WO2023199083A1 - Process for producing lithium salt with high level of lithium-7 isotope - Google Patents
Process for producing lithium salt with high level of lithium-7 isotope Download PDFInfo
- Publication number
- WO2023199083A1 WO2023199083A1 PCT/IB2022/000319 IB2022000319W WO2023199083A1 WO 2023199083 A1 WO2023199083 A1 WO 2023199083A1 IB 2022000319 W IB2022000319 W IB 2022000319W WO 2023199083 A1 WO2023199083 A1 WO 2023199083A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- group
- macrocycle
- crown
- phosphorylated
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 61
- WHXSMMKQMYFTQS-IGMARMGPSA-N lithium-7 atom Chemical compound [7Li] WHXSMMKQMYFTQS-IGMARMGPSA-N 0.000 title claims abstract description 42
- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 36
- 159000000002 lithium salts Chemical class 0.000 title claims abstract description 36
- 150000003983 crown ethers Chemical class 0.000 claims abstract description 45
- 239000007787 solid Substances 0.000 claims abstract description 43
- 150000002678 macrocyclic compounds Chemical class 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-BJUDXGSMSA-N (6Li)Lithium Chemical compound [6Li] WHXSMMKQMYFTQS-BJUDXGSMSA-N 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 125000004429 atom Chemical group 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005864 Sulphur Substances 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000008346 aqueous phase Substances 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 13
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 229940117389 dichlorobenzene Drugs 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 238000012958 reprocessing Methods 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 125000005309 thioalkoxy group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims 2
- 239000000243 solution Substances 0.000 description 29
- 238000000605 extraction Methods 0.000 description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 229910000497 Amalgam Inorganic materials 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 235000019439 ethyl acetate Nutrition 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical class [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000005372 isotope separation Methods 0.000 description 2
- 230000000155 isotopic effect Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- -1 lithium cations Chemical class 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 229910052722 tritium Inorganic materials 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JZVUAOCDNFNSGQ-UHFFFAOYSA-N 7-methoxy-2-phenyl-1h-quinolin-4-one Chemical compound N=1C2=CC(OC)=CC=C2C(O)=CC=1C1=CC=CC=C1 JZVUAOCDNFNSGQ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229940006487 lithium cation Drugs 0.000 description 1
- BOEOGTSNJBLPHD-UHFFFAOYSA-N lithium mercury Chemical compound [Li].[Hg] BOEOGTSNJBLPHD-UHFFFAOYSA-N 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- ZJZXSOKJEJFHCP-UHFFFAOYSA-M lithium;thiocyanate Chemical compound [Li+].[S-]C#N ZJZXSOKJEJFHCP-UHFFFAOYSA-M 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/22—Separation by extracting
- B01D59/24—Separation by extracting by solvent extraction
-
- 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
- B01D11/0288—Applications, solvents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/22—Separation by extracting
- B01D59/26—Separation by extracting by sorption, i.e. absorption, adsorption, persorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
- C22B3/302—Ethers or epoxides
- C22B3/304—Crown ethers
-
- 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
- B01D11/0215—Solid material in other stationary receptacles
- B01D11/0253—Fluidised bed of solid materials
- B01D11/0257—Fluidised bed of solid materials using mixing mechanisms, e.g. stirrers, jets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/10—Separation by diffusion
- B01D59/12—Separation by diffusion by diffusion through barriers
Definitions
- the invention relates the field of isotope separation in the field of chemical industry, in particular to a process for extraction and enriching lithium isotopes.
- the invention relates to a liquid-solid separation process of lithium-6 and lithium-7 isotopes from a solid alkali lithium salt, where an organic solution of a macrocycle in a water non-miscible solvent is contacted with a solid lithium salt, said macrocycle being chosen among phosphorylated crown-ethers in which the macrocycle comprises from 12 to 16 intracyclic atoms, at least one phosphorus atom, at least one oxygen atom and at least three additional heteroatoms selected in the group consisting of oxygen, sulphur and nitrogen.
- the invention also relates to the use of such a macrocycle for the selective trapping of lithium-7 isotope from a suspension of a solid lithium salt in a water non-miscible organic solvent.
- Naturally occurring lithium is composed of two stable isotopes, lithium- 6 ( 6 Li) and lithium-7 ( 7 Li), with the latter being far more abundant on Earth (natural relative abundance: 6 Li at 7.5% and 7 Li at 92.5%).
- Lithium isotopes separation technologies are very challenging and it is of great importance to develop cost-effective and environmentally-friendly processes.
- Lithium-7 has a very low neutron cross section, making it transparent to neutrons. This property is used in lithium highly enriched in lithium-7 (more than 99%) as a coolant in molten salt reactors, but also as a pH stabilizer in pressurized water reactors. In particular, 7 LiOH of high isotopic purity (99.95%) is required as pH adjuster for coolant fluids in nuclear plants (Pressurize Water Reactors: PWR). The presence of the lighter isotope 6 Li for this application is very deleterious because it could produce radioactive tritium which the concentration is strictly regulated.
- FHR fluoride salt-cooled high-temperature reactors
- the salt also called FLIBE
- the acceptable 7 Li purity requirement is at least 99.995%.
- isotopically pure 6 Li can be used as a mean of tritium production which is crucial for nuclear fusion technologies.
- the amalgam is recovered and the lithium-6 is extracted.
- the lithium hydroxide solution is electrolyzed to extract lithium-7.
- a first object of the present invention is a liquid-solid separation multi-stage process of lithium-6 and lithium-7 isotopes from a solid alkali lithium salt, said multi-stage process comprising at least the following steps: i) contacting an organic solution of a macrocycle in a water non-miscible solvent with a solid lithium salt to obtain a suspension of said solid alkali lithium salt in said organic solution, ii) stirring the suspension obtained in step i) for a period of time sufficient to form a complex of lithium-7 enriched isotope with said macrocycle, iii) mechanically separating said solid lithium salt from said organic solution, said organic solution comprising lithium-7 enriched isotope complexed with said macrocycle, iv) contacting said organic solution with an aqueous phase to extract said lithium-7 enriched isotope from the macrocycle present in the organic solution, and obtain an aqueous phase comprising said lithium-7 enriched isotope and an organic solution comprising said macrocycle freed from said lithium; v) e
- the process according to the present invention has the following advantages: - Selectivity for the 7 Li isotope (all other processes are selective for the other isotope, i.e. 6 Li isotope)
- a solution of a phosphorylated crown-ether in a water non-miscible solvent is stirred in presence of solid lithium salt. After allowing a period of contact the lithium cations distribute into the organic phase and form complexes with the phosphorylated crown-ether.
- the complex [ 7 Li/phosphorylated crown-ether] is more stable than the complex [ 6 Li/phosphorylated crown-ether] allowing the 7 Li / 6 Li ratio increases in the organic solution.
- the system is very advantageous due to:
- intracyclic atoms in reference to the macrocycle, refer to the number of atoms engaged in the cycle constituting said macrocycle. It thus excludes any atom that would belong to a substituent of said macrocycle.
- the phosphorylated crown-ether is selected among phosphorylated crown-ethers of formulae (I) to (III) below:
- - X is O, NR 1 or S,
- - Y represents a non-substituted aryl group; an aryl group bearing at least one substituent selected among a halogen atom chosen among Cl, Br and F, a linear or branched alkyl group having from 1 to 18 carbon atoms, and a linear or branched alkenyl or alkynyl group having from 2 to 18 carbon atoms; a linear or branched alkyl group having from 2 to 18 carbon atoms, a linear or branched alkyl group bearing at least one substituent selected among a halogen atom chosen among Cl, Br, F, mesyle and tosyle; or a linear or branched alkenyl or alkynyl group having from 2 to 18 carbon atoms;
- R 1 represents a hydrogen atom, a linear or branched alkyl group having from 1 to 18 carbon atoms, or a linear or branched alkyl group having from 1 to 18 carbon atoms and substituted by one substituent chosen among an alcoxy group having from 1 to 6 carbon atoms and a trialkyl(C 1 -C 6 )siloxane;
- - n is an integer ranging from 0 to 4.
- - Z 1 , Z 2 and Z 3 identical or different, represent (i) a linear or branched alkenyl or alkynyl group having from 2 to 18 carbon atoms, (ii) a 1,2 or 1,3 or 1,4- O-disubstituted aryl group, or a (iii) a linear alkyl chain having 2 ou 3 carbon atoms, said alkyl group being optionally substituted by:
- R 2 represents hydrogen, an alkyl group having from 1 to 6 carbon atoms or a phosphate group
- the phosphorylated crown-ethers of above formulae (I), (II) and (III) can be prepared as described in international application PCT/CL2020/050133.
- the amount of phosphorylated crown-ether in the organic solution ranges from about 0.01 M and about 5, and more preferably from about 0.1 to about 1.0 M.
- the water non-miscible solvent is preferably selected in the group comprising dichloromethane (DCM), chloroform, heptane, cyclohexane, toluene, xylene, ethyl acetate, butyl acetate, chlorobenzene, dichlorobenzene, anisole, methyl tert-butyl ether (MTBE), and nitrobenzene.
- DCM dichloromethane
- chloroform heptane
- cyclohexane toluene
- xylene ethyl acetate
- butyl acetate chlorobenzene
- chlorobenzene dichlorobenzene
- anisole methyl tert-butyl ether
- MTBE methyl tert-butyl ether
- the solid lithium salt may be chosen among LiCI, LiBr, Lil, Li 2 CO 3 , lithium thiocyanate (LiSCN), Li 3 PO 4 , lithium acetate, lithium trifluoroacetate and LiOH.
- LiCI is particularly preferred.
- the solid lithium salt is in the form of particles whose size ranges from about 40 to about 500 pm and more preferably from about 40 to 100 pm.
- the molar ratio [solid lithium salt/phosphorylated crown-ether] is not critical. However, this molar ratio preferably ranges from about 0.1 to 2000 and more preferably from about 10 to 1000, and even more preferably from about 100 to 500.
- the period of time sufficient to form a complex of lithium-7 isotope with said macrocycle at step ii) may range from about 1 to 48 hours, preferably from about 1 to 2 hours.
- the temperature of the suspension of said solid alkali lithium salt in said organic solution during step ii) is not critical. However, according to a particular embodiment of the present invention, the temperature of the suspension of said solid alkali lithium salt in said organic solution during step ii) ranges from about - 20°C and 100°C, and even more preferably from about 20 to 40°C.
- the mechanical separation of said solid alkali lithium salt from said organic solution may be carried out by any appropriate mean, such as for example by filtration or by centrifugation.
- the solid lithium salt recovered from the said organic solution at the end of step (iii) and the organic solution recovered at the end of step iv), i.e. the organic solution comprising said macrocycle freed from said lithium-7 enriched isotope may both be re-engaged at least once in step (i) of the process, preferably from 1 to 2500 times and even more preferably from 50 to 500 times.
- the process of the invention may thus be carried out continuously and in a closed circuit.
- the aqueous phase suitable for back lithium extraction i.e. for extracting said lithium-7 enriched isotope from the organic solution, can be pure water or water comprising at least one additive selected from hydrochloric acid, sulphuric acid, phosphoric acid, ethanoic acid, and dimethyl sulfoxide (DMSO).
- DMSO dimethyl sulfoxide
- a second object of the present invention is the use of a macrocycle selected among phosphorylated crown-ethers in which the macrocycle comprises from 12 to 16 intracyclic atoms, at least one phosphorus atom, at least one oxygen atom and at least three additional heteroatoms selected in the group consisting of oxygen, sulphur and nitrogen for the selective trapping of lithium-7 isotope from a suspension of a solid lithium salt in a water non-miscible organic solvent.
- Phosphorylated crown-ether were prepared as generally described in PCT/CL2020/050133.
- phosphorylated crown-ethers of formula MCI and MC2 were respectfully prepared as described in preparation examples 1 and 2 below.
- Benzo-15-crown-5 (CAS RN: 14098-44-3, Supplier: TCI Europe N.V.) has been used as received.
- Anhydrous LiCI (99%, Supplier: Acros) has been used as received and stored in a glove-box.
- Lithium isotopic ratio was measured by inductively coupled plasma mass spectrometer (ICPMS -).
- Lithium concentration was measured by ionic chromatography (IC).
- [ 7 Li/ 6 Li] initial is the lithium isotope ratio of the commercial natural LiCI salt
- [ 7 Li/ 6 Li] aqueous is the lithium isotope ratio in the aqueous phase after extraction by the macrocycle.
- Ph represents a phenyl cycle.
- DMF dry dimethylformamide
- the reaction mixture was stirred at 80°C until completion (48 hours). DMF was removed under reduced pressure.
- the residue was diluted with ethyl acetate (EtOAc) and washed with water, brine and dried over sodium sulfate.
- EtOAc ethyl acetate
- the crude was purified by flash chromatography (acetone/EtOAc 40/60 v/v) to yield a whit-off powder.
- Stage 1 in a 50 mL Erlenmeyer flask was weighed lithium chloride (420 mg, 10 equivalents) and a solution of phosphorylated crown-ether of formula MCI as prepared according of example 1 (330 mg, 1 mmole, 1 equivalent) in 25 mL chloroform was added. The resulting mixture was stirred for 2 hours and allowed to decantation for further 2 hours.
- Stage 2 To the solid LiCI salt recovered from stage 1, a solution of phosphorylated crown-ether of formula MCI as prepared according of example 1 (30 mg, 0.01 mmole) in 5 mL de chloroform was added.
- the concentrated aqueous phase can be dried for a second stage of isotope separation.
- step 1 the extraction procedure of example 3.5 step 1 has been repeated from 1 to 4 four times with the same salt, organic and aqueous solutions,
- the batch process described here can be automated by a continuous extraction process with in-line phase separation and thus enables high concentrations of lithium salts in the aqueous phase to be achieved (a favourable factor for the upper stages).
- the performance of the phosphorylated crown-ether of formula MCI has been compared to that of the phosphorylated crown-ether of formula MC2 as prepared according to example 2 above, and also as a comparative example, to a non-phosphorylated crown-ether not forming part of the present invention, i.e. Benzo-15-crown-5 (abbreviated B15C5).
- B15C5 can be represented by the following formula :
- each tested crown-ether (MCI, MC2 or B15C5) was engaged in the extraction procedure described in example 3.5. step 1.
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Abstract
The invention relates to a liquid-solid separation multi-stage process of lithium-6 and lithium-7 isotopes from a solid alkali lithium salt, an organic solution of a macrocycle in a water non-miscible solvent is contacted with a solid lithium salt, said macrocycle being chosen among phosphorylated crown-ethers in which the macrocycle comprises from 12 to 16 intracyclic atoms, at least one phosphorus atom, at least one oxygen atom and at least three additional heteroatoms selected in the group consisting of oxygen, sulphur and nitrogen. The invention also relates to the use of such a macrocycle for the selective trapping of lithium-7 isotope from a suspension of a solid lithium salt in a water non-miscible organic solvent.
Description
PROCESS FOR PRODUCING LITHIUM SALT WITH HIGH LEVEL OF LITHIUM-7 ISOTOPE
TECHNICAL FIELD
The invention relates the field of isotope separation in the field of chemical industry, in particular to a process for extraction and enriching lithium isotopes.
More particularly, the invention relates to a liquid-solid separation process of lithium-6 and lithium-7 isotopes from a solid alkali lithium salt, where an organic solution of a macrocycle in a water non-miscible solvent is contacted with a solid lithium salt, said macrocycle being chosen among phosphorylated crown-ethers in which the macrocycle comprises from 12 to 16 intracyclic atoms, at least one phosphorus atom, at least one oxygen atom and at least three additional heteroatoms selected in the group consisting of oxygen, sulphur and nitrogen. The invention also relates to the use of such a macrocycle for the selective trapping of lithium-7 isotope from a suspension of a solid lithium salt in a water non-miscible organic solvent.
BACKGROUND
Naturally occurring lithium (Li) is composed of two stable isotopes, lithium- 6 (6Li) and lithium-7 (7Li), with the latter being far more abundant on Earth (natural relative abundance: 6Li at 7.5% and 7Li at 92.5%).
Lithium isotopes separation technologies are very challenging and it is of great importance to develop cost-effective and environmentally-friendly processes.
Both lithium isotopes have important industrial applications in the field of nuclear industry:
Lithium-7 has a very low neutron cross section, making it transparent to neutrons. This property is used in lithium highly enriched in lithium-7 (more than 99%) as a coolant in molten salt reactors, but also as a pH stabilizer in pressurized water reactors. In particular, 7LiOH of high isotopic purity (99.95%) is required as pH adjuster for coolant fluids in nuclear plants (Pressurize Water Reactors: PWR). The presence of the lighter isotope 6Li for this application is very deleterious because it could produce radioactive tritium which the concentration is strictly regulated. In fluoride salt-cooled high-temperature reactors (FHR), in which the
salt (also called FLIBE) is a mixture of lithium (14 w/w%), fluoride and beryllium, higher enrichment is required. For FHRs, the acceptable 7Li purity requirement is at least 99.995%.
In the meantime, isotopically pure 6Li can be used as a mean of tritium production which is crucial for nuclear fusion technologies.
By the past, the most important industrial method for lithium isotopes separation was the mercury amalgam process also known under the acronym "COLEX" for COLumn Exchange process. Indeed, mercury amalgamates with many metals, including lithium. Lithium-6 has a greater chemical affinity for mercury than lithium-7. When an amalgam of lithium and mercury is added to an aqueous lithium hydroxide solution, lithium-6 becomes more concentrated in the amalgam and lithium-7 more concentrated in the hydroxide solution. The COLEX process exploits this phenomenon by passing a downward flow of lithium-mercury amalgam against an upward flow of aqueous lithium hydroxide in a cascade. Lithium-6 is preferentially carried away by the amalgam, while lithium-7 is preferentially drained by the hydroxide. At the bottom of the column, the amalgam is recovered and the lithium-6 is extracted. At the top of the column, the lithium hydroxide solution is electrolyzed to extract lithium-7. From a technical and economic point of view, the COLEX process is so far the only method allowing the production of enriched lithium on an industrial scale, at affordable costs. The technology has reached a certain maturity allowing it to be adopted by many countries with a nuclear industry. However, large-scale exploitation of this technology would have disastrous consequences for the environment. Thousands tons of mercury are needed and the risks of leaks into the environment are high. Maintenance and cleaning operations are also difficult and expensive.
To date, many researches are conducted in order to find a cost effective and green process: solvent extraction, chromatography, membrane separation or electrochemical depositions are some of the technologies evaluated.
Among those technics, the use of crown-ethers is widely studied. As an example, it has already been proposed lithium isotopes separation by the liquid-liquid extraction technic involving the use of benzo-15-crown-5 ether (B15C5) in chloroform (CN108854536). However, this process is highly selective for lithium-6 isotope and not for lithium-7 isotope. This process thus does not allow
reaching aqueous solutions of lithium salts with a high level of 7Li isotope and does not allow high lithium concentration in aqueous phase.
Therefore, there is a need for a process allowing reaching aqueous solutions of lithium salts with a high level of 7Li isotope, such a process being easy to carry out and to implement continuously, environmentally friendly and economic.
Description of the invention:
A first object of the present invention is a liquid-solid separation multi-stage process of lithium-6 and lithium-7 isotopes from a solid alkali lithium salt, said multi-stage process comprising at least the following steps: i) contacting an organic solution of a macrocycle in a water non-miscible solvent with a solid lithium salt to obtain a suspension of said solid alkali lithium salt in said organic solution, ii) stirring the suspension obtained in step i) for a period of time sufficient to form a complex of lithium-7 enriched isotope with said macrocycle, iii) mechanically separating said solid lithium salt from said organic solution, said organic solution comprising lithium-7 enriched isotope complexed with said macrocycle, iv) contacting said organic solution with an aqueous phase to extract said lithium-7 enriched isotope from the macrocycle present in the organic solution, and obtain an aqueous phase comprising said lithium-7 enriched isotope and an organic solution comprising said macrocycle freed from said lithium; v) evaporating said lithium-7 enriched isotope aqueous phase to produce solid lithium-7 enriched isotope and optionally reprocessing said solid lithium-7 enriched isotope according to step i) to v) until production of lithium-7 salt with the desired purity; wherein said macrocycle is a phosphorylated crown-ether in which the macrocycle comprises from 12 to 16 intracyclic atoms, at least one phosphorus atom, at least one oxygen atom and at least three additional heteroatoms selected in the group consisting of oxygen, sulphur and nitrogen.
The process according to the present invention has the following advantages:
- Selectivity for the 7Li isotope (all other processes are selective for the other isotope, i.e. 6Li isotope)
- Easy to implement (solid/liquid extraction) allowing a continuous process,
- Environmentally friendly (no use of toxic products, can operate in closed circuit).
- Ease of preparation and industrial cost price of phosphorylated macrocycles.
Indeed, according to the process of the invention, a solution of a phosphorylated crown-ether in a water non-miscible solvent is stirred in presence of solid lithium salt. After allowing a period of contact the lithium cations distribute into the organic phase and form complexes with the phosphorylated crown-ether. The complex [7Li/phosphorylated crown-ether] is more stable than the complex [6Li/phosphorylated crown-ether] allowing the 7Li / 6Li ratio increases in the organic solution. The system is very advantageous due to:
- very high extraction efficiency (almost quantitative)
- high single-stage isotopes separation factor (1.016-1.027)
- no needs of additive
- extracting agent (phosphorylated macrocycle) cost
- process can be automated relatively easily
- preferred extraction of 7Li.
In the sense of the invention, the terms "intracyclic atoms" in reference to the macrocycle, refer to the number of atoms engaged in the cycle constituting said macrocycle. It thus excludes any atom that would belong to a substituent of said macrocycle.
According to a preferred embodiment of the invention, the phosphorylated crown-ether is selected among phosphorylated crown-ethers of formulae (I) to (III) below:
Wherein:
- X is O, NR1 or S,
- Y represents a non-substituted aryl group; an aryl group bearing at least one substituent selected among a halogen atom chosen among Cl, Br and F, a linear or branched alkyl group having from 1 to 18 carbon atoms, and a linear or branched alkenyl or alkynyl group having from 2 to 18 carbon atoms; a linear or branched alkyl group having from 2 to 18 carbon atoms, a linear or branched alkyl group bearing at least one substituent selected among a halogen atom chosen among Cl, Br, F, mesyle and tosyle; or a linear or branched alkenyl or alkynyl group having from 2 to 18 carbon atoms;
- R1 represents a hydrogen atom, a linear or branched alkyl group having from 1 to 18 carbon atoms, or a linear or branched alkyl group having from 1 to 18 carbon atoms and substituted by one substituent chosen among an alcoxy group having from 1 to 6 carbon atoms and a trialkyl(C1-C6)siloxane;
- n is an integer ranging from 0 to 4;
- Z1, Z2 and Z3, identical or different, represent (i) a linear or branched alkenyl or alkynyl group having from 2 to 18 carbon atoms, (ii) a 1,2 or 1,3 or 1,4- O-disubstituted aryl group, or a (iii) a linear alkyl chain having 2 ou 3 carbon atoms, said alkyl group being optionally substituted by:
* an OR2 group in which R2 represents hydrogen, an alkyl group having from 1 to 6 carbon atoms or a phosphate group;
* an alkyl group having from 1 to 8 carbon atoms, said alkyl group being optionally substituted by a thioalkoxy(C1-C8) group.
According to a particular and most preferred embodiment of the present invention, the phosphorylated crown-ether is a compound of formula (I) in which Z1 = Z2 = Z3 = -CH2-CH2-, n = 1, 2, 3 or 4, X = O and Y = a phenyl group or a compound of formula (II) in which Z1 = Z2 = Z3 = -CH2-CH2-, n = 1, 2, 3 or 4, X = O and Y = a phenyl group.
Among these particular phosphorylated crown-ethers, the compound of formula (I) in which Z1 = Z2 = Z3 = -CH2-CH2-, n = 2, X = O and Y = a phenyl group and the compound of formula (II) in which Z1 = Z2 = Z3 = -CH2-CH2-, n = 1, X = O and Y is a phenyl group are particularly preferred.
These compounds can be respectively represented by the following formulae MCI and MC2:
The phosphorylated crown-ethers of above formulae (I), (II) and (III) can be prepared as described in international application PCT/CL2020/050133.
According to a preferred embodiment of the present invention, the amount of phosphorylated crown-ether in the organic solution ranges from about 0.01 M and about 5, and more preferably from about 0.1 to about 1.0 M.
According to the invention, the water non-miscible solvent is preferably selected in the group comprising dichloromethane (DCM), chloroform, heptane, cyclohexane, toluene, xylene, ethyl acetate, butyl acetate, chlorobenzene, dichlorobenzene, anisole, methyl tert-butyl ether (MTBE), and nitrobenzene. Among these particular solvents, dichloromethane, chloroform and chlorobenzene are particularly preferred.
The solid lithium salt may be chosen among LiCI, LiBr, Lil, Li2CO3, lithium thiocyanate (LiSCN), Li3PO4, lithium acetate, lithium trifluoroacetate and LiOH. Among these particular lithium salts, LiCI is particularly preferred.
According to a preferred embodiment of the present invention, the solid lithium salt is in the form of particles whose size ranges from about 40 to about 500 pm and more preferably from about 40 to 100 pm.
The molar ratio [solid lithium salt/phosphorylated crown-ether] is not critical. However, this molar ratio preferably ranges from about 0.1 to 2000 and more preferably from about 10 to 1000, and even more preferably from about 100 to 500.
According to a preferred embodiment of the present invention, the period of time sufficient to form a complex of lithium-7 isotope with said macrocycle at step ii) may range from about 1 to 48 hours, preferably from about 1 to 2 hours.
The temperature of the suspension of said solid alkali lithium salt in said organic solution during step ii) is not critical. However, according to a particular embodiment of the present invention, the temperature of the suspension of said solid alkali lithium salt in said organic solution during step ii) ranges from about - 20°C and 100°C, and even more preferably from about 20 to 40°C.
At step iii), the mechanical separation of said solid alkali lithium salt from said organic solution may be carried out by any appropriate mean, such as for example by filtration or by centrifugation.
According to a particular and preferred embodiment of the present invention, the solid lithium salt recovered from the said organic solution at the end of step (iii) and the organic solution recovered at the end of step iv), i.e. the organic solution comprising said macrocycle freed from said lithium-7 enriched isotope, may both be re-engaged at least once in step (i) of the process, preferably from 1 to 2500 times and even more preferably from 50 to 500 times. According to this embodiment, the process of the invention may thus be carried out continuously and in a closed circuit.
The aqueous phase suitable for back lithium extraction, i.e. for extracting said lithium-7 enriched isotope from the organic solution, can be pure water or water comprising at least one additive selected from hydrochloric acid, sulphuric acid, phosphoric acid, ethanoic acid, and dimethyl sulfoxide (DMSO).
As above-explained, the process according to the first object of the present invention allows the separation of lithium-7 isotope from a solid lithium salt.
Therefore, a second objet of the present invention is the use of a macrocycle selected among phosphorylated crown-ethers in which the macrocycle comprises from 12 to 16 intracyclic atoms, at least one phosphorus atom, at least one oxygen atom and at least three additional heteroatoms selected in the group consisting of oxygen, sulphur and nitrogen for the selective trapping of lithium-7 isotope from a suspension of a solid lithium salt in a water non-miscible organic solvent.
According to a preferred embodiment of this use, the phosphorylated crown- ethers are selected among phosphorylated crown-ethers of formulae (I) to (III) as defined here-above according to the first object of the present invention, in particular among compounds of formula (I) in which Z1 = Z2 = Z3 = -CH2-CH2-, n = 1, 2, 3 or 4, X = P and Y = a phenyl group and a compound of formula (II) in which Z1 = Z2 = Z3 = -CH2-CH2-, n = 1, X = O and Y = a phenyl group, and even more particularly among the compound of formula (I) in which Z1 = Z2 = Z3 = - CH2-CH2-, n = 1, X = O and Y = a phenyl group and the compound of formula (II) in which Z1 = Z2 = Z3 = -CH2-CH2-, n = 2, X = O and Y = a phenyl group.
Other advantages and embodiments of the present invention are given by the following examples.
EXAMPLES:
Chemicals
Phosphorylated crown-ether were prepared as generally described in PCT/CL2020/050133. In particular, phosphorylated crown-ethers of formula MCI and MC2 were respectfully prepared as described in preparation examples 1 and 2 below.
Benzo-15-crown-5 (CAS RN: 14098-44-3, Supplier: TCI Europe N.V.) has been used as received.
Anhydrous LiCI (99%, Supplier: Acros) has been used as received and stored in a glove-box.
Solvents, HPLC grade, were used as received. Ultra-pure Water (<lpS/cm) from Chem-Lab has been used for extraction.
Analytical equipment:
Lithium isotopic ratio was measured by inductively coupled plasma mass spectrometer (ICPMS -).
Lithium concentration was measured by ionic chromatography (IC).
Extraction procedure:
In a vial lithium chloride and a 0.5 M solution of macrocycle were added. The mixture was stirred at room temperature with a magnetic stirring for a definite time. The mixture was then allowed for decantation during 2 h. After filtration (0.22mm filter) the solution was extracted with ultrapure water. After phase separation the aqueous phase was washed with chloroform in order to remove any traces of macrocycle. The later aqueous phase was analysed by ICPMS and IC.
The separation factor a (alpha,) measures the ability of a single-stage process to selectively transfer one isotope to one of the two phases alpha =
[7Li/6Li]initial is the lithium isotope ratio of the commercial natural LiCI salt,
[7Li/6Li]aqueous is the lithium isotope ratio in the aqueous phase after extraction by the macrocycle.
EXAMPLE 1: Preparation of a phosphorylated crown-ether of formula MCI
A phosphorylated crown-ether of the following formula MCI has been prepared according to the process represented below on Scheme 1:
SCHEME 1
The following procedure has been applied:
A dichloromethane (DCM) solution (20 mL) of Compound 1 (X = 0, Hal = Cl, Y = Phenyl, 10.0 mmoles, 1.95 g) was added drop-wise (3.5h) to a DCM solution (250 mL) of Compound 2 ( Z1 = Z2 = Z3 = -CH2-CH2-, n=2, 10.0 mmoles, 1.94 g, 0.04M) at 35°C under argon. The reaction mixture was stirred overnight. The solvent was then evaporated until a crude oil was obtained. The crude oil was purified by flash chromatography using a mixture of DCM and methanol (DCM- MeOH : 98/2 v/v) as eluent to yield a colorless oil (1,28 g, 40 %).
1H NMR (300 MHz, Chloroform-d) 7.84-7.78 (m, 2H), 7.56-7.41 (m, 3H), 4.52-4.42 (m, 2H), 4.13-4.08 (m, 2H), 3.87-3.75 (m, 4H), 3.70 (m, 8H).
31P NMR (121 MHz, Chloroform-d) δ 19.03.
13C NMR (75 MHz, Chloroform-d) δ 132.31 (d, J - 3.1 Hz), 131.41 (d, J = 10.0 Hz), 128.33 (d, J = 15.3 Hz), 128.07 (d, J = 193.2 Hz), 70.62 (d, J = 12.7 Hz), 70.19 (d, J = 5.4 Hz), 65.16 (d, J = 6.4 Hz).
HRMS [M+H+]: Calculated: 317.1154, Experimental: 317.1144 for C14H22O6P
EXAMPLE 2: Preparation of a phosphorylated crown-ether of formula MC2
A phosphorylated crown-ether of the following formula MC2 has been prepared according to the process represented below on Scheme 2:
SCHEME 2
In formula MC2 above, Ph represents a phenyl cycle.
K2CO3 (1.38 g, 10 mmoles) was added to a solution of Compound 4 in which ( Z1 = Z2 = Z3 = -CH2-CH2- and n = l (310 mg, 1 equivalent) and Compound 3 (X = O and Y = phenyl, 310 mg, 1 equivalent) in dry dimethylformamide (DMF) (30 ml) under argon atmosphere. The reaction mixture was stirred at 80°C until completion (48 hours). DMF was removed under reduced pressure. The residue was diluted with ethyl acetate (EtOAc) and washed with water, brine and dried over sodium sulfate. The crude was purified by flash chromatography (acetone/EtOAc 40/60 v/v) to yield a whit-off powder.
NMR (300 MHz, Chloroform-d) 8.14-8.07 (m, 2H), 77.67-7.60 (m, 2H), 7.47-7.37 (m, 5H), 7.03-6.90 (m, 4H), 4.14-3.91 (m, 4H), 3.44-3.18 (m, 4H), 3.19-3.00 (m, 4H).
31P NMR (121 MHz, Chloroform-d) 5 24.72
13C NMR (75 MHz, Chloroform-d) 6 159.86, 133.81 (d, J = 7.8 Hz), 134.15 (d, J = 110.1 Hz), 132.71 (d, J = 2.0 Hz), 132.13 (d, J = 10.6 Hz), 130.87 (d, J = 2.9 Hz), 127.75 (d, J = 12.8 Hz), 122.01 (d, J = 107.9 Hz), 120.11 (d, J = 12.2 Hz), 112.23 (d, J = 6.6 Hz), 70.82, 70.57, 66.11.
HRMS [M + H+] : Calculated: 425.1518, Experimental: 425.1525 for C24H26O5P
Melting point: 195-198°C
EXAMPLE 3: Extraction of lithium 7 according to the process of the invention
In this example different extraction experiments have been performed according to the process of the invention, using phosphorylated crown-ethers of formulae MCI or MC2, and as a comparative example not forming part of the present invention, using a crown-ether not useful according to the process of the invention, namely Benzo-15-crown-5.
3.1 Evaluation of the influence of the nature of the solvents
The extraction process has been carried out according to the "Extraction procedure" detailed above using MCI, in different solvents (DCM, Methyl tert-butyl ether (MTBE), n-heptane, toluene and chloroform. The initial molar ratio 7Li/ 6Li before the start of the extraction process was 12.1773 corresponding to an initial amount of 7Li of 92.41 %.
The results are presented in the following Table 1 :
TABLE 1
Here the efficiency (%) is described by the ratio of the concentration of LiCI in the aqueous phase to the maximum theoretical concentration of LiCI (assuming that one equivalent of macrocycle could extract one equivalent of lithium cation).
These results demonstrate that all the tested solvent are efficient to extract lithium-7 according to the process of the invention. However, the data suggest that the best compromise is to use chloroform as solvent (the separation factor is lower than MTBE but the efficiency is by far much better).
3.2. Evaluation of the influence of the number of LiCI equivalents
In this experiment, the influence of the number of LiCI equivalents compare to the extracting agent was evaluated. For this experiment, phosphorylated crown- ether of formula MCI as prepared according to example 1 was engaged in the extraction procedure detailed above; solvent was chloroform, and the contact time between LiCI and MCI under stirring was set to 60 hours.
The results are reported in the following Table 2:
TABLE 2
As it appears in Table 2, the number of LiCI equivalents is not critical according to the process of the invention. However, a very large excess compare to the extracting agent is favourable to reach higher single-stage separation factor.
3.3 Evaluation of the influence of the time of contact
In this experiment, the influence of the contact time between the LiCI salt and the phosphorylated macrocycle was evaluated (stirring time). For this experiment, phosphorylated crown-ether of formula MCI as prepared according to example 1 was engaged in the extraction procedure detailed above; solvent was chloroform, 5 equivalents of LiCI was used and the contact time between LiCI and the phosphorylated crown-ether of formula MCI varied from 1 to 24 hours.
The corresponding results are presented in the following Table 3:
TABLE 3
These results show that the maximum lithium concentration is reached within 1 hour, the equilibrium exchange reaching a plateau after 24 h.
3.4, Evaluation of the influence of the temperature
In this experiment, the influence of the temperature was evaluated. For this experiment, phosphorylated crown-ether of formula MCI as prepared according to example 1 was engaged in the extraction procedure detailed above; solvent was dichlorobenzene, 500 equivalents of LiCI were used and the contact time between LiCI and the phosphorylated crown-ether of formula MCI was 7 hours. The temperatures were 0, 20 or 40°C.
The corresponding results are given in the following Table 4:
TABLE 4
Although the choice of the temperature is not critical according to the process of the invention, these results show that the formation of the complex [MCl-7Li]CI is favoured with the rise of temperature.
3.5 Extraction of lithium-7 according to a two-stage process
Stage 1 : in a 50 mL Erlenmeyer flask was weighed lithium chloride (420 mg, 10 equivalents) and a solution of phosphorylated crown-ether of formula MCI as prepared according of example 1 (330 mg, 1 mmole, 1 equivalent) in 25 mL chloroform was added. The resulting mixture was stirred for 2 hours and allowed to decantation for further 2 hours.
20 mL of the organic solution were withdrawn and LiCI was extracted with 30.0 mL of deionized water. Resulting solid LiCI salt was then washed with 5 mL of chloroform.
A 0.5 mL aliquot of aqueous solution was diluted to 4.0mL with deionized water for analysis by ICPMS
The whole aqueous solution was evaporated to dryness to yield 26 mg of solid LiCI (62 % of maximum mass).
Stage 2: To the solid LiCI salt recovered from stage 1, a solution of phosphorylated crown-ether of formula MCI as prepared according of example 1 (30 mg, 0.01 mmole) in 5 mL de chloroform was added.
The resulting mixture was stirred for 2 hours and allowed to decantation for further 2 hours and then filtrated (22 pm).
LiCI was extracted with 2.0 mL of deionized water.
The corresponding results are presented in following Table 5:
TABLE 5
These results show that 7Li enrichment process is still operating during the second stage.
3.6 Concentration process of LICI in the aqueous phase
It is advantageous to concentrate the aqueous phase at each stage by repeating the procedure with the same organic and aqueous solutions.
After a determined numbers of cycles, the concentrated aqueous phase can be dried for a second stage of isotope separation.
In the example, the extraction procedure of example 3.5 step 1 has been repeated from 1 to 4 four times with the same salt, organic and aqueous solutions,
The corresponding results are reported in the following Table 6:
TABLE 6
This batch process clearly indicates the increasing amount of LiCI in aqueous phase after 4 cycles. A continuous flow extraction process could be advantageous to reach higher salt concentration in aqueous phase.
The batch process described here can be automated by a continuous extraction process with in-line phase separation and thus enables high
concentrations of lithium salts in the aqueous phase to be achieved (a favourable factor for the upper stages).
3.7 Evaluation of the nature of macrocycle
In the example, the performance of the phosphorylated crown-ether of formula MCI has been compared to that of the phosphorylated crown-ether of formula MC2 as prepared according to example 2 above, and also as a comparative example, to a non-phosphorylated crown-ether not forming part of the present invention, i.e. Benzo-15-crown-5 (abbreviated B15C5).
B15C5 can be represented by the following formula :
For this experiment, each tested crown-ether (MCI, MC2 or B15C5) was engaged in the extraction procedure described in example 3.5. step 1.
The results are presented in Table 7 below:
TABLE 7
In numerous papers B15C5 was described as a potent candidate that can separate lithium isotopes in a liquid/liquid process. These results show that in the solid/liquid lithium isotopes separation process of the invention only phosphorylated macrocycles (for example of formulae MCI or MC2) are efficient; B15C5 is not active at all.
Claims
1. Liquid-solid separation multi-stage process of lithium-6 and lithium-7 isotopes from a solid alkali lithium salt, said multi-stage process comprising at least the following steps: i) contacting an organic solution of a macrocycle in a water non-miscible solvent with a solid lithium salt to obtain a suspension of said solid alkali lithium salt in said organic solution, ii) stirring the suspension obtained in step i) for a period of time sufficient to form a complex of lithium-7 enriched isotope with said macrocycle, iii) mechanically separating said solid lithium salt from said organic solution, said organic solution comprising lithium-7 enriched isotope complexed with said macrocycle, iv) contacting said organic solution with an aqueous phase to extract said lithium-7 enriched isotope from the macrocycle present in the organic solution, and obtain an aqueous phase comprising said lithium-7 enriched isotope and an organic solution comprising said macrocycle freed from said lithium; v) evaporating said lithium-7 enriched isotope aqueous phase to produce solid lithium-7 enriched isotope and optionally reprocessing said solid lithium-7 enriched isotope according to step i) to v) until production of lithium-7 salt with the desired purity. wherein said macrocycle is a phosphorylated crown-ether in which the macrocycle comprises from 12 to 16 intracyclic atoms, at least one phosphorus atom, at least one oxygen atom and at least three additional heteroatoms selected in the group consisting of oxygen, sulphur and nitrogen,
2. The process of claim 1, wherein the phosphorylated crown-ether is selected among phosphorylated crown-ethers of formulae (I) to (III) below:
Wherein:
- X is O, NR1 or S,
- Y represents a non-substituted aryl group; an aryl group bearing at least one substituent selected among a halogen atom chosen among Cl, Br and F, a linear or branched alkyl group having from 1 to 18 carbon atoms, and a linear or branched alkenyl or alkynyl group having from 2 to 18 carbon atoms; a linear or branched alkyl group having from 2 to 18 carbon atoms, a linear or branched alkyl group bearing at least one substituent selected among a halogen atom chosen among Cl, Br, F, mesyle and tosyle; or a linear or branched alkenyl or alkynyl group having from 2 to 18 carbon atoms;
- R1 represents a hydrogen atom, a linear or branched alkyl group having from 1 to 18 carbon atoms, or a linear or branched alkyl group having from 1 to 18 carbon atoms and substituted by one substituent chosen among an alcoxy group having from 1 to 6 carbon atoms and a trialkyl(C1-C6)siloxane ;
- n is an integer ranging from 0 to 4;
- Z1, Z2 and Z3, identical or different, represent (i) a linear or branched alkenyl or alkynyl group having from 2 to 18 carbon atoms, (ii) a 1,2 or 1,3 or 1,4- O-disubstituted aryl group, or a (iii) a linear alkyl chain having 2 ou 3 carbon atoms, said alkyl group being optionally substituted by:
* an OR2 group in which R2 represents hydrogen, an alkyl group having from 1 to 6 carbon atoms or a phosphate group;
* an alkyl group having from 1 to 8 carbon atoms, said alkyl group being optionally substituted by a thioalkoxy(C1-C8) group.
3. The process according to claim 2, wherein the phosphorylated crown- ether is a compound of formula (I) in which Z1 = Z2 = Z3 = -CH2-CH2-, n = 1, 2, 3 or 4, X = O and Y = a phenyl group or a compound of formula (II) in which Z1 = Z2 = Z3 = -CH2-CH2-, n = 1, 2, 3 or 4, X = 0 and Y = a phenyl group.
4. The process according to claim 3, wherein the phosphorylated crown- ether is a compound of formula (I) in which Z1 = Z2 = Z3 = -CH2-CH2-, n = 2, X = O and Y = a phenyl group or a compound of formula (II) in which Z1 = Z2 = Z3 = -CH2-CH2-, n = 1, X = O and Y is a phenyl group.
5. The process according to any one of claims 1 to 4, wherein the water non-miscible solvent is selected in the group comprising dichloromethane, chloroform, heptane, cyclohexane, toluene, xylene, ethyl acetate, butyl acetate, chlorobenzene, dichlorobenzene, anisole, methyl tert-butyl ether, and nitrobenzene.
6. The process according to any one of claims 1 to 5, wherein the solid lithium salt is LiCl.
7. The process according to any one of claims 1 to 6, wherein the molar ratio [solid lithium salt/phosphorylated crown-ether] ranges from 0.1 to 2000.
8. The process according to any one of claims 1 to 7, wherein the period of time sufficient to form a complex of lithium-7 isotope with said macrocycle at step ii) ranges from 1 to 48 hours.
9. The process according to any one of claims 1 to 8, wherein the temperature of the suspension of said solid alkali lithium salt in said organic solution during step ii) ranges from 20 to 40°C.
10. The process according to any one of claims 1 to 9, wherein the solid lithium salt recovered from the said organic solution at the end of step (iii) and the organic solution recovered at the end of step iv), are both re-engaged at least once in step (i) of the process.
11. The process according to any one of claims 1 to 9, wherein the solid lithium salt recovered from the said organic solution at the end of step (iii) and the organic solution recovered at the end of step iv), are both re-engaged 1 to 2500 times in step (i) of the process.
12. The process according to any one of claims 1 to 11, wherein the aqueous phase is pure water or water comprising at least one additive selected from hydrochloric acid, sulphuric acid, phosphoric acid, ethanoic acid, octanol and dimethyl sulfoxide.
13. Use of a macrocycle selected among phosphorylated crown-ethers in which the macrocycle comprises from 12 to 16 intracyclic atoms, at least one phosphorus atom, at least one oxygen atom and at least three additional heteroatoms selected in the group consisting of oxygen, sulphur and nitrogen for the selective trapping of lithium-7 isotope from a suspension of a solid lithium salt in a water non-miscible organic solvent.
14. The use of claim 13, wherein the phosphorylated crown-ethers are selected among compounds of formula (I) as defined in claim 2 and in which Z1 = Z2 = Z3 = -CH2-CH2-, n = 1, 2, 3 or 4, X = O and Y = a phenyl group and a compound of formula (II) as defined in claim 2 and in which Z1 = Z2 = Z3 = -CH2- CH2-, n = 1, 2, 3 or 4, X = O and Y is a phenyl group.
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| CN108854536A (en) | 2017-05-15 | 2018-11-23 | 中国科学院上海有机化学研究所 | A kind of complexes of extracting and enriching lithium isotope |
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