WO2013167516A1 - Nouveaux composés bifonctionnels utiles comme ligands de l'uranium(vi), leurs procédés de synthèse et leurs utilisations - Google Patents
Nouveaux composés bifonctionnels utiles comme ligands de l'uranium(vi), leurs procédés de synthèse et leurs utilisations Download PDFInfo
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- WO2013167516A1 WO2013167516A1 PCT/EP2013/059352 EP2013059352W WO2013167516A1 WO 2013167516 A1 WO2013167516 A1 WO 2013167516A1 EP 2013059352 W EP2013059352 W EP 2013059352W WO 2013167516 A1 WO2013167516 A1 WO 2013167516A1
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- WIPO (PCT)
- Prior art keywords
- group
- uranium
- compound
- particular formula
- hydrogen atom
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 169
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000003446 ligand Substances 0.000 title claims abstract description 6
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims description 67
- 229910052770 Uranium Inorganic materials 0.000 title claims description 66
- 230000001588 bifunctional effect Effects 0.000 title description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 114
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 57
- AAORDHMTTHGXCV-UHFFFAOYSA-N uranium(6+) Chemical compound [U+6] AAORDHMTTHGXCV-UHFFFAOYSA-N 0.000 claims abstract description 56
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 23
- 125000002950 monocyclic group Chemical group 0.000 claims abstract description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 10
- 239000012074 organic phase Substances 0.000 claims description 66
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 56
- 239000007864 aqueous solution Substances 0.000 claims description 51
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 45
- -1 2-ethylhexyl Chemical group 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 34
- 229910019142 PO4 Inorganic materials 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 229920006395 saturated elastomer Polymers 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- OLGGYSFJQGDOFX-UHFFFAOYSA-N nonylphosphonic acid Chemical compound CCCCCCCCCP(O)(O)=O OLGGYSFJQGDOFX-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 claims description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- OGBVRMYSNSKIEF-UHFFFAOYSA-L benzyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-L 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- NJPQAIBZIHNJDO-UHFFFAOYSA-N 1-dodecylpyrrolidin-2-one Chemical compound CCCCCCCCCCCCN1CCCC1=O NJPQAIBZIHNJDO-UHFFFAOYSA-N 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 56
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 54
- 239000000203 mixture Substances 0.000 description 49
- 239000008346 aqueous phase Substances 0.000 description 40
- 238000000605 extraction Methods 0.000 description 39
- 238000012512 characterization method Methods 0.000 description 38
- 229910052742 iron Inorganic materials 0.000 description 23
- 235000021317 phosphate Nutrition 0.000 description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000012360 testing method Methods 0.000 description 19
- 238000010992 reflux Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 150000002430 hydrocarbons Chemical group 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 12
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 230000002195 synergetic effect Effects 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229940126214 compound 3 Drugs 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 150000004820 halides Chemical class 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- HNVACBPOIKOMQP-UHFFFAOYSA-N uranium(4+) Chemical compound [U+4] HNVACBPOIKOMQP-UHFFFAOYSA-N 0.000 description 7
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 6
- 238000004876 x-ray fluorescence Methods 0.000 description 6
- PEZCPZAKKGSMOD-UHFFFAOYSA-N 4-chloro-N,N-diethyloctanamide Chemical compound CCCCC(Cl)CCC(=O)N(CC)CC PEZCPZAKKGSMOD-UHFFFAOYSA-N 0.000 description 5
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 235000012501 ammonium carbonate Nutrition 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 229940125898 compound 5 Drugs 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012312 sodium hydride Substances 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- UWLHSHAHTBJTBA-UHFFFAOYSA-N 1-iodooctane Chemical compound CCCCCCCCI UWLHSHAHTBJTBA-UHFFFAOYSA-N 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 235000019647 acidic taste Nutrition 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000012230 colorless oil Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229940072033 potash Drugs 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 3
- RNHDAKUGFHSZEV-UHFFFAOYSA-N 1,4-dioxane;hydrate Chemical compound O.C1COCCO1 RNHDAKUGFHSZEV-UHFFFAOYSA-N 0.000 description 2
- NPNBLTJGRBYCJB-UHFFFAOYSA-N 1-[butoxy(methyl)phosphoryl]oxybutane Chemical compound CCCCOP(C)(=O)OCCCC NPNBLTJGRBYCJB-UHFFFAOYSA-N 0.000 description 2
- ZGQVQRKCUZEQLW-UHFFFAOYSA-N 2-chloro-n,n-dihexylacetamide Chemical compound CCCCCCN(C(=O)CCl)CCCCCC ZGQVQRKCUZEQLW-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- CBZZMAZCMXHKBU-UHFFFAOYSA-N butoxy(nonyl)phosphinic acid Chemical compound CCCCCCCCCP(=O)(O)OCCCC CBZZMAZCMXHKBU-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
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- 238000011017 operating method Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
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- 125000006850 spacer group Chemical group 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
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- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 1
- JPGXOMADPRULAC-UHFFFAOYSA-N 1-[butoxy(butyl)phosphoryl]oxybutane Chemical compound CCCCOP(=O)(CCCC)OCCCC JPGXOMADPRULAC-UHFFFAOYSA-N 0.000 description 1
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- JLWWOZVKNXYDSA-UHFFFAOYSA-N 1-dibutoxyphosphorylnonane Chemical compound CCCCCCCCCP(=O)(OCCCC)OCCCC JLWWOZVKNXYDSA-UHFFFAOYSA-N 0.000 description 1
- HZLCBGOVVJFATC-UHFFFAOYSA-N 1-dodecan-2-ylpyrrolidin-2-one Chemical compound CC(CCCCCCCCCC)N1C(CCC1)=O HZLCBGOVVJFATC-UHFFFAOYSA-N 0.000 description 1
- TXLHNFOLHRXMAU-UHFFFAOYSA-N 2-(4-benzylphenoxy)-n,n-diethylethanamine;hydron;chloride Chemical compound Cl.C1=CC(OCCN(CC)CC)=CC=C1CC1=CC=CC=C1 TXLHNFOLHRXMAU-UHFFFAOYSA-N 0.000 description 1
- OZGMODDEIHYPRY-UHFFFAOYSA-N 2-bromopropanoyl chloride Chemical compound CC(Br)C(Cl)=O OZGMODDEIHYPRY-UHFFFAOYSA-N 0.000 description 1
- FGEAOSXMQZWHIQ-UHFFFAOYSA-N 2-chloro-2-phenylacetyl chloride Chemical compound ClC(=O)C(Cl)C1=CC=CC=C1 FGEAOSXMQZWHIQ-UHFFFAOYSA-N 0.000 description 1
- ODFVPYXRPILYNK-UHFFFAOYSA-N 2-chloro-N,N-bis(2-ethylhexyl)-2-phenylacetamide Chemical compound CCCCC(CC)CN(CC(CC)CCCC)C(=O)C(Cl)c1ccccc1 ODFVPYXRPILYNK-UHFFFAOYSA-N 0.000 description 1
- ASYPQLBYSSYEBE-UHFFFAOYSA-N 2-chloro-n,n-dioctylacetamide Chemical compound CCCCCCCCN(C(=O)CCl)CCCCCCCC ASYPQLBYSSYEBE-UHFFFAOYSA-N 0.000 description 1
- NBJYMLJVPOYQDR-UHFFFAOYSA-M 2-ethylhexoxy(methyl)phosphinate Chemical compound CCCCC(CC)COP(C)([O-])=O NBJYMLJVPOYQDR-UHFFFAOYSA-M 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- LAGFZZYIGLTTHN-UHFFFAOYSA-N 3-bromo-N,N-bis(2-ethylhexyl)propanamide Chemical compound CCCCC(CC)CN(CC(CC)CCCC)C(=O)CCBr LAGFZZYIGLTTHN-UHFFFAOYSA-N 0.000 description 1
- IHBVNSPHKMCPST-UHFFFAOYSA-N 3-bromopropanoyl chloride Chemical compound ClC(=O)CCBr IHBVNSPHKMCPST-UHFFFAOYSA-N 0.000 description 1
- CDIIZULDSLKBKV-UHFFFAOYSA-N 4-chlorobutanoyl chloride Chemical compound ClCCCC(Cl)=O CDIIZULDSLKBKV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RIDMEZLVWLAMIC-UHFFFAOYSA-N C(C)C1C(N(CC1)CCCCCCCCCCCC)=O Chemical compound C(C)C1C(N(CC1)CCCCCCCCCCCC)=O RIDMEZLVWLAMIC-UHFFFAOYSA-N 0.000 description 1
- VTIJFLNLHCYVPF-UHFFFAOYSA-N C[SiH](C)C.Br Chemical compound C[SiH](C)C.Br VTIJFLNLHCYVPF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 1
- 238000010934 O-alkylation reaction Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- WSOJYRTVHMMFST-UHFFFAOYSA-N benzyl(ethoxy)phosphinic acid Chemical compound CCOP(O)(=O)CC1=CC=CC=C1 WSOJYRTVHMMFST-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 description 1
- AIPRAPZUGUTQKX-UHFFFAOYSA-N diethoxyphosphorylmethylbenzene Chemical compound CCOP(=O)(OCC)CC1=CC=CC=C1 AIPRAPZUGUTQKX-UHFFFAOYSA-N 0.000 description 1
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 1
- RGFUIVSMTQYSTN-UHFFFAOYSA-N dihexyl(8-methoxyoctyl)phosphane Chemical compound CCCCCCP(CCCCCC)CCCCCCCCOC RGFUIVSMTQYSTN-UHFFFAOYSA-N 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-L diphosphonate(2-) Chemical compound [O-]P(=O)OP([O-])=O XQRLCLUYWUNEEH-UHFFFAOYSA-L 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- YJCXKNNURGCXFQ-UHFFFAOYSA-N ethoxy(ethyl)phosphinic acid Chemical compound CCOP(O)(=O)CC YJCXKNNURGCXFQ-UHFFFAOYSA-N 0.000 description 1
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical compound O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- GVUSLZFCAGPYNM-UHFFFAOYSA-N n-(2-ethylhexyl)butanamide Chemical compound CCCCC(CC)CNC(=O)CCC GVUSLZFCAGPYNM-UHFFFAOYSA-N 0.000 description 1
- DEDLQVRGYXTZRP-UHFFFAOYSA-N n-(2-ethylhexyl)propanamide Chemical compound CCCCC(CC)CNC(=O)CC DEDLQVRGYXTZRP-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FEMOMIGRRWSMCU-UHFFFAOYSA-N ninhydrin Chemical compound C1=CC=C2C(=O)C(O)(O)C(=O)C2=C1 FEMOMIGRRWSMCU-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- NSETWVJZUWGCKE-UHFFFAOYSA-N propylphosphonic acid Chemical compound CCCP(O)(O)=O NSETWVJZUWGCKE-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000011160 research Methods 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
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000000956 solid--liquid extraction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000003507 tetrahydrothiofenyl group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
- C22B60/026—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries liquid-liquid extraction with or without dissolution in organic solvents
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
-
- 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
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0221—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching
- C22B60/0226—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors
- C22B60/0243—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors phosphorated ion as active agent
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/007—Recovery of isotopes from radioactive waste, e.g. fission products
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
- G21F9/125—Processing by absorption; by adsorption; by ion-exchange by solvent extraction
Definitions
- the invention relates to the field of the extraction of uranium from aqueous media containing phosphoric acid.
- the invention relates to novel bifunctional compounds which are capable of extracting alone (i.e., in the absence of any other extracting molecule) uranium (VI) from an aqueous solution.
- uranium (VI) uranium (VI)
- phosphoric acid and this both very effectively and with high selectivity vis-à-vis other metal cations may be present in this solution and, in particular, vis-à-vis the iron (III).
- It also relates to a method for recovering the uranium present in an aqueous solution of phosphoric acid resulting from the attack of a natural phosphate with sulfuric acid and which implements said compounds.
- the invention finds particular application in the treatment of natural phosphates in order to recover the uranium present in these phosphates.
- Natural phosphates which are used for the manufacture of phosphoric acid and fertilizers, contain uranium for grades that can range from a few tens of ppm to several thousand ppm as well as varying amounts of other metals.
- the uranium present in natural phosphates is found almost entirely in the aqueous solutions of phosphoric acid which result from the sulfuric attack of these phosphates.
- the recovery potential of the uranium contained in these phosphate ores is 14,000 tonnes / year, or about 25% of the current annual uranium production, which represents a significant source of uranium.
- the temperature of this stream is then reduced to 40-45 ° C and the uranium (VI) is extracted, in a first extraction cycle, by a synergistic mixture of di- (2-ethylhexyl) phosphoric acid (or HDEHP) and trioctylphosphine oxide (or TOPO).
- the maximum synergistic effect of this mixture with regard to uranium (VI) (and U / Fe selectivity) is obtained in a relative proportion of 4 molecules of HDEHP for 1 molecule of TOPO and the composition of the reference organic phase is as follows: 0.5 mol / L of HDEHP + 0.125 mol / L of TOPO in ⁇ -dodecane or in an equivalent aliphatic diluent.
- the uranium is then extracted by an aqueous phosphoric solution containing Fe 2+ ions which reduce the uranium (VI) to uranium (IV) and thus promote its desextraction in the aqueous phase.
- This desextraction makes it possible to concentrate uranium by a factor of about 70.
- the aqueous stream containing the uranium (IV) thus desextracted is in turn subjected to an oxidation operation to convert to the oxidation state VI all the uranium it contains, then the uranium (VI) is extracted with the synergistic mixture HDEHP / TOPO.
- a way of improving the extraction of uranium from an aqueous solution of phosphoric acid would therefore consist in replacing the synergistic mixture HDEHP / TOPO by combining the two functions "cationic exchanger" and "solvent extractant" within one and the same compound.
- a bifunctional extractant would have several advantages, namely the fact of having to manage only one compound instead of two, and the fact of offering the possibility of transposing the liquid-liquid extraction system to a liquid system.
- solid-liquid extraction because the properties of a solid on which a single compound is grafted (or adsorbed) are easier to control than those of a solid on which two grafted (or adsorbed) compounds act synergistically.
- Tunick et al. have proposed in U.S. Patent 4,316,877 (reference [4]), to extract the uranium from an aqueous solution of phosphoric acid with a di- or carrier triphosphonic acid alkyl C 8 to C 8, with or without the addition of a co-extractant such as tri-n-butyl phosphate (or TBP) or di-n-butylbutylphosphonate (or DBBP).
- TBP tri-n-butyl phosphate
- DBBP di-n-butylbutylphosphonate
- diphosphonates With regard to diphosphonates, the best results are obtained with an organic phase which comprises a diphosphonate diluted to 97% by volume in kerosene and which leads to a distribution coefficient of 53.6 for uranium (IV) and a selectivity uranium / iron of 151.6, while for triphosphonates, the best results are obtained with an organic phase which comprises a triphosphonate, kerosene and chloroform (as a co-solvent), in a voluminal report 3 / 94.5 / 2.5, which leads to a distribution coefficient of uranium (IV) of 25 and a selectivity uranium / iron of 2.5.
- an organic phase which comprises a diphosphonate diluted to 97% by volume in kerosene and which leads to a distribution coefficient of 53.6 for uranium (IV) and a selectivity uranium / iron of 151.6
- triphosphonates the best results are obtained with an organic phase which comprises a triphosphonate, ke
- Warshawsky et al. have proposed, in the French patent application 2 604 919 (reference [7]), a bifunctional compound comprising a phosphine oxide function and a phosphoric or thiophosphoric function, these two functions being connected to one another by a spacer group ether, thioether, polyether or polythioether.
- This type of compound has two disadvantages. Indeed, the tests that were carried out with one of these compounds showed that, if this compound is solubilized in ⁇ -dodecane, a third phase is formed during the extraction of the uranium, while it is solubilized in chloroform, it also forms a third phase but during the removal of uranium. Now the appearance of a third phase is totally unacceptable for a process intended to be implemented on an industrial scale. Moreover, the presence within the spacer group of a P-0 or PS link, which is easily hydrolyzable renders these compounds extremely sensitive to hydrolysis.
- the inventors have therefore set themselves the goal of providing new bifunctional compounds which can advantageously be used in place of the synergistic HDEHP / TOPO system for recovering the uranium present in an aqueous solution of phosphoric acid. obtained from a natural phosphate, especially in that they have a greater affinity for uranium (VI) doubled, if possible, a lower affinity for iron (III) and for possible other cations likely to be present in this type of solution.
- n an integer equal to 0, 1 or 2;
- R 1 and R 2 which may be identical or different, represent a hydrocarbon group, saturated or unsaturated, linear or branched, comprising from 6 to 12 carbon atoms
- R 3 represents:
- hydrocarbon group saturated or unsaturated, linear or branched, comprising from 1 to 12 carbon atoms and optionally one or more heteroatoms
- hydrocarbon group, saturated or unsaturated, monocyclic, comprising from 3 to 8 carbon atoms and optionally one or more heteroatoms or
- R 2 and R 3 together form a group - (CH 2 ) n - wherein n is an integer from 1 to 4;
- R 4 represents a hydrogen atom, a hydrocarbon group, saturated or unsaturated, linear or branched, comprising from 2 to 8 carbon atoms, or a monocyclic aromatic group
- R 5 represents a hydrogen atom or a hydrocarbon group, saturated or unsaturated, linear or branched, comprising from 1 to 12 carbon atoms.
- R 1 , R 4 and R 5 are as previously defined;
- R 2 represents a hydrocarbon group, saturated or unsaturated, linear or branched, comprising from 6 to 12 carbon atoms;
- R 3 represents:
- hydrocarbon group saturated or unsaturated, linear or branched, comprising from 1 to 12 carbon atoms and optionally one or more heteroatoms;
- hydrocarbon group saturated or unsaturated, monocyclic comprising from 3 to 8 carbon atoms and optionally one or more heteroatoms;
- hydrocarbon group saturated or unsaturated, linear or branched, comprising from 6 to 12 carbon atoms
- linear or branched, saturated or unsaturated hydrocarbon group comprising from 2 to 8 carbon atoms means any linear or branched chain alkyl, alkenyl or alkynyl group which comprises 2, 3, 4 , 5, 6, 7 or 8 carbon atoms.
- saturated or unsaturated hydrocarbon group linear or branched, comprising from 1 to 12 carbon atoms and optionally one or more heteroatoms
- heteroatom means any atom other than carbon and hydrogen, this atom typically being a nitrogen, oxygen or sulfur atom.
- hydrocarbon group saturated or unsaturated, monocyclic, comprising from 3 to 8 carbon atoms and optionally one or more heteroatoms
- This cycle may be saturated or, on the contrary, comprise one or more double or triple bonds, and may include one or more heteroatoms or to be substituted by one or more heteroatoms or by one or more substituents comprising a heteroatom, this or these heteroatoms being typically N, O or S.
- this group may in particular be a cycloalkyl, cycloalkenyl or cycloalkynyl group (for example for example, cyclopropane, cyclopentane, cyclohexane, cyclopropenyl, cyclopentenyl or cyclohexenyl), saturated heterocyclic group (e.g., tetrahydrofuryl, tetrahydrothiophenyl, pyrrolidinyl or piperidinyl), unsaturated but nonaromatic heterocyclic group (e.g., pyrrolinyl). or pyridinyl), an aromatic group or a heteroaromatic group.
- cycloalkyl for example for example, cyclopropane, cyclopentane, cyclohexane, cyclopropenyl, cyclopentenyl or cyclohexenyl
- saturated heterocyclic group e.g., tetrahydrofuryl
- aromatic group means any group whose cycle satisfies Huckel's aromaticity rule and therefore has a number of delocalized ⁇ electrons equal to An + 2 (for example, a phenyl or benzyl group), while the term “heteroaromatic group” means any aromatic group such as has just been defined but whose ring comprises one or more heteroatoms, this or these heteroatoms being typically selected from the group consisting of nitrogen, oxygen and sulfur (for example, a furanyl, thiophenyl or pyrrolyl group).
- the group - (CH 2 ) n - wherein n is an integer from 1 to 4 may be methylene, ethylene, propylene or butylene.
- R 1 and R 2 which may be identical or different, advantageously represent a linear or branched alkyl group comprising from 6 to 12 carbon atoms.
- R 1 and R 2 are identical to each other and that they both represent a branched alkyl group comprising from 8 to 10 carbon atoms, the 2-ethylhexyl group being very particularly preferred.
- n is preferably 0;
- R 3 advantageously represents a hydrogen atom, a linear or branched alkyl group comprising from 1 to 12 carbon atoms, or a monocyclic aryl group, preferably phenyl or ortho-, meta- or para-tolyl; while
- R 5 preferably represents a hydrogen atom. More preferably, it is preferred that R 3 represents a hydrogen atom, a methyl group, ⁇ -octyl or phenyl.
- R 4 represents, preferably, a linear or branched alkyl group comprising from 2 to 8 carbon atoms and, more preferably, from 2 to 4 carbon atoms such that an ethyl, n-propyl, isopropyl, ⁇ -butyl, sec-butyl, isobutyl or ieri-butyl group, the ethyl and n-butyl groups being very particularly preferred.
- ethyl 1 - (/ V, / V-diethylhexylcarbamoyl) benzylphosphonate which corresponds to the particular formula (la) above in which m is equal to 0, R 1 and R 2 both represent a group 2- ethyl-hexyl, R 3 is phenyl, R 4 is ethyl, and R 5 is hydrogen;
- ethyl 1 - (/ V, / V-diethylhexylcarbamoyl) ethylphosphonate which corresponds to the particular formula (la) above in which m is equal to 0, R 1 and R 2 both represent a group 2- ethyl-hexyl, R 3 represents a methyl group, R 4 represents an ethyl group while R 5 represents a hydrogen atom;
- ethyl 1 - (/ V, / V-diethylhexylcarbamoyl) nonylphosphonate which corresponds to the above particular formula (Ia) in which m is equal to 0, R 1 and R 2 both represent a 2- group; ethyl-hexyl, R 3 represents a ⁇ -octyl group, R 4 represents an ethyl group while R 5 represents a hydrogen atom;
- R 1 advantageously represents a linear or branched alkyl group comprising from 6 to 12 carbon atoms.
- n is preferably 0;
- R 4 preferably represents a linear or branched alkyl group comprising from 2 to 8 carbon atoms and, more preferably, from 2 to 4 carbon atoms, while
- R 5 represents, preferably, a hydrogen atom.
- a compound of particular formula (Ib) above which has these characteristics is in particular ethyl (N -dodecylpyrrolidone) -1-phosphonate which corresponds to the particular formula (Ib) in which R 1 represents an n-dodecyl group , R 2 and R 3 together form an ethylene group (-CH 2 -CH 2 -), R 4 represents an ethyl group while R 5 represents a hydrogen atom.
- the compounds according to the invention can in particular be obtained by the processes which are described in the examples below and in FIGS. 1 to 3 attached in the appendix.
- the compounds according to the invention have a particularly high affinity and selectivity for uranium (VI).
- the compounds according to the invention are capable of very efficiently extracting uranium (VI) from an aqueous solution of phosphoric acid and, in particular, from an aqueous solution comprising from 0.01 to 9 mol / L phosphoric acid.
- the subject of the invention is still the use of a compound as defined above as a ligand for uranium (VI) and, in particular, for extracting uranium (VI) from an aqueous solution of phosphoric acid, this aqueous solution preferably comprising from 0.01 to 9 mol / l of phosphoric acid.
- Such an aqueous solution may in particular be a solution which results from the attack of a natural phosphate with sulfuric acid.
- the compounds according to the invention can in particular be used in a process for recovering uranium present in an aqueous solution of phosphoric acid resulting from the attack of a natural phosphate with sulfuric acid, which process comprises :
- step b) washing the organic phase obtained at the end of step a) which is carried out, for example, with water, an aqueous acidic solution, for example an aqueous sulfuric acid solution or a aqueous solution of ammonium oxalate;
- an aqueous acidic solution for example an aqueous sulfuric acid solution or a aqueous solution of ammonium oxalate;
- step b) the desextraction of the uranium (VI) present in the organic phase obtained at the end of step b) by contacting this organic phase with an aqueous solution comprising a carbonate or a mixture of carbonates, for example an ammonium or sodium carbonate, and then separating said organic phase and said aqueous solution; and, optionally,
- the compound is advantageously used in solution, at a concentration of 0.01 to 1 mol / L, in an organic diluent, which diluent is preferably of the aliphatic type such as ⁇ -dodecane, hydrogenated tetrapropylene or kerosene, for example the one marketed by TOTAL under the trade name Isane IP-185.
- organic diluent which diluent is preferably of the aliphatic type such as ⁇ -dodecane, hydrogenated tetrapropylene or kerosene, for example the one marketed by TOTAL under the trade name Isane IP-185.
- the aqueous solution of phosphoric acid, which is used in step a), preferably comprises from 0.01 to 9 mol / l of phosphoric acid, while the aqueous solution comprising the carbonate, which is used in step c) preferably comprises from 0.1 to 1.5 mol / l of carbonate (s).
- this process makes it possible to concentrate uranium (VI) strongly, that is to say, to obtain at the end of step c) an aqueous solution whose concentration of uranium (VI) is greater than that presented by the aqueous solution of phosphoric acid which is used in step a).
- this can be achieved by choosing a volume ratio between the organic phase and the aqueous phosphoric acid solution of less than 1 in step a), and a volume ratio between the organic phase. and the aqueous solution comprising the carbonate (s) greater than 1 in step c). This makes it possible to induce an increase in the concentration of uranium (VI) in the organic phase in step a) and in the aqueous phase in step c).
- FIG. 1 illustrates the steps of processes for synthesizing the compounds according to the invention which correspond to the particular formula (I-a).
- FIG. 3 illustrates the steps of methods of synthesis of the compounds according to the invention which correspond to the particular formula (I-b).
- FIG. 4 illustrates the variation of the logarithm of the distribution coefficient of uranium (VI), denoted log (Du), as obtained during extractions carried out with a compound according to the invention, as a function of the logarithm of the concentration. molar in this compound of the organic phase, noted log ([DEHCNPB]).
- FIG. 5 illustrates the uranium partitioning isotherm (VI), that is to say the change in the concentration of uranium in the organic phase, noted [U org ], according to the concentration of this element in aqueous phase, denoted [U aq ]), as obtained during extractions carried out with a compound according to the invention.
- VI uranium partitioning isotherm
- FIG. 6 illustrates the evolution of the logarithm of the distribution coefficient of uranium (VI), denoted log (Du), as obtained during extractions carried out with a compound according to the invention, as a function of the logarithm of the molar acid concentration of the equilibrium aqueous phase after extraction, log ([H + ] e q .).
- the change of symbol in the figure highlights the change of slope.
- FIG. 7 illustrates the evolution of the distribution coefficient of uranium (VI), denoted Du, as obtained during extractions carried out with a compound according to the invention, as a function of the contact time, expressed in minutes, between the aqueous and organic phases.
- VI uranium
- FIG. 8 illustrates the scheme used for a continuous implementation test of the process according to the invention which has been carried out on a pilot scale, using laboratory mixer-settler batteries.
- this synthesis consists in reacting, in a first step, labeled A, an amine, denoted 1, with a halide (for example, a chloride or bromide) of acid, denoted 2, which is functionalized at , in ⁇ or in ⁇ (depending on the value of m da ns the compound that it is desired to synthesize) by a leaving group X (for example, a chlorine or bromine atom) to obtain compound 3 in which R 5 is a hydrogen atom.
- a halide for example, a chloride or bromide
- compound 3 is subjected to an Arbusov reaction to obtain compound 4 in which R 4 is different from a hydrogen atom while R 5 is an atom of hydrogen.
- This Arbusov reaction is carried out by carrying a mixture composed of compound 3 and a phosphite P (OR 4 ) 3 in which R 4 is different from a hydrogen atom (1.2 to 10 eq depending on the case) at 160 ° C. under reflux for 3 to 72 hours as the case may be.
- R 4 is different from a hydrogen atom (1.2 to 10 eq depending on the case) at 160 ° C. under reflux for 3 to 72 hours as the case may be.
- the compound 4 can be used as it is in the next step or, on the contrary, needs to be purified beforehand, in which case this purification is carried out by column chromatography with a cyclohexane / acetate elution gradient.
- ethyl 100/0 to 60/40, v / v.
- Step C (C-alkylation) is carried out by adding, dropwise and with stirring, a solution of compound 4 (previously dried for 2.5 hours at 80 ° C. under vacuum) in tetrahydrofuran (THF-1 eq. 1 mol / L) to a suspension of sodium hydride (2 eq - previously washed with pentane) in anhydrous THF (2 mol / L). The mixture is stirred for 1 hour at room temperature and then the solution is cooled to 0 ° C and a solution of Hal-R 5 halide (1.5 eq) is added dropwise.
- THF-1 eq. 1 mol / L tetrahydrofuran
- Step D (hydrolysis) is carried out by adding, dropwise and with stirring, to a solution of compound 4 at 0.25 mol / L in dichloromethane, trimethylsilane bromide (6 eq.) And then maintaining the stirring mixture overnight. Methanol is then added to the mixture and further stirred for 2 hours. We concentrate it. The crude is then diluted in dichloromethane, washed once with water and once with 1 mol / l hydrochloric acid. The aqueous and organic phases are separated and the organic phase is dried over Na 2 SO 4 , filtered and concentrated.
- Step E (monosaponification) is carried out by adding, to a solution of compound 4 at 0.4 mol / l in ethanol, a solution of the strong base (6 to 8 eq.). The mixture is refluxed for 2.5 to 12 hours as appropriate. After cooling, the mixture is acidified to pH 1 with an aqueous solution of hydrochloric acid. 1 mol / L, then extracted twice with dichloromethane. The aqueous and organic phases are separated and the organic phase is dried over Na 2 SO 4 , filtered and concentrated.
- step C Compound 5 obtained in step C is then subjected to either step D described above to obtain the compound which is noted 8 in FIG. 1 and in which R 4 is a hydrogen atom while R 5 is different from a hydrogen atom, ie in step E described above to obtain the compound which is noted 9 in this figure and in which R 4 and R 5 are both different from a hydrogen atom .
- R 4 represents a group other than the group R 4 which is present in compound 4 (and which is provided by phosphite P (OR 4 ) 3 to Step B) either compound 6 or compound 8 (depending on whether or not R 5 is a hydrogen atom) to a further O-alkylation step, denoted F in Figure 1, by the action of an alcohol R 4 -OH in which R 4 is different from a hydrogen atom, to obtain either the compound in which R 4 is different from a hydrogen atom while R 5 is a hydrogen atom, ie compound 11 in which R 4 and R 5 are both different from a hydrogen atom.
- Step A is carried out starting from 2,2'-diethylhexylamine and chloroacetyl chloride and gives 2-chloro-N, N-diethylhexylacetamide (Yield: 97%), whose characterizations by RM N 1 H and 13 C are given below.
- Step B is carried out using triethylphosphite (1.2 eq for 1 eq of 2-chloro-N, N-diethylhexylacetamide - 3 hours reflux).
- Step D leads to the title compound (Yield: quantitative) whose characterizations by 1 H NMR, 13 C, 31 P are given below.
- ADEHMCBP ADEHMCBP
- Step A is carried out from 2,2'-diethylhexylamine and ⁇ -chlorophenylacetyl chloride and gives 2-chloro-N, N-bis (2-ethylhexyl) -2-phenylacetamide (Yt: 96%) whose characterizations by RM N 1 H and 13 C are given below.
- Step B is carried out using triethylphosphite (10 eq per 1 eq of 2-chloro-N, 2-V-bis (2-ethylhexyl) -2-phenylacetamide-72 hours of reflux) and led to (/ V, / V-diethylhexylcarbamoyl) diethyl benzylphosphonate (Yield: 47%) whose characterizations by RM N 1 H, 13 C and 31 P are given below.
- Step A is carried out from 2,2'-diethylhexylamine and 2-bromopropionyl chloride and gives 2-bromo- [(V-bis (2-ethylhexyl) propanamide (Yield: 98%) 1 H and 13 C NMR characterizations are given below.
- Step B is carried out using triethylphosphite (10 eq per 1 eq of 2-bromo- / V, / V-bis (2-ethylhexyl) propanamide-72 hr reflux) and led to 1 - (/ V , / V-diéthylhexylcarbamoyl) phosphonate diethyl ester (yield: 54%) whose characterization by 1 H NMR, 13 C and 31 P are given below.
- Step E is carried out using potash (4 eq for 1 eq of
- Step A is carried out starting from dihexylamine and chloroacetyl chloride and leads to 2-chloro-N, N-dihexylacetamide (yield: 97%) whose characterizations by RM N 1 H and 13 C are given below. after.
- Step B is carried out using triethylphosphite (1.2 eq for 2-chloro-N, N-dihexylacetamide eq.
- Step E is carried out using potash (4 eq for 1 eq of
- Steps A and B are identical to Steps A and B described in
- Step E is carried out using potassium hydroxide (4 eq for 1 eq of diethyl 1 - (/ V, / V-diethylhexylcarbamoyl) methylphosphonate - 2.5 hours reflux) and gives the title compound (Yield: 97%) whose characterizations by 1 H NMR, 13 C, 31 P are given below.
- Steps A and B are identical to the steps described in point 1.1.3 above.
- Step C is carried out using iodomethane and leads to
- Steps A and B are identical to Steps A and B described in
- Step E is carried out using potassium hydroxide (10 eq for 1 eq of diethyl 1 - (/ V, diethylhexylcarbamoyl) benzylphosphonate - 24 hour reflux) and gives the title compound (yield: 91%). ) whose characterizations by 1 H, 13 C and 31 P NMR are given below.
- Steps A and B are the same as Steps A and B described in
- Step C is carried out using octyl iodide and leads to diethyl 1- (N, N-diethylhexylcarbamoyl) nonylphosphonate (Yield: 99%), the characterizations of which are carried out by RM N 1 H, 13 C and 31 P are given below.
- Step E is carried out using sodium hydroxide (8 eq for 1 eq of diethyl 1- (N, N-diethylhexylcarbamoyl) nonylphosphonate, 12 hours reflux) and gives the title compound (Yield: 99%). ) whose characterizations by 1 H, 13 C and 31 P NMR are given below.
- Step A is the same as step A described in point 1.1.1 above.
- Step B is carried out using tributyl phosphite (3 eq for 1 eq of 2-chloro-N, N-diethylhexylacetamide - 4 hours reflux) and yields 1 - (/ V, / V-diethyl- hexylcarbamoyl) dibutyl methylphosphonate (Yield: quantitative) whose characterizations by RM N 1 H, 13 C and 31 P are given below.
- Step E is carried out using soda 6 eq. for 1 eq. dibutyl 1 - (/ V, N-diethylhexylcarbamoyl) methylphosphonate - reflux for 3 hours in a dioxane-water mixture) and gives the title compound (yield: 99%), the characterizations of which were carried out by 1 H, 13 C and 31 NMR. P are given below.
- Step A is the same as step A described in point 1.1.1 above.
- Step B is the same as Step B described in 1.1.10 above.
- Step C is carried out using octyl iodide and leads to dibutyl l - (/ V, / V-diethylhexylcarbamoyl) nonylphosphonate (yield: 99%), whose characterizations by RM N 1 H, 13 C and 31 P are given below.
- Step E is carried out using sodium hydroxide (8 eq for 1 eq of
- Step A is carried out starting from dioctylamine and chloroacetyl chloride and leads to 2-chloro-N, N-dioctylacetamide (yield: 96%) whose characterizations by RM N 1 H and 13 C are given below. after.
- NMR 1 400 MHz, CDCl 3 ) ⁇ (ppm): 0.81-0.86 (m, 6H, CH 3 ); 1.21 - 1.27 (m, 20H, CH 2 ); 1.45 - 1.58 (m, 4H, CH 2 -CH 2 N); 3.20 - 3.29 (m, 4H, CH 2 -N); 4.01 (s, 2H, CH 2 Cl).
- Step B is carried out using tributyl phosphite (3 eq for 1 eq of 2-chloro-N, N-dioctylacetamide-4 hours reflux) and yields 1 - (/ V, / V-dioctyl- carbamoyl) dibutyl methylphosphonate (Yield: quantitative) whose characterizations by RM N 1 H, 13 C and 31 P are given below.
- Step C is carried out using octyl iodide and leads to dibutyl l - (/ V, / V-dioctylcarbamoyl) nonylphosphonate (Yield: 99%), the characterizations of which are carried out by 1 H, 13 C and 31 M NMR. P are given below.
- Step E is carried out using sodium hydroxide (8 eq for 1 eq of 1 - (/ V, / V-dioctylcarbamoyl) nonylphosphonate dibutyl - reflux of 15 hours) and leads to the title compound (Yield: 99% ) whose characterizations by 1 H, 13 C and 31 P NMR are given below.
- Step A is carried out starting from 2,2'-diethylhexylamine and 3-bromopropanoyl chloride and leads to 3-bromo-N, N-bis (2-ethylhexyl) propanamide (Yield: 97%) whose characterizations by RM N 1 H and 13 C are given below:
- Step B is carried out using triethylphosphite (4 eq for 1 eq of 3-bromo- / V, / V-bis (2-ethylhexyl) propanamide-6 hour reflux) and leads to 2 - (/ V Diethyl (N-diethylhexylcarbamoyl) ethylphosphonate (Yield: quantitative), the characterizations of which are given by RM N 1 H, 13 C and 31 P are given below.
- Step D leads to the title compound (Yield: quantitative) whose characterizations by 1 H NMR, 13 C, 31 P are given below.
- Step A is carried out starting from 2,2'-diethylhexylamine and 4-chlorobutanoyl chloride and leads to 4-chloro- / V, / V-bis (2-ethylhexyl) butanamide (yield: quantitative) whose characterizations by 1 H NMR and 13 C NMR are given below:
- Step B is carried out using triethylphosphite (4 eq for 1 eq of 4-chloro-N, V-bis (2-ethylhexyl) butanamide-48 hour reflux) and yields 3- (N, Diethyl N-diethylhexylcarbamoyl) propylphosphonate (Yield: 68%), the characterizations of which by RM N 1 H, 13 C and 31 P are given below.
- Step D leads to the title compound (Yield: quantitative) whose characterizations by RM N 1 H, 13 C, 31 P are given below.
- this synthesis consists in reacting, in a first step, labeled A, an amine, denoted 1, with a haloacetyl halide (for example, a chloroacetyl chloride), denoted 2, to obtain the compound 3 .
- a haloacetyl halide for example, a chloroacetyl chloride
- This step is, for example, carried out in the presence of triethylamine in an organic solvent of the dichloromethane type.
- This step is, for example, carried out in the presence of n-butyllithium and 2,2'-bipyridine (the latter serving as a colored indicator), or sodium hydride, in an organic solvent of the tetrahydrofuran type.
- Step D is, for example, carried out in the presence of n-butyllithium and 2,2'-pyridine, or sodium hydride and 2,2'-pyridine, in an organic solvent of the tetrahydrofuran type.
- the dichloromethane phases are washed with 50 ml of distilled water, dried over magnesium sulphate, filtered and evaporated to dryness on a rotary evaporator.
- the 7.26 g of yellow oil thus obtained are subjected to chromatography on a column of silica gel (80 g - 63-200 ⁇ of particle size) with a dichloromethane / methanol mixture 98/2 v / v as eluent.
- Step B Synthesis of dibutyl l- (/ V, / V-diethylhexylcarbamoyl) methylphosphonate
- the 2.69 g of yellow oil thus obtained are subjected to chromatography on a silica column (125 g - 63-200 ⁇ of particle size) using a cyclohexane / ethyl acetate mixture 8/2 v / v as eluent. .
- Step D Synthesis of dibutyl 1 - (/ V, / V-diethylhexylcarbamoyl) nonylphosphonate
- the 3.45 g of yellow oil thus obtained are subjected to chromatography on a silica column (125 g - 63-200 ⁇ m of particle size) using a cyclohexane / ethyl acetate mixture 9/1 v / v as eluent. .
- Step E Synthesis of butyl 1- (/ V, / V-diethylhexylcarbamoyl) nonylphosphonate 0.4 g (1 eq.) Of 1 - (/ V, / V-diethylhexylcarbamoyl) was introduced into a microwave CEM Discover TM reactor. dibutyl nonylphosphonate, 5 ml of distilled water, 5 ml of dimethylformamide and 0.23 g (6 eq) of potassium hydroxide, which is heated at 150 ° C. for 15 hours. After which, the reaction mixture is poured into 100 ml of distilled water and acidified by addition of 1N HCl in an amount sufficient to obtain an acidic pH.
- the aqueous phase is extracted twice with 50 ml of ethyl ether.
- the ethereal phases are washed twice with 50 ml of distilled water, dried over magnesium sulphate, filtered and evaporated to dryness on a rotary evaporator.
- the 0.34 g of oil thus obtained are subjected to chromatography on a silica column (17 g - 63-200 ⁇ of particle size) using a 97/3 v / v dichloromethane / methanol mixture as eluent.
- this synthesis consists in reacting in a first step, noted A, a lactam, denoted 1, with a halide (for example, a bromide) Hal-R 1 to obtain compound 2.
- a halide for example, a bromide
- Step A is carried out by adding, under stirring, tetrabutylammonium bromide (950 mg - 3 mmol - 0.05 eq.) and powdered potash (23.1 g - 411 mmol - 7 eq.) to a solution of 2-pyrrolidinone (5.00 g) 58.8 mmol) and bromododecane (18.5 mL, 76.4 mmol, 1.3 eq.) In toluene (60 mL). The mixture is then heated at 50 ° C overnight.
- tetrabutylammonium bromide 950 mg - 3 mmol - 0.05 eq.
- powdered potash 23.1 g - 411 mmol - 7 eq.
- Step B is carried out by adding dropwise with stirring a solution of ⁇ -dodecylpyrrolidinone (1.91 g - 7.5 mmol) in anhydrous THF (7.5 ml) to a solution of disopropylamide of lithium (7.5 mL - 2 M in THF) at -80 ° C under argon. Then the mixture is allowed to warm to room temperature and stirred for 1 hour. It is then cooled to -80 ° C and added with the diethyl chlorophosphate (1.25 mL - 8.6 mmol). After 15 minutes, the mixture is allowed to warm to room temperature and kept stirring overnight.
- Step C is carried out using potassium hydroxide (4 eq for 1 eq. Of (A / -dodecylpyrrolidinone) -1 diethyl phosphonate - 2.5 hours reflux) and leads to (A / -dodecylpyrrolidone) - 1-ethyl phosphonate (Yield: 99%) whose characterizations by 1 , 13 C and 31 P NMR are given below
- test compound is first solubilized in n-dodecane (without the use of a phase-modifying or heating agent) at a level of 0.25 mol / L.
- Table I shows, for each compound tested, the distribution coefficient of uranium (VI), denoted by Du, and the separation factor between uranium (VI) and iron (III), denoted FSu / Fe, which are obtained from the uranium and iron contents thus measured.
- the distribution coefficient Du and the separation factor FSu / Fe which are obtained under the same conditions with the synergistic mixture HDEHP / TOPO, are also specified in this table. It will be recalled that, in the field of liquid-liquid extractions, the distribution coefficient D M of an element M corresponds to the ratio of the concentrations of this element in the organic and aqueous phases that have been brought into contact with each other. , and that the separation factor FS M i / M2 between two metal elements M 1 and M2 corresponds to D M i / D M 2, that is to say to the ratio of the distribution coefficients of the metallic elements M 1 and M 2 obtained during the same extraction.
- This table shows that the compounds according to the invention have a capacity to extract uranium (VI) from an aqueous phosphoric acid solution much higher than that of the synergistic mixture HDEHP / TOPO and, for most of them, a U / Fe selectivity which is also much higher than that of the synergistic mixture HDEH P / TOPO.
- Table II shows the distribution coefficients Du and the FSu / Fe separation factors that are obtained with each of the compounds tested and, for the same compound, with each of the concentrations at which it was used.
- This table shows that the ratios between the distribution coefficients Du obtained with the compounds according to the invention and those obtained with the mixture HDEHP / TOPO are even higher than the concentration at which these compounds and this mixture are used is lower.
- the compound DEHCNPE is 90 times more effective and 47 times more selective than the TOPO / HDEHP mixture.
- the uranium / iron selectivity thus reaches the value of 30,000 with the compound DEHCNPB when it is used at a concentration of 0.05 mol / l.
- FIG. 5 shows that the concentration of uranium (VI) in the aqueous phase ([U aq ]) is lower than the concentration of uranium (VI) in the organic phase ([U or g] ) in a concentration range of uranium (VI) in the organic phase of less than 4.5 g / L of uranium (VI).
- the observed distribution coefficient Du is greater than 1.
- the influence of the phosphoric acid concentration initially present in the aqueous phosphoric acid solution on the extracting properties of the compounds according to the invention is assessed by extraction tests which are carried out in the same way as in ll.l above, but using an aqueous phase containing 10 times more uranium than that used in point ll.l above, ie 2.5 g / l of uranium, and by varying the initial concentration in phosphoric acid of the aqueous phase.
- This example illustrates the possibility of operating in a wide range of acidities to extract uranium (VI) from an aqueous solution of phosphoric acid with the compound DEHCPNB.
- Desextraction tests are performed using: a plurality of organic phases comprising from 0.01 to 0.1 mol / L of DEHCNPB compound in ⁇ -dodecane and which have been previously loaded with uranium (VI) and with iron, by contact with a solution comprising 5 mol / L phosphoric acid, 0.25 g / L uranium (VI) and 2.5 g / L iron (III) in water; and
- an aqueous phase comprising 0.5 mol / l of ammonium carbonate (NH 4 ) 2 CO 3 .
- the compound DEHCNPB should therefore make it possible to overcome the problems related to the presence of iron (III) in aqueous solutions of phosphoric acid which are obtained from natural phosphates while improving the extraction of uranium (VI) of these solutions compared to that obtained with the synergistic mixture HDEHP / TOPO. 11.6 - Kinetics of extraction:
- the kinetics of extraction of uranium (VI) by the compounds according to the invention are assessed by extraction tests which are carried out in the same manner as in point II.l above, but by controlling continuous aqueous operation (FAC) and using an aqueous phase containing 10 times more uranium than that used in point ll.l above.
- This aqueous phase therefore contains 5 mol / L of phosphoric acid, 2.5 g / L of uranium and 2.5 g / L of iron.
- the organic and aqueous phases are contacted in a 25 mL jacketed cell, thermostatically controlled at 25 ° C, with vortex blade and trebuchet agitation (2000 rpm).
- the kinetics of extraction of uranium (VI) by the compound DEHCNPB is therefore not a limiting factor and allows to consider a use of this compound as an extractant in industrial contactors with reduced residence time.
- This aqueous phase comprises 5 mol / l of phosphoric acid. Its composition in metal cations is presented in Table III below.
- a phase comprising the compound DEHCPNB at a concentration of 0.1 mol / L in n-dodecane is used.
- the cation content is measured by ICP-AES in the initial aqueous phase, before it is brought into contact with the organic phase, and in the aqueous phase obtained after extraction, that is to say after its separation from the organic phase.
- the compound DEHCNPB has a capacity to extract uranium (VI) from an aqueous solution of phosphoric acid obtained from a phosphate rock which is comparable to that observed with a synthetic solution.
- the DEHCNPB compound thus has an excellent selectivity for uranium (VI) vis-à-vis other metal cations likely to be present in an aqueous solution of phosphoric acid obtained from a natural phosphate.
- the objective of this test was to verify the extraction performance of uranium (VI) and, more particularly, the selectivity of the solvent vis-à-vis iron, the element mainly present in ores. It involved obtaining, from an aqueous solution of phosphoric acid, a concentrated solution of uranium (VI) characterized by an iron content of less than 0.15%.
- the process was controlled by monitoring the uranium and iron concentrations of the aqueous solutions leaving the three mixer-settler batteries as well as the organic phase from the mixer-settler battery allocated to the extraction.
- the test was carried out on a solution of industrial phosphoric acid having a uranium concentration of 119 mg / L, an iron concentration of 5.7 g / L and an acidity of 5.2 mol / L.
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Priority Applications (8)
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AU2013258153A AU2013258153B2 (en) | 2012-05-07 | 2013-05-06 | New bifunctional compounds useful as ligands of uranium (VI), methods of synthesising same and uses thereof |
BR112014027732-0A BR112014027732B1 (pt) | 2012-05-07 | 2013-05-06 | Composto, uso de um composto e processo de recuperação do urânio |
US14/399,935 US9441285B2 (en) | 2012-05-07 | 2013-05-06 | Bifunctional compounds useful as ligands of uranium (VI), methods of synthesising same and uses thereof |
CN201380035914.5A CN104470936B (zh) | 2012-05-07 | 2013-05-06 | 可用作铀(vi)配体的新的双官能化合物,合成其的方法及其用途 |
CA2872084A CA2872084C (fr) | 2012-05-07 | 2013-05-06 | Composes bifonctionnels carbamoyl/acide phosphonique ou phosphonate utiles comme ligands de l'uranium(vi), leurs procedes de synthese et leurs utilisations |
TN2014000463A TN2014000463A1 (fr) | 2012-05-07 | 2014-10-31 | Nouveaux composés bifonctionnels utiles comme ligands de l'uranium(vi), leurs procédés de synthèse et leurs utilisations |
ZA2014/07955A ZA201407955B (en) | 2012-05-07 | 2014-10-31 | New bifunctional compounds useful as ligands of uranium (vi), methods of synthesising same and uses thereof |
IL235520A IL235520B (en) | 2012-05-07 | 2014-11-05 | Bifunctional compounds useful as uranium(vi) binders and their uses |
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FR1254176 | 2012-05-07 | ||
FR1254176A FR2990206B1 (fr) | 2012-05-07 | 2012-05-07 | Nouveaux composes bifonctionnels utiles comme ligands de l'uranium(vi), leurs procedes de synthese et leurs utilisations |
FR1262362A FR2990207B1 (fr) | 2012-05-07 | 2012-12-19 | Nouveaux composes bifonctionnels utiles comme ligands de l'uranium(vi), leurs procedes de synthese et leurs utilisations |
FR1262362 | 2012-12-19 |
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US (1) | US9441285B2 (fr) |
CN (1) | CN104470936B (fr) |
AU (1) | AU2013258153B2 (fr) |
BR (1) | BR112014027732B1 (fr) |
CA (1) | CA2872084C (fr) |
FR (2) | FR2990206B1 (fr) |
IL (1) | IL235520B (fr) |
PE (1) | PE20150282A1 (fr) |
TN (1) | TN2014000463A1 (fr) |
WO (1) | WO2013167516A1 (fr) |
ZA (1) | ZA201407955B (fr) |
Cited By (10)
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WO2014139869A1 (fr) * | 2013-03-11 | 2014-09-18 | Areva Mines | Utilisation de composés à fonctions amide et phosphonate pour extraire l'uranium(vi) de solutions aqueuses d'acide sulfurique, issues notamment de la lixiviation sulfurique de minerais uranifères |
US9441285B2 (en) | 2012-05-07 | 2016-09-13 | Areva Mines | Bifunctional compounds useful as ligands of uranium (VI), methods of synthesising same and uses thereof |
US20160289796A1 (en) * | 2013-11-08 | 2016-10-06 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Use of an organic-inorganic hybrid material for extracting uranium(vi) from a sulfuric acid aqueous solution, issued notably from the sulfuric leaching of a uranium-bearing ore |
WO2016156591A1 (fr) * | 2015-04-03 | 2016-10-06 | Commissariat à l'énergie atomique et aux énergies alternatives | Composés à fonctions oxyde de phosphine et amine, utiles comme ligands de l'uranium(vi), et leurs utilisations, notamment pour extraire l'uranium(vi) de solutions aqueuses d'acide sulfurique |
WO2017001494A1 (fr) | 2015-06-30 | 2017-01-05 | Areva Mines | Procede de separation du fer d'une phase organique contenant de l'uranium et procede d'extraction de l'uranium d'une solution aqueuse d'acide mineral contenant de l'uranium et du fer |
WO2017085312A1 (fr) | 2015-11-19 | 2017-05-26 | Areva Mines | Nouveau matériau organique pour extraire l'uranium d'une solution aqueuse d'acide phosphorique, procédés d'extraction et de récupération de l'uranium associés et précurseur d'un tel matériau organique |
WO2017085311A1 (fr) | 2015-11-19 | 2017-05-26 | Areva Mines | Procédés d'extraction et de récupération de l'uranium présent dans une solution aqueuse comprenant de l'acide phosphorique |
WO2019025714A1 (fr) | 2017-07-31 | 2019-02-07 | Orano Mining | Composés bifonctionnels à fonction thiophosphine, utiles comme extractants de l'uranium(vi), leurs procédés de synthèse et leurs utilisations |
FR3116834A1 (fr) | 2020-12-02 | 2022-06-03 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Procédé de récupération sélective des terres rares et de l’uranium(VI) d’une solution aqueuse d’acide phosphorique |
US11466341B2 (en) * | 2016-09-15 | 2022-10-11 | Commissariat á l'énergie atomique et aux énergies alternatives | Extractant for rare earth extraction from aqueous phosphoric acid solutions and method of extraction |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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FR3002463B1 (fr) * | 2013-02-25 | 2016-08-19 | Commissariat Energie Atomique | Materiau hybride organique-inorganique, utile pour extraire l'uranium(vi) de milieux aqueux contenant de l'acide phosphorique, ses procedes de preparation et ses utilisations |
FR3060006B1 (fr) | 2016-12-13 | 2020-02-28 | Orano Mining | Materiau organique mesoporeux, utile notamment pour extraire l'uranium(vi) de milieux aqueux comprenant de l'acide phosphorique, et ses utilisations |
CN106749407B (zh) * | 2017-01-06 | 2019-06-18 | 中国工程物理研究院核物理与化学研究所 | 一种氨基磷酸基功能化离子液体及其制备方法和用途 |
EP3441396A1 (fr) * | 2017-08-07 | 2019-02-13 | Université de Montpellier | Procé?dé? de sé?paration d'uranium et/ou de thorium |
CN114797486B (zh) * | 2022-04-13 | 2023-02-03 | 合肥凯华环保科技有限公司 | 废水脱氨用亲水后可重新疏水的疏水膜 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3711591A (en) | 1970-07-08 | 1973-01-16 | Atomic Energy Commission | Reductive stripping process for the recovery of uranium from wet-process phosphoric acid |
SU376387A1 (ru) * | 1971-06-21 | 1973-04-05 | Институт органической , физической химии А. Е. Арбузова | Способ получения фосфорилированных дифениламинов |
FR2396803A1 (fr) | 1977-07-05 | 1979-02-02 | Cogema | Procede d'extraction d'uranium a partir d'acide phosphorique de voie humide |
FR2460960A1 (fr) | 1979-07-09 | 1981-01-30 | Elf Aquitaine | Nouveaux esthers triphosphoniques, utiles a l'extraction des metaux lourds |
FR2460958A1 (fr) | 1979-07-09 | 1981-01-30 | Elf Aquitaine | Nouveaux composes diphosphoniques, utiles a l'extraction des metaux lourds |
US4316877A (en) | 1979-11-23 | 1982-02-23 | Allied Corporation | Extraction of uranium values from phosphoric acid |
FR2596383A1 (fr) | 1986-03-28 | 1987-10-02 | Cogema | Procede de separation du fer a partir d'une solution organique contenant de l'uranium |
FR2604919A1 (fr) | 1986-09-10 | 1988-04-15 | Yeda Res & Dev | Agents d'extraction organo-phosphores bifonctionnels et polymeres pour la recuperation d'uranium |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3235136A1 (de) * | 1982-09-23 | 1984-03-29 | Hoechst Ag, 6230 Frankfurt | Verfahren zur abtrennung von gallium und indium aus waessrigen loesungen |
FR2973377B1 (fr) | 2011-04-01 | 2013-05-17 | Commissariat Energie Atomique | Derives de la 2,9-dipyridyl-1,10-phenanthroline utiles comme ligands des actinides, leur procede de synthese et leurs utilisations |
FR2990206B1 (fr) | 2012-05-07 | 2014-06-06 | Commissariat Energie Atomique | Nouveaux composes bifonctionnels utiles comme ligands de l'uranium(vi), leurs procedes de synthese et leurs utilisations |
-
2012
- 2012-05-07 FR FR1254176A patent/FR2990206B1/fr active Active
- 2012-12-19 FR FR1262362A patent/FR2990207B1/fr active Active
-
2013
- 2013-05-06 PE PE2014001977A patent/PE20150282A1/es active IP Right Grant
- 2013-05-06 AU AU2013258153A patent/AU2013258153B2/en active Active
- 2013-05-06 CA CA2872084A patent/CA2872084C/fr active Active
- 2013-05-06 WO PCT/EP2013/059352 patent/WO2013167516A1/fr active Application Filing
- 2013-05-06 BR BR112014027732-0A patent/BR112014027732B1/pt active IP Right Grant
- 2013-05-06 US US14/399,935 patent/US9441285B2/en active Active
- 2013-05-06 CN CN201380035914.5A patent/CN104470936B/zh active Active
-
2014
- 2014-10-31 ZA ZA2014/07955A patent/ZA201407955B/en unknown
- 2014-10-31 TN TN2014000463A patent/TN2014000463A1/fr unknown
- 2014-11-05 IL IL235520A patent/IL235520B/en active IP Right Grant
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3711591A (en) | 1970-07-08 | 1973-01-16 | Atomic Energy Commission | Reductive stripping process for the recovery of uranium from wet-process phosphoric acid |
SU376387A1 (ru) * | 1971-06-21 | 1973-04-05 | Институт органической , физической химии А. Е. Арбузова | Способ получения фосфорилированных дифениламинов |
FR2396803A1 (fr) | 1977-07-05 | 1979-02-02 | Cogema | Procede d'extraction d'uranium a partir d'acide phosphorique de voie humide |
FR2460960A1 (fr) | 1979-07-09 | 1981-01-30 | Elf Aquitaine | Nouveaux esthers triphosphoniques, utiles a l'extraction des metaux lourds |
FR2460958A1 (fr) | 1979-07-09 | 1981-01-30 | Elf Aquitaine | Nouveaux composes diphosphoniques, utiles a l'extraction des metaux lourds |
US4316877A (en) | 1979-11-23 | 1982-02-23 | Allied Corporation | Extraction of uranium values from phosphoric acid |
FR2596383A1 (fr) | 1986-03-28 | 1987-10-02 | Cogema | Procede de separation du fer a partir d'une solution organique contenant de l'uranium |
FR2604919A1 (fr) | 1986-09-10 | 1988-04-15 | Yeda Res & Dev | Agents d'extraction organo-phosphores bifonctionnels et polymeres pour la recuperation d'uranium |
Non-Patent Citations (7)
Title |
---|
AKHILA MAHESWARI, M. ET AL: "Selective enrichment of U(VI), Th(IV) and La(III) from high acidic streams using a new chelating ion-exchange polymeric matrix", TALANTA , 64(1), 202-209 CODEN: TLNTA2; ISSN: 0039-9140, 2004, XP055065626 * |
BAHNER, C. T. ET AL: "Impurities that cause difficulty in stripping actinides from commercial tetraalkylcarbamoylmethylphosphonates", REPORT , ORNL/TM-5878, 24 PP. AVAIL.: NTIS FROM: ENERGY RES. ABSTR. 1978, 3(2), ABSTR. NO. 2583, 1977 * |
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 1978, BAHNER, C. T. ET AL: "Impurities that cause difficulty in stripping actinides from commercial tetraalkylcarbamoylmethylphosphonates", XP002689743, retrieved from STN Database accession no. 1978:159249 * |
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 1980, FILIPPOV, E. A. ET AL: "Organophosphorus pseudo acids in the extraction of protonic and aprotic acids", XP002689742, retrieved from STN Database accession no. 1980:432437 * |
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; AKHILA MAHESWARI, M. ET AL: "Selective enrichment of U(VI), Th(IV) and La(III) from high acidic streams using a new chelating ion-exchange polymeric matrix", XP002698825, retrieved from STN Database accession no. 2004:638796 * |
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; YARMUKHAMETOVA, D. KH. ET AL: "Phosphorylated diphenylamines", XP002698826, retrieved from STN Database accession no. 1973:452981 * |
FILIPPOV, E. A. ET AL: "Organophosphorus pseudo acids in the extraction of protonic and aprotic acids", RADIOKHIMIYA , 22(2), 218-24 CODEN: RADKAU; ISSN: 0033-8311, 1980 * |
Cited By (15)
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US9441285B2 (en) | 2012-05-07 | 2016-09-13 | Areva Mines | Bifunctional compounds useful as ligands of uranium (VI), methods of synthesising same and uses thereof |
WO2014139869A1 (fr) * | 2013-03-11 | 2014-09-18 | Areva Mines | Utilisation de composés à fonctions amide et phosphonate pour extraire l'uranium(vi) de solutions aqueuses d'acide sulfurique, issues notamment de la lixiviation sulfurique de minerais uranifères |
US10006103B2 (en) * | 2013-11-08 | 2018-06-26 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Use of an organic-inorganic hybrid material for extracting uranium(VI) from a sulfuric acid aqueous solution, issued notably from the sulfuric leaching of a uranium-bearing ore |
US20160289796A1 (en) * | 2013-11-08 | 2016-10-06 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Use of an organic-inorganic hybrid material for extracting uranium(vi) from a sulfuric acid aqueous solution, issued notably from the sulfuric leaching of a uranium-bearing ore |
WO2016156591A1 (fr) * | 2015-04-03 | 2016-10-06 | Commissariat à l'énergie atomique et aux énergies alternatives | Composés à fonctions oxyde de phosphine et amine, utiles comme ligands de l'uranium(vi), et leurs utilisations, notamment pour extraire l'uranium(vi) de solutions aqueuses d'acide sulfurique |
FR3034417A1 (fr) * | 2015-04-03 | 2016-10-07 | Commissariat Energie Atomique | Composes a fonctions oxyde de phosphine et amine, utiles comme ligands de l'uranium(vi), et leurs utilisations, notamment pour extraire l'uranium(vi) de solutions aqueuses d'acide sulfurique |
US10183959B2 (en) | 2015-04-03 | 2019-01-22 | Commissariat à l'énergie atomique et aux énergies alternatives | Compounds with phosphine oxide and amine functions, useful as uranium (VI) ligands, and uses thereof, in particular for extracting uranium(VI) from aqueous solutions of sulphuric acid |
WO2017001494A1 (fr) | 2015-06-30 | 2017-01-05 | Areva Mines | Procede de separation du fer d'une phase organique contenant de l'uranium et procede d'extraction de l'uranium d'une solution aqueuse d'acide mineral contenant de l'uranium et du fer |
WO2017085312A1 (fr) | 2015-11-19 | 2017-05-26 | Areva Mines | Nouveau matériau organique pour extraire l'uranium d'une solution aqueuse d'acide phosphorique, procédés d'extraction et de récupération de l'uranium associés et précurseur d'un tel matériau organique |
FR3044006A1 (fr) * | 2015-11-19 | 2017-05-26 | Areva Mines | Nouveau materiau organique pour extraire l'uranium d'une solution aqueuse d'acide phosphorique, procedes d'extraction et de recuperation de l'uranium associes et precurseur d'un tel materiau organique |
WO2017085311A1 (fr) | 2015-11-19 | 2017-05-26 | Areva Mines | Procédés d'extraction et de récupération de l'uranium présent dans une solution aqueuse comprenant de l'acide phosphorique |
US11466341B2 (en) * | 2016-09-15 | 2022-10-11 | Commissariat á l'énergie atomique et aux énergies alternatives | Extractant for rare earth extraction from aqueous phosphoric acid solutions and method of extraction |
WO2019025714A1 (fr) | 2017-07-31 | 2019-02-07 | Orano Mining | Composés bifonctionnels à fonction thiophosphine, utiles comme extractants de l'uranium(vi), leurs procédés de synthèse et leurs utilisations |
FR3116834A1 (fr) | 2020-12-02 | 2022-06-03 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Procédé de récupération sélective des terres rares et de l’uranium(VI) d’une solution aqueuse d’acide phosphorique |
WO2022117948A1 (fr) | 2020-12-02 | 2022-06-09 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Procédé de récupération sélective des terres rares et de l'uranium(vi) d'une solution aqueuse d'acide phosphorique |
Also Published As
Publication number | Publication date |
---|---|
CA2872084C (fr) | 2020-09-22 |
BR112014027732B1 (pt) | 2022-01-18 |
AU2013258153A1 (en) | 2014-11-20 |
US9441285B2 (en) | 2016-09-13 |
FR2990206A1 (fr) | 2013-11-08 |
IL235520B (en) | 2018-01-31 |
TN2014000463A1 (fr) | 2016-03-30 |
PE20150282A1 (es) | 2015-03-08 |
IL235520A0 (en) | 2015-02-01 |
US20150133688A1 (en) | 2015-05-14 |
CN104470936B (zh) | 2019-04-19 |
FR2990207A1 (fr) | 2013-11-08 |
AU2013258153B2 (en) | 2017-05-11 |
CA2872084A1 (fr) | 2013-11-14 |
FR2990206B1 (fr) | 2014-06-06 |
FR2990207B1 (fr) | 2015-08-21 |
CN104470936A (zh) | 2015-03-25 |
ZA201407955B (en) | 2015-10-28 |
BR112014027732A2 (pt) | 2017-06-27 |
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