AU609100B2 - Process for separation of rare earths - Google Patents
Process for separation of rare earths Download PDFInfo
- Publication number
- AU609100B2 AU609100B2 AU13388/88A AU1338888A AU609100B2 AU 609100 B2 AU609100 B2 AU 609100B2 AU 13388/88 A AU13388/88 A AU 13388/88A AU 1338888 A AU1338888 A AU 1338888A AU 609100 B2 AU609100 B2 AU 609100B2
- Authority
- AU
- Australia
- Prior art keywords
- aqueous solution
- rare earth
- concentration
- organic phase
- extraction
- 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.)
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- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000000926 separation method Methods 0.000 title claims description 27
- 238000000605 extraction Methods 0.000 claims abstract description 66
- -1 rare-earth nitrates Chemical class 0.000 claims abstract description 58
- 239000012074 organic phase Substances 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000008346 aqueous phase Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000000622 liquid--liquid extraction Methods 0.000 claims abstract description 10
- 238000000638 solvent extraction Methods 0.000 claims abstract description 10
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 21
- 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 15
- 150000002910 rare earth metals Chemical class 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- PPDZLUVUQQGIOJ-UHFFFAOYSA-N 1-dihexylphosphorylhexane Chemical compound CCCCCCP(=O)(CCCCCC)CCCCCC PPDZLUVUQQGIOJ-UHFFFAOYSA-N 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
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- RKXBYSUETPOUCS-UHFFFAOYSA-N C(CCCCCCC)[PH2]=O Chemical compound C(CCCCCCC)[PH2]=O RKXBYSUETPOUCS-UHFFFAOYSA-N 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 230000001172 regenerating effect Effects 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 description 9
- 229910052747 lanthanoid Inorganic materials 0.000 description 5
- 150000002602 lanthanoids Chemical class 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 4
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 125000004429 atom Chemical group 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
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 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
- 150000002500 ions Chemical class 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- 229940093635 tributyl phosphate Drugs 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001126326 Cyanea <Cnidaria> Species 0.000 description 1
- 101000634404 Datura stramonium Tropinone reductase 1 Proteins 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101000848007 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) Thioredoxin-1 Proteins 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 239000000969 carrier Substances 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
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 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
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 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
- 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
- 125000004123 n-propyl group Chemical group [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
- 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
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-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
- UXBZSSBXGPYSIL-UHFFFAOYSA-N phosphoric acid;yttrium(3+) Chemical compound [Y+3].OP(O)(O)=O UXBZSSBXGPYSIL-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 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
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 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
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 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
- LLZBVBSJCNUKLL-UHFFFAOYSA-N thulium(3+);trinitrate Chemical compound [Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LLZBVBSJCNUKLL-UHFFFAOYSA-N 0.000 description 1
- FPZZZGJWXOHLDJ-UHFFFAOYSA-N trihexylphosphane Chemical compound CCCCCCP(CCCCCC)CCCCCC FPZZZGJWXOHLDJ-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-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
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
COMMONWEALTH OF AUSTRAL O 1 FORM COMPL E T PATENTS ACT 1952 E SPECIFICATION FOR OFFICE USE: Class Int.Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: I, I rlS, Priority: a c ",,Related Art: *0 qi o a 005
O
0
O
0 0 U 0 00 0 00 ,,Name of Applicant: RHONE-POULENC CHIMIE Address of Applicant: 25, quai Paul Doumer 92408, Courbevoie, SFrance Actual Inventor: Thierry Delloye and Jean-Louis Sabot a 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 it known to me/us:- 1 "1- 1A PROCESS FOR SEPARATION OF RARE EARTHS 4 0 a 0 0 N a o 4
N
*0 0 4 0
N
4 tC C 4 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 the elements.
The term "rare earths" used in accordance with the invention includes rare earthelements by the name of lanthanides which have atomic numbers from 57 to 71 inclusive and yttrium with the atomic number 39.
In the description of this invention which follows, .i by "ceric rare earths", we indicate the lighter elements of rare earths, starting with lanthane, through to neodymium, in accordance S with the atomic numbers and by "yttric rare earths", we designate the heaviest elements of rare earths, starting with samarium and c ending with lutecium and including yttrium.
It is a well known fact that rare earths are difficult to separate due to the difference in the properties of one rare earth in relation to those next to it being extremely slight.
0 Methods for the separation of these very similar S elements have been developed which have taken on particular S importance in the separation of rare earths, i.e. liquid-liquid S extraction methods. They are based on the selective extraction 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.
4 As an extraction solvent, certain Crganophosphorus S compounds are already used in solution with an organic diluent to separate rare earths from one another. The use of tri noctylphosphine 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 0000 0 000 0 0 00 0 0000 04 0 e 0 2 0 0 0 0 0 00 0 0 S0 0 S0 .1 00 00 0 0 0 o 0 0 0 00 00 o o 000000 0 0 o o 0 0 o* 0 00 o00 0 0o 0 00 0 0 0 00 a 0 0 0 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 correlated to 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 present invention consists in a method for the separation of rare earths contained in an aqueous solution having at least two of the rare earths, said method comprising the step of extracting the rare earths by liquid-liquid extraction between the aqueous phase containing rare earth nitrates to be separated and an organic phase comprising an extraction agent comprising at least two organoophosphorus compounds having the formula and respectively; 1 R P O 2
R
3 R P 0 i 3 wherein formula
R
I
R
2 and R 3 are identical or different and are, hydrogen or an optionally substituted, linear or branch(.
hydrocarbon radical saturated or unsaturated, or a cyclic hydrocarbon radical, saturated or unsaturated, wherein the sum of the carbon atoms of the radicals R
I
R
2 and R 3 is at least 12 carbon atoms, and wherein formula
R
4
R
5 and R 6 are identical or different and are hydrogen or an optionally substituted, linear or branched, 00 ,o hydrocarbon radical, saturated or unsaturated, wherein *he 0a 0 sum of the carbon atoms of the radicals R 4
R
5 and R 6 0 o 4 5 6 a 00 0o 00 is at least 12 carbon atoms.
S°
0 It should be noted that the radicals R 1
R
2
R
3 4e 0o 21 3 0o 0 o R 4
R
5 and R6 can be carriers of substituent groupings, 0 00 0 o0 0 0 such as, for example, hydroxy or nitro; halogen atoms, in particular chloride and fluorine; lower alkoxy radicals S having a low carbon condensation for example, 1 to 4 atoms; ooo00 o o .oa. cyano groups etc...
0 0 o* The R 1
R
2 R3, R 4
R
5 and R 6 have a number 000006 S* of carbon atoms which usually vary between 1 and 18 atoms of carbon but for preference between 2 and 8 carbon atoms.
They are chosen so that the total number of carbon atoms of the radica ls R, R 2
R
3
R
4
R
5
R
6 is 12 and preferably more than 18.
i- ~aLlr~ 4 For examples of the radicals Rl, R 2
R
3
R
4
R
5
R
6 there are methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, methyl- 1-butyl, isopentyl, tert-pentyl, neo-pentyl radicals, the following normal alkyl radicals 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 branched alkyl radicals which correspond and the cycloalkyl radicals, the cyclohexyl radical in particular.
The following is particularly well suited for use in this S e e Ot invention, a mixture of two extraction agents, one of the extraction agents answering to formula in which R S R 2
R
3 are identical linear alkyl radicals, which means S that the radicals R 1
R
2
R
3 are linear alkyl radicals S with the same carbon condensation, the other answering to formula in which R R 5
R
6 are identical alkyl radicals, which means that the radicals R 4
R
5
R
6 are S4 5 6 linear alkyl radicals with the same carbon condensation but these have a different carbon condensation to the radical R R R 3 j To the extraction agent of formula in which RI, C c R2' R 3 are identical linear alkyl radicals may be t associated an extraction agent with the formula in which:
R
4
R
5
R
6 are identical branched alkyl radicals, that is, the radicals R 4
R
5 are branched alkyl radicals with the same carbon condensation.
1 I
N
4a 0O O oo 0 00 0 00 0 0~ e 0 000 00 0 0 0 0 0) U Uf U 000~ O U0 Un 0 0 U 0 0r 0 00
R
4
R
5 R6, are different branched alkyls, that is, at least one of the radicals is different from the two others,
R
4
R
5
R
6 are linear and branched alkyl radicals, that is, there is a simultaneous presence of at least one linear alkyl radical and at least one branched alkyl radical.
The proportion of the organophosphorus compounds in formula and is determined in such a way that a mixture of phosphine oxides which is liquid at the ambient temperature is obtained. The mixture obtained is miscible with the usual diluents in all proportions.
As examples of preferred phosphine oxides in accordance with the invention we quote a mixture of tri(n-hexyl) phosphine and tri(n-octyl) phosphine oxide, in particular tne product known as CYANEX 923 (Registered Trade Mark), marketed by AMERICAN CYANAMID.
Another extraction agent which is favoured is the product known as CYANEX 925 (Registered Trade Mark) which is a mixture composed of 85% of bis(trimethyl-2,4,4 pentyl) oxide n-octylphosphine and 10% tri(trimethyl 1-2,4,4 pentyl) phosphine.
The applicant has found that these extraction agents offer a very good selectivity in relation to the whole of rare earths and in particular to yttrium and the yttric rare earths, notably from gadolinium to lutecium, in contrast to the more usual neutral organophosphorus extraction agents such, for example, as tributyl phosphate.
4b An app'tication, well adapted to th3 method used in this invention is the method for thEI separation of yttrium from the other yttric rare earths yttrium can represent from to 80% of the total weight of the yttric rare earths :the percentage being expressed in weight of the yttrium oxide in relation to tit 4 4 i 4 A i weight of the yttric rare earth oxides, including yttrium.
Another advantage of the extraction agents is that they function in the presence of aqueous phases which have a high concentration of rare earth nitrates (more than 300 g/1) and very concentrated organic phases can be obtained, from more than 50 g to 100 g/1 and more of rare eartis expressed in oxides.
In accordance with the method used in this invention, the aqueous phase which is placed in contact with the extraction agent can be composed of an aqueous solution supplied by the redissolution with nitric acid, of the hydroxides obtained by a sodic attack on the ores containing rare earths such as monazite, bastnaesite and xenotime. Any other rare earth salt solution may be used after the anion present has been changed to a nitrate 0 o0 anion.
o o 0 00<' ThE nethod used in this invention applies to solutions Q C a as they are L after they have undergone a previous concentration U 0a Usually, the liquid-liquid extraction process is used o on aqueous solutions of rare earth nitrates with a concentration ic expressed in rare earth oxides which varies between 20 g/1 and 2 0 500 g/l the limits given are not critical. For preference they "oS" have a concentration between 100 g/l and 500 g/l.
They have an acidity which usually varies between 0.01 N and 3.0 N.
m In accordance with the invention, the organic phase 1o00000 o a may contain, as well as the extraction agent, an organic diluent.
0o0° S Diluents which can be used are those usually employed for liquid- S liquid extraction. Among these we quote the aliphatic or cyclo- 0 OQco aliphatic hydrocarbons such for example as hexane, heptane, dodecane, cyclohxane, isoparafin and petroleum cuttings or the o 30 kerosene or isoparafin type the aromatic hydrocarbons such, for O0 0 o example as benzene, toluene, ethylbenzene, xylene, petroleum 0 cuttings composed of alkylbenzene mixtures, notably cuttings of 0 the SOLVESSO type (Trade name registered by EXXON) and the halogenated hydrocarbons such as chloroform, carbon tetrachloride, ethylme dich.oro-1,2, monochlorobenzene.
A mixture of these diluents may also be used.
For preference, an aliphatic hydrocarbon is used.
UU~~
The potency of extraction of the organic solution in relation to the rare earths, increases as the concentration of the extraction agent is increased in the organic phase nevertheless, the factors of separation of the elements between each other are not modified in any noticeable way by the concentration of the extraction agent. Thus, the concentration of the extraction agent in the organic phase is not a critical factor according to the invention and may vary within wide limits. It can vary from of the volume of the organic phase when the extraction agent is in solution in a diluent, up to approximately 100 whFe the extraction agent is used neat.
For preference, the concentration is selected between and 100 of the volume of the organic phase.
In accordance with the invention, the organic phase may also contains various modifying agents, the principal aim of which is to improve the hydrodynamic properties of the system without altering the extracting properties of the organophosphorus compounds. Among the compounds which work well are the compounds with an alcohol function, particularly the heavy alcohols which have a number of atom carbons between 4 and 15 and the heavy phenols, as well as other various compounds such as certain phosphoric esters such as tri-butylphosphate. A proportion between 3 and 20 by volume in relation to the organic phase is usually favourable.
When cho.,. ng the conditions for the extraction, the concentration of nitrate ions is important as it can facilitate the extraction of the or the several rare earths to be extracted in the orgaiic phast. The concentration of nitrate ions can vary between 1 and 10 moles /litre and for preference is selected between 2 and 9 moles/litre.
SIf necessary, the concentration of nitrate ions can be Sincreased by adding these for example with the addition of an aqueous solution of nitric acid, an aqueous solution of a salt in the form of a nitrate, notably ammonium nitrate.
During the extraction phase, the organic phase and the aqueous phase are placain contact at a temperature which is not critical it is usually selected between 30 0 C and 60 0
C.
C Q 7 The ratio of flow of the organic phase and the 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 in accordance with the equipment usually used for the liquid-liquid extraction.
When certain rare eartis have been extracted in the organic phase in small quantities when they should have remained in the aqueous phase, it is sometime necessary to introduce a washing stage after the extrajtion stage.
In the washing stage, the organic phase is washed with water, preferably de-ionised water or with an aqueous solution containing nitrate ions, such as an aqueous solution of diluted Snitric acid or an aqueous solution of rare earth nitrates of the same type as the rare earths to be extracted and which can be contained in the part of the aqueous phase obtained in the regeneration stage of the extraction solvent which follows.
When the washing is done with a nitric acid solution, S the concentration is selected at less than 1 N and for preference, Sbetween 10 3 and 10"1N. When an aqueous solution of rare earth nitrates is used, the concentration expressed in rare earth oxides can be included between 5 and 500 g/l, preferably between 100 and g/1.
After the extration and washing followed by the separation of the aqueous phase from the organic phase, the extraction Ssolvent undergoes a regeneration stage.
The single or several rare earths extracted in the organic phase are separated by placing this last in contact with water, preferably de-ionised or with an acid aqueous solution such as, for example, an aqueous solution of nitric acid, sulphuric acid, hydrochloric acid c perchloric acid. For preference, nitric acid is used.
The concentration of the acid solution is selected at less than 1 N and, preferably between 10-3 and 10-1 N.
The one or several rare earths extracted are recovered in the aqueous phase while the extraction solvent can be recycled at the extraction stage. This recycling is not essential to 8 this invention but is desirable for reasons of economy.
A plan follows which allows for the separation, in accordance with the method as previously described in this invention, 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 reLtion between the coefficient of distribution of TR 1 and TR2 PTRi F o TR2 1 0 n ,The co-efficient of distribution is equal to the ratio between the concentration of TR I (or TR 2 in he organic phase 6 ae and the concentration of TRI or (TR 2 in the aqueous phase.
0 So that the separation between TR 1 and TR2 may be 000000 0 possible, F must be different from 1.
If TR1 is the rare earth which has the highest co- S efficient of distribution, F in this case is greater than 1.
In accordance with the invention, at least two rare Qoo earths TRI and TR 2 are separated by liquid-liquid extraction, between an aqueous phase containing at least the nitrates of these S" rare earths and an organic phase containing the aforesaid extraction agent by proceeding as follows in the first stage, the separation of TR 1 and TR 2 is done BQ O a by extracting TRI in the organic phase TR 2 remaining essentially :i in the aqueous phase at the second stage, selective washing or the organic phase containing TR 1 and a small quantity of TR 2 is carried out using an aqueous solution containing nitrate ions which allows the 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 an acid aqueous solution.
The methods of operation for each stage have previously been described.
i I_ 9 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 1 and TR 2 If a mixture of n rare earths are to be separated individually, the sequence of three stage which have just been described is followed, 1) times in order to separate all the rare earths from oneanother.
The practical application of the invention can ha carried out using the usual counter-current technique as explained above but co-current and cross-current techniques well know to the experts can also be used.
s The various contact stages can be effected in the usual liquid-liquid extraction equipment operating counter-current.
This equipment usually includes several tiers of mixer-decanting systems or lined columns and/or agitated, set up for an extract- S ion operation, for selective washing and the recovery of rare t C C earth elements in an aqueous phase and for the regeneration of C C, the extraction solvent.
The examples which follow are given only as indications and should not be considered as limiting the area or concept of the invention.
6 4 *0 1 In these examples, the percentages given are expressed in weight, unless otherwise indicated.
EXAMPLE 1 Factor of separation of yttrium in relation to a lanthanide in a nitrate medium using a mixture of liqcid 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/1 distributed as follows ceric rare earths La23 2 0 23.0 Co02 46.5 Prg 6 11 5.1 Nd2O 18.4 1 I I ~-aslyrr~ i :ttric rare earths Sm2 3 M 2.3 Eu203 0.07 Gd2 0 3 1.7 Tb 4 0 7 0.16 Dy 2 0 3 0.52 Ho 2 0 3 0.09 Er2 0 3 0.13 Tm 0 0.013% 2 3 1 Yb 2
Q
3 0.061% 4u 2 0 3 0.006% Y 2 0 3 2.0 As an e;itraction agent, the following is used a mixture of trialkytphosphine oxides cuw ,m ed of 60 tri(n-hexyl)phosphine oxide and 40 tri(n-octyl)phosphine marketed by the american company Cyanamid under the name of Y NEX 923.
This extraction agent is placid in solution in an aromatic hydrocarbon, the petroleum cutting SOV8SSQ 150, composed of a mixture of alkylbeaiizene, in particular dymethylbenene and tetramethyl benzone at the rate of 1 mole/litre and the resulting mixture is the extraction solvent.
The aqueous phaae composed of the solution of rare earth nitrates is placed n contact with the organic phase composed of the extraction solvent the ratio of the volume of the phases being equal to one unit, The extraction is done at ambient temperature.
This allows the factor of separation tn/ n be determined for the lanthanide pair (Ln/yttrium which are shown in the tollowing table Ex Sn rac tion La Ce Pr Nd Sm Eu Od Tb Dy Ho Er Tm Yb bu agent: Mixture of tri- Thosph- 0.02 0.09 0.12 0.18 0.59 0.48 0.48 0.75 1.00 1.16 1.44 2.94 2.90 2.2 Ine
CYANEX
923 I *i" 1 11 Tha values of the factors of separation given above allow for t .e calculation of the requirement for the separation of yttrium from the other rare earths according to the usual liquidliquid extraction techniques.
It is to be noted that the mixture of phosphine oxides mentioned has a very good selectivity in relation to the yttrium for t.e yttric rare earths which are the heaviest.
EXAMPLE 2 Factor of separation of yttrium in relation to a lanthanide in a nitrate medium using a mixture of phosphine oxide, liquid, 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.
At a temperature of 500, the aqueous phase composed of the rare earth nitrate solution as defined in example 1 is placed in contact with the organic phase composed of the extraction solvent the ratio of the volume of the phases being equal to the unit.
The following table gives the factors of separation FLn/y of the lanthanide couple (Ln)/yttr'.um as well as the charge of the solvent of extraction, at equilibrium, expressed in g of rare earth oxide per litre.
Ln EX Charge trac of ion Nd Sm Eu Gd Tb Dy Ho Er Tn Yb Lu lvent agent g slvent Mixture of trialkyl phosphine CYANEA 0.35 0.54 0.73 0.67 0.94 1.12 1.32 1.71 3.1 1.71 '.93 98.8 23 It is to be noted that the mixture of phosphine oxides given in accordance with the invention is well adapted to a separation yttrium/yttric rare earths, the heaviest.
I
0P 0 0 0o 0 40 L 12 EXAMPLE 3 Method of separation of yttrium from a mixture containing thulium nitrate, ytterbium and lutecium.
This example is executed using the method described in figure 1.
The equipment used for separating these rare earths includes a first liquid-liquid extraction battery with several tiers of the mixing-decanting type, operating countercurrent and composed of an extraction section with cc, C, CV 36 theoretic stage and a washing section with ct 14 theoretic stages, a regeneration-recovery section for the extraction C C c solvent composed of 10 theoretic stages.
The initial mixture or rare earths to be separated is a PCS" solution of rare earth nitrates with an acidity of 0.1 N and a concentration expressed in rare earth oxides of 270 g/l distributed as follows yttrium oxide 95.0 ,O thulium oxide 0.8 ytterbium oxide 3.8 ce lutecium oxide 0.4 The extraction agent used is the mixture of tri-alkyl phosphine oxides (CYANEX 923) as sused in example 1.
,c i This extractions agent is placed in solution in kerosene S at 75 of volume and this mixture is the extraction solvent.
Before describing the various processes, it should be noted that the direction of the organic phase is used for the entry and exit of the extraction-washing nd regeneration-recovery units.
The sequence of the stages is at the exit of the extraction unit at the solution of rare earth nitrates to be separated are introduced at a flow rate of 161 1/h at the entry of the extraction unit at the extraction solvent in introduced at a rate of 2135 1/h; at the exit of the counter extraction section and counter-current to the organic phase, S 13 de-ionised water is introduced at a rate of 1060 1/h at the entry to the counter-extraction section (b) at an aqueous solution of rare earth nitrates is recovered and concentrated by evaporation until a concentration expressed in rare earth oxides of 450 g/l is obtained having the following distribution 8.0
Y
2 0 3 ,15.0 Tm 2 0 3 70 Yb 2 0 3 and 7 Lu 2 0 3 5 1/h are recovered, this being the production and the remainder, 550 1/h, supply at the washing unit to form the back-flow at the entry of the washing unit at at a flow of 711 1/h a very pure aqueous solution of yttrium nitrate is recovered with a concentration expressed in
Y
2 0 3 of 59 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(7) the purified extraction solvent is recovered and can be recycled at in the extraction unit at the same rate of flow this recycling is not, however, essential to this 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 an excellent extraction output of 93.8 and a very high purity which is 99.9999
Claims (24)
1. A method for the separation of rare earths contained in an aqueous solution having at least two of the rare earths said method comprising the step of extracting the rare earths by liquid-liquid extraction between the aqueous phase containing rare earth nitrates to be separated and an organic phase comprising an extraction agent comprising at least two organophosphorus compounds having the formula and respectively: R R 1 4 R P R P 0 2 0 o0 R R o o0 3 6 o S^ wherein formula S R, R 2 and R 3 are identical or different and are, 1- a q0 hydrogen or an optionally substituted linear or branched hydrocarbon radical saturated or unsaturated or a cyclic hydrocarbon radical, saturated or unsaturated; wherein the 0 sum of the carbon atoms of the radicals R 1 R 2 and R Sis at least 12 carbon atoms, and wherein formula S. R 4 R 5 and R 6 are identical or different and are 0 00 e o hydrogen or an optionally substituted, linear or branched 0 hydrocarbon radical, saturated or unsaturated, wherein the sum of the carbon atoms of the radicals R 4 R 5 and R 6 is at least 12 carbon atoms. rr- i 1~ 15
2. A method according to claim 1 wherein the organophosphorus compounds of formulae and R 1 R 2 R 3 R 4 R 5 and R 6 each have from 1 to 18 carbon atoms.
3. A method according to claim 2 wherein R 1 R 2 R 3 R 4 R 5 and R 6 each have from 1 to 8 carbon atoms.
4. A method according to any one of the claims 1 to 3 wherein the organophosphorus compound of formula the sum of the carbon atoms of the radicals R 1 R 2 and R 3 is at least 18 carbon atoms. A method according to any one of the claims 1 to 4, wherein the organophosphorus compound of formula the 0 S* sum of the carbon atoms of the radicals R R 5 and R 6 o 1 4 5 6 0oo', is at least 18 carbon atoms. o 0 o oe 6. A method according to any one of the claims 1 to wherein the extraction agent comprises an organophosphorus 0 0 compound of formula in which R 1 R 2 and R 3 are identical linear alkyl radicals and an organophosphorus oos0 compound of formula in which R 4 R 5 and R 6 are 0p" t identical linear alkyl radicals with a carbon condensation a: which is different to the radicals R 2 and R 3 o 3
7. A method according to any one of the claims 1 to S wherein the extraction agent comprises an organophosphorus compound of formula in which R 1 R 2 and R 3 are identical linear alkyl radicals and an organophosphorus compound of formula in which R 4 R 5 and R 6 are identical branched alkyl radicals or different branched alkyl radicals, or branched or linear alkyl radicals. i i 16
8. A method according to any one of the claims 1 to 7, wherein the extraction agent is a mixture of tri(n-hexyl) phosphine oxide and tri(n-octyl) phosphine oxide or a mixture of bis(trimethyl-2,4,4 pentyl) n-octylphosphine oxide and tri(trimethyl-2,4,4 pentyl) phosphine.
9. A method according to uny one of the claims 1 to 8, wherein the aqueous solution of rare earth nitrates has a concentration, expressed in rare earth oxides between 20 g/l and 500 g/l. A method according to claim 9 wherein the concentration of rare earth nitrates is between 100 g/l and 500 g/l. 'c o 11. A method according to claims 9 or 10 wherein the aqueous S solution of rare earth nitrates has an acidity between 0.01 N and 3.0 N.
12. A method according to any one of the preceding claims wherein the organic phase further comprises at least one organic diluent selected from the group comprising aliphatic or cycloaliphatic hydrocarbons, petroleum cuttings of the kerosene or isoparaffin type, aromatic hydrocarbons, petroleum cuttings consisting of alkylbenzene mixtures and halogenated hydrocarbons.
13. A method according to claim 1 wherein the concentration of the extraction agent in the organic phase is between 5 and 100% by volume of the organic phase.
14. A method according to claim 13 wherein the concentration of the extraction agent is between 50 and 100%. 17 A method according to any one of the claims 1 to 14 wherein the organic phase further comprises at least one modifying agent selected from the group comprising the compounds with an alcohol function and the phosphoric esters.
16. A method according to claim 15 wherein the concentration of the modifying agent in tha organic phase is between 3 and by volume of the organic phase.
17. A method according to any one of the claims 1 to 16 wherein the ion nitrate concentration of the aqueous phase during the extraction is between 1 and 10 moles/litre.
18. A method according to claim 17 wherein the concentration B 8t Oo« of nitrate ions is between 2 and 9 moles/litre.
19. A method according to any one of the claims 1 to 18 i t wherein the extraction temperature is between 10°C and 80 0 C. A method according to any one of the claims 1 to 19 further comprising the step of washing the orgunic phase with water using an aqueous solution containing nitrate ions.
21. A method according to claim 21 wherein the concentration of the nitric acid aqueous solution is less than 1 N.
22. A method according to claim 21 wherein the concentration of the nitric acid aqueous solution is between 10 3 and i N.
23. A method according to claim 20 wherein the washing solution is an aqueous solution of rare earth nitrates with a concentration expressed in rare earth oxides of between 5 and 500 g/l. 4 o^J .L I, 18
24. A method according to claim 23 wherein the concentration of the aqueous solution of rare earth nitrates is between 100 and 500 g/l. A method according co any one of the claims 1 to 24 further comprising the steps of sepaTating the aqueous phase and the organic phase then regenerating the extraction solvent by placing the organic phase in contact with water or with an acid aqueous solution.
26. A method according to claim 25 wherein the acid aqueous solution is a nitric acid aqueous solution, or a sulphuric acid or hydrochloric acid or perchloric acid solution.
27. A method according to claim 26 wherein the acid aqueous solution is a nitric acid solution,
28. A method according to claim 26 or 27 wherein the concentration of the acid aqueous solution is less than 1 N.
29. A method according tc claim 28 wherein the concentration of the acid aqueous solution is between 10 3 N and 101 N. A method according to any one of the claims 1 to 29 oItt, wherein in a first stage, in order to separate at least two A 4 rare earths or two rare earth sub-groups, the aqueous solution of rare earth nitrates is placed in cont .c with an organic phase composed of a diluent of the extraction agent in order to extract, in the otganic phase, the rare earth or S the rare earth sub-group having a co-efficient of distribution which is the highest; the other rare earth or rare earth sub-group remaining essentially in the aqueous phase; in a second stage, the organic phase is selectively washed using an aqueous solution containing nitrate ions in QI i 3 19 order to eliminate the small quantity of the rare-earth or rare earth sub-group the least extracted in the organic phase by the passage into the aqueous phase, the organic phase and the aqueous phase are then separated; in a third stage, the extraction solvent is regenerated by putting the organic solvent in contact with water or with an acid aqueous solution.
31. A method according to claim 30, wherein yttrium is separated from the yttric rare earths.
32. A method according to claim 31 wherein the yttrium expressed in oxide represents from 5 to 80% of the total 0 6 weight of the yttric rare earths expressed in oxides. S33. A method substantially as herein described with reference to any one of the examples. a 4 DATED this 16th day of JANUARY, 1991 RHONE-POULENC CHIMIE Attorney: WILLIAM S. LLOYD Fellow Institute of Patent Attorneys of Australia .c of SHELSTON WATERS S C 0D7
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 |
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| Publication Number | Publication Date |
|---|---|
| AU1338888A AU1338888A (en) | 1988-09-22 |
| AU609100B2 true AU609100B2 (en) | 1991-04-26 |
Family
ID=9349288
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|---|---|---|---|
| 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 After (1)
| Application Number | Title | Priority Date | Filing Date |
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| AU13387/88A Ceased AU601270B2 (en) | 1987-03-23 | 1988-03-22 | Process for separation of rare earths |
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| Country | Link |
|---|---|
| EP (2) | EP0284503B1 (en) |
| JP (2) | JPH0755825B2 (en) |
| KR (1) | KR920000536B1 (en) |
| CN (2) | CN88101564A (en) |
| AT (2) | ATE77413T1 (en) |
| AU (2) | AU609100B2 (en) |
| BR (2) | BR8801284A (en) |
| CA (2) | CA1309595C (en) |
| DE (2) | DE3872014T2 (en) |
| FI (1) | FI881367A (en) |
| FR (1) | FR2612911B1 (en) |
| MY (2) | MY103243A (en) |
| NO (2) | NO881236L (en) |
| ZA (2) | ZA882060B (en) |
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| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU8985382A (en) * | 1981-10-30 | 1983-05-05 | Rhone-Poulenc Specialites Chimiques | Solvent extraction process |
| AU4055385A (en) * | 1984-04-02 | 1986-10-09 | Rhone-Poulenc Specialites Chimiques | Separation of rare earth values by liquid liquid extraction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61281833A (en) * | 1985-06-08 | 1986-12-12 | Seitetsu Kagaku Co Ltd | Purifying method for cerium |
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1987
- 1987-03-23 FR FR8703959A patent/FR2612911B1/en not_active Expired - Lifetime
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1988
- 1988-03-18 DE DE8888400646T patent/DE3872014T2/en not_active Expired - Fee Related
- 1988-03-18 AT AT88400645T patent/ATE77413T1/en not_active IP Right Cessation
- 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 AT AT88400646T patent/ATE77414T1/en not_active IP Right Cessation
- 1988-03-21 NO NO881236A patent/NO881236L/en unknown
- 1988-03-21 NO NO881237A patent/NO881237L/en unknown
- 1988-03-22 JP JP63065971A patent/JPH0755825B2/en not_active Expired - Lifetime
- 1988-03-22 BR BR8801284A patent/BR8801284A/en unknown
- 1988-03-22 BR BR8801283A patent/BR8801283A/en unknown
- 1988-03-22 AU AU13388/88A patent/AU609100B2/en not_active Ceased
- 1988-03-22 JP JP63065970A patent/JPH0761865B2/en not_active Expired - Lifetime
- 1988-03-22 CA CA000562127A patent/CA1309595C/en not_active Expired - Lifetime
- 1988-03-22 AU AU13387/88A patent/AU601270B2/en not_active Ceased
- 1988-03-22 FI FI881367A patent/FI881367A/en not_active IP Right Cessation
- 1988-03-22 MY MYPI88000294A patent/MY103243A/en unknown
- 1988-03-22 CA CA000562128A patent/CA1309596C/en not_active Expired - Lifetime
- 1988-03-22 MY MYPI88000293A patent/MY103242A/en unknown
- 1988-03-23 ZA ZA882060A patent/ZA882060B/en unknown
- 1988-03-23 KR KR1019880003135A patent/KR920000536B1/en not_active IP Right Cessation
- 1988-03-23 CN CN198888101564A patent/CN88101564A/en active Pending
- 1988-03-23 CN CN198888101566A patent/CN88101566A/en active Pending
- 1988-03-23 ZA ZA882063A patent/ZA882063B/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU8985382A (en) * | 1981-10-30 | 1983-05-05 | Rhone-Poulenc Specialites Chimiques | Solvent extraction process |
| AU4055385A (en) * | 1984-04-02 | 1986-10-09 | Rhone-Poulenc Specialites Chimiques | Separation of rare earth values by liquid liquid extraction |
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