 The values of the factors of separation given above allow for the calculation of the requirements for the separ'ation of yttrium from the other rare earths aiccord~ing to the usual liquiLd-liquid extraction methods.
It is to be nloted Oc~t the phosphine oxide mentioned has a very good selectivity in relation to yttrium for the heaviest yttric rare earths.* EXAMPLE,2 Factor -of separation of yttrium in retntion to) a lanthanide In a nitrate medium-oging a liquid phosphino oxide in an aliphatic hydrocarbon (kerosene).
The same extraction agent as that mentioned in eXample 1 is placed in solution In the kerosene, at a rate of 75 of volume and the mixture obtained Is the extraction solvent.
The aqueous phase composed of the solution of rare earth nitrate$ given In example 1 and the organic phase which is the extraction solvent are plaoct In contact at S0OC the ratio of the volumes of the phases being equal to the u.nit.
The following table shows the factors Of seParation of the FL, fly for the lanthanide (ILn/yttr'ium pair as well as t'ho load of the extraction agent, at equilibrium expressed In g of rare earth oxide per litre.
_1I~1. .ii -_lglL~ -I-L I11C^-i- ~I i--.l
S
11 Ex trac Charge of ion Nd Sm eu Gd Tb Dy Ho Er Tm Yb Lu solv nt agent g 1 DEHEPO 0.97 1.41 1.12 1.12 1.26 1 26 1.28 1.59 2.79 1.59 1.97 t 108.6 Note that the phosphine oxide defined by the invention is Well adapted to a separation yttrium/ the heaviest yttric rare earths, EXAMPLE 3 Method for the separation of yttrium from a mixture containing thulium, ytterbium and lutecium nitrates.
This exal;-e takes place by following the method shown in figure 1.
The equipmenL Lsed for the separation of the rare earths mentioned include a first liquid-liquid extraction battery with several tiers of rhe mixer-decanter type operating counter-current and 4 made up of an extraction section with 47 theoretical tiers and a washing section with 16 theoretical tiers, a regeneration-recovery section for the extraction solvent with 10 theoretic tiers.
The initial mixture of rare earths to be separated is a solution of rare earth nitrates with an acidity of 0.1 N and a -oncentration expressed in rare earth oxides of 270 g/1 dist- 20 ributed as follows a- yttrium oxide 95.0 e 4- thulium oxide 0.8 ytterbium oxide 3,8 lutecium oxide 0.4 ThQ extraction agent used is bioxide (ethyli-2 hexyl) aethylphosphine.
This extraction agent is put in pslution in kerosene, at 75 of volume and the resulting mixtute will be referred to as the extraction solvent.
12 Before giving details of the various processes, it should be noted that for the entry and exit of the extractionwashing and regeneration-recovery unite, the direction of the organic phase is used.
The sequence of the stages is as follows at the exit of the extraction unit at the solution of rare earth nitrates to be separated is introduced at a flow rate of 161 1/h at the entry of the extraction unit the extraction solvent is introduced at a icce of 2008 1/h.
at at the exit of the counter-extraction section and counter-current to the organic phase, deionised water is introduced at a rate of 1004 1/h at the entry of counter-extraction section at 6 an aqueous solution of rare earth nitrates is recovered, it is concentrated by evaporation until a concentration, expressed in rare earth oxides of 450 g/l is obtained having the following distribution 8.0 of Y203 15.0 of Tm 2 0 3 /0 Yb 2 0 3 and 7.0 Lu 2 0 3 5 1/h are recovered, this being the production and the remainder, 529 1/h supply at the washing unit (a to form the back-flo at the entry of the washing unit at at a rate of flow of 695 1/h an aqueous solution of yttrium nitrate is recovered with a concentration expressed in Y203 of 61 g/l and containing less than 10 4 of the other rare earths expressed in oxides at the exit of the regeneration-recovery section (b) at the purified extraction solvent is recovered and may be recycled at in the extraction unit (a) at the same rate of flow this recycling, however, is not an essential part of the invention but is desirable for reasons of economy.
The method, such as it is described allows yttrium to be obtained from a mixture of rare earths with ar excellent extraction output as it is of 99.8 and of a high degree of purity which is 99.9999
Claims (5)
1. Method of separation of rare earths contained in an aqueous solution having at least two of the rare earths, by liquid-liquid extraction between an aqueous phase containing rare earth nitrates to be separated and an organic phase containing an extraction agent made up of an organophosphorus compound, characterised by said extraction agent being composed of an organophosphorus compound of formula R 1 o. 10 RP 0 (I) a t R in which: R R 2 R 3 represent a hydrogen atom or a possibly 0O^« substituted radical which can be a linear or ramified hydrocarbon containing radical, saturated or unsaturated or a cyclic hydrocarbon containing radical, saturated or unsaturated; oO* the total number of carbon atoms of the radical R,, 1 R 2 R 3 being at least 12 carbon atoms; at least two of the radicals R 1 R 2 R 3 are different; and S wherein the concentration at equilibrium of nitrate ions S- of the aqueous phase during the extraction varies between 1 and 10 moles/litre,
2. Method in accordance with claim 1, characterised by the fact that R 1 R 2 R 3 have from 1 to 18 carbon atoms. i
14- 3. Method in accordance with claim 2, characteriseI by the fact that R 1 R 2 R 3 have 2 to 8 carbon atoms. 4. Method in accordance with one of the claims 1 to 3, characterised by the fact that in the organophosphorus co. pound of formula the total number of atomic carbon atoms of the radicals R 1 R 2 R 3 is equal to 18 carbon atoms. Method in accordance with one of the claims 1 to 4, characterised by the fact that in the organophosphorus compound mentioned of formula at least two of the radicals R 1 R 2 R 3 represent alkyl radicals, linear or ramified having at least 6 carbon atoms or cycloalkyl radicals with at least 6 carbon atoms. S6. Method in accordance with one of the claims 1 to characterised by the fact that in the organophosphorus compound of formula R 1 R 2 R 3 are different alkyl linear radicals; different ramified alkyl radicals; linear or ramified alkyl radicals. 7. Method in accordance with one of the claims 1 to 6, characterised by the fact that the organophosphorus compound is bi-(ethyl-2 hexyl)-ethylphosphine oxide and bi-(trimethyl-2,4,4 pentyl)-n-octylphosphine oxide. 8. Method in accordance with one of the claims 1 to 7, characterised by the fact that the aqueous solution of rare earth nitrate has a concentration expressed in rare earth oxides between 20 g/l and 500 g/l. 9. Method in accordance with claim 8, characterised by the fact that the concentration of rare earth nitrates is between 100 g/l and 500 g/l. Method in accordance with one of the claim 8 and 9, characterised by the fact that the aqueous solution of rare earth nitrates shows an acidity between 0.01 N and N. 11. Method in accordance with one of the claims 1 to characterised by the fact that the organic phase also has at least one organic diluent chosen from the group composed of aliphatic or cycloaliphatic hydrocarbons, petroleum cuttings of the kerosene type, aromatic hydrocarbons, petroleum cuttings of the SOLVESSO type, halogenated hydrocarbons. 12. Method in accordance with claim 1, characterised by the fact that the concentration of the organophosphorus compound in the organic phase is between 5 and 100% of the volume of the organic phase. 13. Method in accordance with claim 12, characterised by the fact that the concentration of the organophosphorus 4 compound is between 50 and 100%. 14. Method in accordance with one of the claims 1 to 13, characterised by the fact that the organic phase has also at least one modifying agent selected from the group composed of the compounds with an alcohol function, the S, phosphoric esters. Method in accordance with claim 14, characterised by the fact that the concentration of the modifying agent in the organic phase is between 3 and 20% of the volume of the organic phase. 16 99 9 r 9 9 ,9 30 9 09 *c 0 o p 9 09 Qae 0 OB o 99 0 0 09 99I 9 9
16. Method in accordance with any one of claims 1 to characterised by the fact that the concentration, at equilibrium, of nitrate ions is between 2 and 9 moles/litre.
37. Method in accordance with one of the claims 1 to 16, characterised by the fact that the temperature of extraction is between 10°C and 18. Method in accordance with one of the claims 1 to 17, characterised by the fact that after the extraction stage, the organic phase is washed with water or with an aqueous solution containing nitrate ions. 19. Method in accordance with claim 18, characterised by the fact that the washing solution is a nitric acid aqueous solution with a concentration of less than 1 N. Method in accordance with claim 19, characterised by the fact that the concentration of nitric acid aqueous solution is between 10 3 and 10 N. 21. Method in accordance with claim 18, characterised by the fact that the washing solution is an aqueous solution of rare earth nitrates, the concentration of which, expressed in rare earth oxides is between 5 and 500 g/l. 22. Method in accordance with claim 21, characterised by the fact that the concentration of the aqueous solution of rare earth nitrates is between 100 and 500 g/l. 23. Method in accordance with one of the claims 1 to 22, characterised by the fact that after the consecutive extraction and washing stages, followed by the separation of the aqueous and organic phases, there is a regeneration 17 stage for the extraction solvent which is placed in contact with the organic phase or with water or with an acid aqueous solution. 24. Method in accordance with claim 22, characterised by the fact that the acid aqueous solution is a solution of nitric acid, sulphuric acid, hydrochloric acid, perchloric acid. Method in accordance with claim 24, characterised by the fact that the acid aqueous solution is a solution of nitric acid. 26, Method in accordance with one of the claims 24 and characterised by the fact that the concentration of the acid aqueous solution is less than 1 N. 27. Method in accordance with claim 26, characterised by the fact that the concentration of the acid aqueous *3 1 solution is between 10 and 10 28. Method in accordance with one of the claims 1 to 27, characterised by the fact that in a first stage, with the aim of separating at least two of the rare earths or two sub-groups of rare earths, the aqueous solution of rare earth nitrates is put in contact with an organic phase composed of a diluent and the aforementioned organophosphorus compound so as to extract, in the organic phase, the rare earth or sub-group of tre earths which has the highest co-efficient of distribution the other rare earth or sub-group of earths remaining essentially in the aqueous phase; at a second stage, the organic phase is selectively washed using an aqueous solution containing LII I ,u~p nitrate ions in order to eliminate the small quantity of the rare earth or the sub-group of rare earths which were least extracted in the organic phase by their passage into the aqueous phase; the organic phase is then separated from the aqueous phase; at a third stage the extraction solvent is regenerated by putting the organic phase in contact with water or with an acid aqueous solution. 29. Method in accordance with claim 28, characterised by the fact that yttrium is separated from the yttric rare earths. at 30. Method in accordance with claim 29, characterised by a the fact that yttrium, expressed as an oxide, represents from 5 to 80% of the total weight of the yttric rare earths expressed in oxides. 31. A method of separation of rare earths substantially as herein described with reference -o any one of Examples 1 to 3. 32. A method of separation of rare earths substantially as herein described with reference to the accompanying drawing. DATED this 30th day of May, 1990. ba* t RHONE-POULENC CHIMIE a a 0 1 Attorney: LEON K. ALLEN Fellow Institute of Patent Attorneys of Australia of SHELSTON WATERS
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8703959A FR2612911B1 (en) | 1987-03-23 | 1987-03-23 | PROCESS FOR SEPARATING RARE EARTH BY LIQUID-LIQUID EXTRACTION |
| FR8703959 | 1987-03-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU1338788A AU1338788A (en) | 1988-09-22 |
| AU601270B2 true AU601270B2 (en) | 1990-09-06 |
Family
ID=9349288
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU13388/88A Ceased AU609100B2 (en) | 1987-03-23 | 1988-03-22 | Process for separation of rare earths |
| AU13387/88A Ceased AU601270B2 (en) | 1987-03-23 | 1988-03-22 | Process for separation of rare earths |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU13388/88A Ceased AU609100B2 (en) | 1987-03-23 | 1988-03-22 | Process for separation of rare earths |
Country Status (14)
| Country | Link |
|---|---|
| EP (2) | EP0284503B1 (en) |
| JP (2) | JPH0761865B2 (en) |
| KR (1) | KR920000536B1 (en) |
| CN (2) | CN88101564A (en) |
| AT (2) | ATE77414T1 (en) |
| AU (2) | AU609100B2 (en) |
| BR (2) | BR8801283A (en) |
| CA (2) | CA1309595C (en) |
| DE (2) | DE3872013T2 (en) |
| FI (1) | FI881367A (en) |
| FR (1) | FR2612911B1 (en) |
| MY (2) | MY103242A (en) |
| NO (2) | NO881237L (en) |
| ZA (2) | ZA882063B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2627478B1 (en) * | 1988-02-19 | 1991-02-15 | Rhone Poulenc Chimie | PROCESS FOR THE TREATMENT OF RESIDUES CONTAINING RARE EARTH AND COBALT |
| FR2643911B1 (en) * | 1989-03-03 | 1992-06-12 | Rhone Poulenc Chimie | PROCESS FOR TREATING RARE EARTH ORES |
| CN1045626C (en) * | 1994-11-30 | 1999-10-13 | 中国科学院上海有机化学研究所 | Neutral phosphorus type extracting agent for separating yttrium |
| CN103441330A (en) * | 2013-08-06 | 2013-12-11 | 华为终端有限公司 | Wireless communication equipment |
| JP5684885B1 (en) * | 2013-08-12 | 2015-03-18 | 国立大学法人九州大学 | Rare earth extractant and rare earth extraction method |
| FR3035880B1 (en) | 2015-05-07 | 2017-06-02 | Commissariat Energie Atomique | USE OF NOVEL COMPOUNDS FOR THE SELECTIVE EXTRACTION OF RARE EARTHS FROM AQUEOUS SOLUTIONS COMPRISING PHOSPHORIC ACID AND METHOD OF EXTRACTING THE SAME |
| US9968887B2 (en) * | 2015-05-29 | 2018-05-15 | Ut-Battelle, Llc | Membrane assisted solvent extraction for rare earth element recovery |
| FR3055906B1 (en) * | 2016-09-15 | 2018-09-28 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | NOVEL EXTRACTOR USEFUL FOR EXTRACTING RARE EARTHS FROM AQUEOUS PHOSPHORIC ACID SOLUTION, AND APPLICATIONS THEREOF |
| CN114737056B (en) * | 2021-01-08 | 2023-11-03 | 厦门稀土材料研究所 | Organic extractant, and method and application thereof for recovering metal elements |
| CN113584327B (en) * | 2021-06-28 | 2022-10-28 | 中国恩菲工程技术有限公司 | Method for purifying scandium oxide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2515630B1 (en) * | 1981-10-30 | 1985-10-04 | Rhone Poulenc Spec Chim | PROCESS FOR EXTRACTING AND SEPARATING URANIUM, THORIUM AND RARE EARTHS BY TREATING AQUEOUS CHLORIDE SOLUTIONS THEREOF |
| FR2562059B1 (en) * | 1984-04-02 | 1989-12-01 | Rhone Poulenc Spec Chim | PROCESS FOR SEPARATING RARE EARTH BY LIQUID-LIQUID EXTRACTION |
| JPS61281833A (en) * | 1985-06-08 | 1986-12-12 | Seitetsu Kagaku Co Ltd | Purifying method for cerium |
-
1987
- 1987-03-23 FR FR8703959A patent/FR2612911B1/en not_active Expired - Lifetime
-
1988
- 1988-03-18 EP EP88400645A patent/EP0284503B1/en not_active Expired - Lifetime
- 1988-03-18 DE DE8888400645T patent/DE3872013T2/en not_active Expired - Fee Related
- 1988-03-18 EP EP88400646A patent/EP0284504B1/en not_active Expired - Lifetime
- 1988-03-18 DE DE8888400646T patent/DE3872014T2/en not_active Expired - Fee Related
- 1988-03-18 AT AT88400646T patent/ATE77414T1/en not_active IP Right Cessation
- 1988-03-18 AT AT88400645T patent/ATE77413T1/en not_active IP Right Cessation
- 1988-03-21 NO NO881237A patent/NO881237L/en unknown
- 1988-03-21 NO NO881236A patent/NO881236L/en unknown
- 1988-03-22 MY MYPI88000293A patent/MY103242A/en unknown
- 1988-03-22 CA CA000562127A patent/CA1309595C/en not_active Expired - Lifetime
- 1988-03-22 FI FI881367A patent/FI881367A/en not_active IP Right Cessation
- 1988-03-22 AU AU13388/88A patent/AU609100B2/en not_active Ceased
- 1988-03-22 AU AU13387/88A patent/AU601270B2/en not_active Ceased
- 1988-03-22 BR BR8801283A patent/BR8801283A/en unknown
- 1988-03-22 JP JP63065970A patent/JPH0761865B2/en not_active Expired - Lifetime
- 1988-03-22 CA CA000562128A patent/CA1309596C/en not_active Expired - Lifetime
- 1988-03-22 JP JP63065971A patent/JPH0755825B2/en not_active Expired - Lifetime
- 1988-03-22 BR BR8801284A patent/BR8801284A/en unknown
- 1988-03-22 MY MYPI88000294A patent/MY103243A/en unknown
- 1988-03-23 CN CN198888101564A patent/CN88101564A/en active Pending
- 1988-03-23 KR KR1019880003135A patent/KR920000536B1/en not_active IP Right Cessation
- 1988-03-23 CN CN198888101566A patent/CN88101566A/en active Pending
- 1988-03-23 ZA ZA882063A patent/ZA882063B/en unknown
- 1988-03-23 ZA ZA882060A patent/ZA882060B/en unknown
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5192443A (en) | Separation of rare earth values by liquid/liquid extraction | |
| FI77898B (en) | FOERFARANDE FOER SEPARERING AV SAELLSYNTA JORDARTSMETALLER MED HJAELP AV VAETSKE-VAETSKE-EXTRAKTION. | |
| Fontana et al. | Separation of middle rare earths by solvent extraction using 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester as an extractant | |
| AU601270B2 (en) | Process for separation of rare earths | |
| CN1131326C (en) | Technological process for directly producing mixed rare earth oxide | |
| US4243637A (en) | Uranium recovery from pre-treated phosphoric acid | |
| US6093376A (en) | Selective separation of rare earth elements by ion exchange in an iminodiacetic resin | |
| FI68663B (en) | FOERFARANDE FOER AVSKILJANDE AV MINST ETT TILL GRUPPEN AV LANTANIDER OCH YTTRIUM HOERANDE GRUNDAEMNE GENOM EXTRAKTION | |
| CN115652113B (en) | Method for extracting and separating rare earth from ocean rare earth sulfuric acid leaching solution | |
| US3615170A (en) | Process for separating metals using double solvent extraction with bridging solvent medium | |
| US5258167A (en) | Extractant for rare earth metal and method for extracting the same | |
| Zahir et al. | Extractive separation of trivalent lanthanide metals with a combination of Di (2-ethylhexyl) phosphoric acid and 1, 10-phenanthroline | |
| Bautista | Separation chemistry | |
| US5188735A (en) | Separation of rare earth values by liquid/liquid extraction | |
| AU644147B2 (en) | Process for the separation of yttrium | |
| Preston et al. | The recovery of a mixed rare-earth oxide and the preparation of cerium, europium and neodymium oxides from a South African phosphoric acid sludge by solvent extraction | |
| Ismail et al. | Experimental and Theoretical Study on Sm/Eu-Gd Extraction by P204 and [A336][P204] | |
| AU593061B2 (en) | Method for the removal of lead chlorides from rare earths | |
| US6312654B1 (en) | Method of separating a trivalent actinide from a trivalent lanthanide and/or yttrium in aqueous solution | |
| Amiliana | Extraction of Yttrium from Nd Hydroxide concentrate by using D2EHPA | |
| CN1015801B (en) | Preparation method of high purity yttrium oxide and lanthanum oxide | |
| US3150159A (en) | Removal of hydrocarbon degradation products from organic solutions | |
| AU2021390705A2 (en) | Method for selectively recovering rare earth metals and uranium(vi) from an aqueous solution of phosphoric acid | |
| JPS6135253B2 (en) | ||
| Campbell | Precipitation of Enriched Lutetium by Direct Oxalate Extraction |