CN114540619B - Functional ionic liquid and preparation method and application thereof - Google Patents
Functional ionic liquid and preparation method and application thereof Download PDFInfo
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- CN114540619B CN114540619B CN202011345768.4A CN202011345768A CN114540619B CN 114540619 B CN114540619 B CN 114540619B CN 202011345768 A CN202011345768 A CN 202011345768A CN 114540619 B CN114540619 B CN 114540619B
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- rare earth
- ionic liquid
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- extraction
- ions
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 64
- -1 carboxylic acid ion Chemical class 0.000 claims abstract description 61
- 150000001768 cations Chemical class 0.000 claims abstract description 26
- 150000001450 anions Chemical class 0.000 claims abstract description 21
- 239000012074 organic phase Substances 0.000 claims description 33
- 238000000926 separation method Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000008346 aqueous phase Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 13
- 229910052765 Lutetium Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052775 Thulium Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 62
- 150000002910 rare earth metals Chemical class 0.000 abstract description 16
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 6
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 abstract description 5
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract description 4
- HYGWNUKOUCZBND-UHFFFAOYSA-N azanide Chemical compound [NH2-] HYGWNUKOUCZBND-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 239000000284 extract Substances 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 238000005192 partition Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 230000007246 mechanism Effects 0.000 description 8
- 238000005185 salting out Methods 0.000 description 8
- 238000000638 solvent extraction Methods 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 6
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 239000012527 feed solution Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical group CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- AAIUWVOMXTVLRG-UHFFFAOYSA-N 8,8-dimethylnonan-1-amine Chemical compound CC(C)(C)CCCCCCCN AAIUWVOMXTVLRG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PINITSMLVXAASM-UHFFFAOYSA-N 1-bromo-2-diethoxyphosphorylethane Chemical compound CCOP(=O)(CCBr)OCC PINITSMLVXAASM-UHFFFAOYSA-N 0.000 description 1
- UIWJXEAMDJCNOV-UHFFFAOYSA-N 1-chloro-3-(chloromethyl)-2,4,5,6-tetrafluorobenzene Chemical compound FC1=C(F)C(Cl)=C(F)C(CCl)=C1F UIWJXEAMDJCNOV-UHFFFAOYSA-N 0.000 description 1
- VRZYWIAVUGQHKB-UHFFFAOYSA-N 2-[2-(dioctylamino)-2-oxoethoxy]-n,n-dioctylacetamide Chemical compound CCCCCCCCN(CCCCCCCC)C(=O)COCC(=O)N(CCCCCCCC)CCCCCCCC VRZYWIAVUGQHKB-UHFFFAOYSA-N 0.000 description 1
- YCQVNMKLANFADW-UHFFFAOYSA-N 2-bromoethyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCCBr YCQVNMKLANFADW-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- XBEDEUGIOGUZSN-UHFFFAOYSA-N CCCCC(CC)COP(O)=O Chemical compound CCCCC(CC)COP(O)=O XBEDEUGIOGUZSN-UHFFFAOYSA-N 0.000 description 1
- 241000409333 Cabeza Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001541138 Cypho Species 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000795633 Olea <sea slug> Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 102100040653 Tryptophan 2,3-dioxygenase Human genes 0.000 description 1
- 101710136122 Tryptophan 2,3-dioxygenase Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JYXGEPNZGMUFEK-UHFFFAOYSA-N [Lu].[Yb].[Tm] Chemical compound [Lu].[Yb].[Tm] JYXGEPNZGMUFEK-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- YOYGIPRFEXDEIU-UHFFFAOYSA-N chloro-trihexyl-tetradecyl-$l^{5}-phosphane Chemical compound CCCCCCCCCCCCCCP(Cl)(CCCCCC)(CCCCCC)CCCCCC YOYGIPRFEXDEIU-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 1
- 238000000658 coextraction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- IOIFRTZBJMZZFO-UHFFFAOYSA-N dysprosium(3+) Chemical compound [Dy+3] IOIFRTZBJMZZFO-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 239000013316 polymer of intrinsic microporosity Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention discloses a functional ionic liquid and a preparation method and application thereof, wherein cations in the ionic liquid are selected from phosphonate ion functionalized quaternary ammonium, carboxylic acid ion functionalized quaternary ammonium and/or amide ion functionalized quaternary ammonium, and anions in the ionic liquid are selected from 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507), bis (2, 4-trimethylpentyl) phosphinic acid (Cyanex 272) and/or sec-octyl phenoxy substituted acetic acid (CA-12). The ionic liquid can efficiently extract and separate rare earth heavy metals; the extraction capacity of the synthesized ionic liquid is far higher than that of the precursor; the extractant can achieve extraction balance in a short time by jointly extracting rare earth ions with anions and cations, has good extraction capacity, load capacity and selectivity, and can be back-extracted at lower acidity; the catalyst is stable after repeated use, and has good regeneration performance.
Description
Technical Field
The invention belongs to the field of rare earth metal extraction, and particularly relates to a functional ionic liquid and a preparation method and application thereof.
Background
Rare earth elements are considered as "industrial vitamins" and are widely used in the fields of alloy materials, metallurgy, glass, ceramics, chemical industry, nuclear industry, electronics, agriculture, optics, medicine, etc. Ion adsorption type rare earth minerals are the most important primary heavy rare earth resources, and are mainly produced in south China, and the global yield of Heavy Rare Earth Elements (HREE) is far lower than that of light rare earth elements. Lutetium is the element with the largest atomic number in lanthanoid, and is widely applied to high-end science and technology fields such as scintillators, photodynamic therapy (PDT), optical limiters, sensors, controllable broadband absorbing materials and the like, and the purity of lutetium is one of the important reasons for influencing the application of lutetium in the high-end fields, so that the lutetium is particularly important for separating lutetium from other heavy rare earth, however, pure single rare earth compounds are difficult to separate due to similar physical and chemical properties of HREE.
The separation of rare earth is industrially carried out by separating rare earth ions from leachate with ammonium bicarbonate or oxalic acid, calcining to prepare mixed rare earth oxide, and finally producing rare earth metals and alloys by solvent extraction and electrodeposition processes (Vahidi, E.; zhao, F. Environmental life cycle assessment on the separation of rare earth oxides through solvent extraction. J environmental Manage 2017,203 (Pt 1), 255-263). Mono-2-ethylhexyl phosphonate (P507) has been the most widely used extractant in REs separations (Sato, T.liquid-liquid extraction of rare-earth elements from aqueous acid solutions by acid organophosphorus components. Hydrodynamics 1989,22 (1-2), 121-140). Taking P507 as an example, in the solvent extraction stage, the industrial heavy rare earth separation method generally comprises the steps of firstly grouping various rare earths, then separating the individual heavy rare earths through a cascade extraction process, wherein lutetium is finally separated from thulium ytterbium lutetium concentrate (Wang, y.l.; li, f.j.; zhao, z.y.; dong, y.m.; sun, x.q.the novel extraction process based on)572for separating heavy rare earths from ion-doped reduced position. Sep. Purif. Technique. 2015,151, 303-308). But because the separation coefficient of P507 in heavy rare earth is smaller, the dissolution needs higher acidity, thereforeThe extractant used for replacing P507 to separate heavy Rare Earth is researched, for example, cytec Industries develop a novel extractant Cyanex272, the separation coefficient between heavy Rare Earth is greatly improved, the leaching acidity is low, but the extraction capacity is low, the extraction load is small, and a third phase (Zhang, X.F.; li, D.Q.extraction of Rare-Earth Ions (III) with Bis (2.4.4-trimethylpenyl) Phosphinic acid. Chinese Journal of Applied Chemistry 1993,10,72-72) is easy to form. The single extractant is difficult to improve the performance of the extractant in all aspects, and the synergistic extraction is an effective extraction method for separating rare earth. For example, for mixtures of Cyanex272 and other extractants (e.g., HEHEHP, D2EHPA, TBP, sec-octylphenoxy substituted acetic acid (CA-12), etc.), a number of synergistic extraction systems have been reported (Zhu, z.w. Separation of cobalt and zinc from concentrated nickel sulfate solutions with Cyanex.272.j. Chem. Tech. Biotechnol.2011,86 (1), 75-81.Zhang, c.; wang, L.S., huang, X.W., yttrium extraction from chloride solution with a synergistic system of 2-ethylhexyl phosphonic acid mono- (2-ethylhexyl) ester and bis (2, 4-trimethylpenyl) phosphonic acid.hydrometric 2014,147-148,7-12.Zaheri, P., abolghasemi, H., ghannadi Maraghe, M., mohammadi, T.interaction of Europium extraction through a supported liquid membrane using mixture of D, EHPA and Cyanex272 as carrier.chemical Engineering and Processing: process Intensification 2015,92,18-24.Shaeriab, M., torMosta edi M., rahbar Kelisami, A.solvent extraction of thorium from nitrate medium by TBP, cyanex and ir. J.radiation.Nucl.Chem.2014).
Ionic Liquids (ILs) are molten salts with melting temperatures below 100 ℃, typically consisting of asymmetric cations and anions, which due to their unique physicochemical properties can be widely used in the fields of electrochemistry, bioavailable, analytical, solvent and catalyst, engineering, physicochemical, etc. The low flammability, non-volatility and high thermal stability make its use in solvent extraction environmentally friendly. Moreover, the prominent feature of ILs is the adjustability of the anionic and cationic structure, which is regarded as a "solvent" due to this adjustability, i.e. the ability to attach specific functional groups to the anions and cations of ILs, called functionalized ionic liquids (TSILs), as the case may be, in order to achieve specific purposes. The nature of this tunable synthesis of ILs, as compared to molecular extractant MEs, will confer unique behavior to ILs during solvent extraction. ILs show a higher partition ratio and better selectivity than organic solvents, an increase in selectivity leading to a reduction in the separation stage, whereas an increase in partition ratio enables a reduction in the volume of diluent added during separation, leading to the possibility of recycling the extractant. There have been many studies on the separation of rare earths using ionic liquids. The ionic liquids prepared by Cyphos IL101 (trihexyl (tetradecyl) phosphorus chloride) were reported to successfully separate cobalt (ii), neodymium (iii) and dysprosium (iii) from iron-free leachate in nitric acid (quejada-Maldonado, e.; olea, f.; sep lveda, r.; castillo, j.; cabezas, r.; merlet, g.; romero, j.poissieilitis and challenges for ionic liquids in hydrodynamics. Guo et al studied the extractive separation of REs (III) in nitrate and chloride media using [ A336] [ P507] or [ A336] [ P204] as extractant, and were one of the positive factors for industrial use (Xiong, Y.; kuang, W.Q.; zhao, J.M.; liu, H.Z.Ionic liquid-based synergistic extraction of rare earths nitrates without diluent: typing-association mechanism.Sep. Purif. Technology.2017, 179, 349-356). Recently, two ionic liquids, primene 81 R.D2 EHPA IL and Primene 81 R.Cyanex572 IL, were used as extractants and successfully applied to the actual waste stream in fluorescent lamp waste, ce (III), eu (III) and Y (III) were selectively recovered from the chloride medium leachate by a four stage cross-flow solvent extraction process, and the purity was not less than 99.9%. The ionic liquid can also form an acid-base coupled bifunctional ionic liquid (ABC-BILs) with a molecular extractant TRPO for separation of rare earth elements, a new form of co-extraction with ionic liquid extractants and molecular extractants (Guo, l.; chen, j.; shen, l.; zhang, j.p.; zhang, d.l.; deng, y.f. highly Selective Extraction and Separation of Rare Earths (III) Using Bifunctional Ionic Liquid extractant.acs sustaiable chem.eng.2014,2 (8), 1968-1975). In recent years, ionic liquids have been embedded in PIMs and used in metal ion adsorption separations.
Ionic liquids as extractant or as diluent for metal separation, the cations being mostly imidazole and some quaternary ammonium or phosphonium cations with long chain alkyl groups, etc., the anions being phosphate-bearing functions such as ehehehp, bis (2, 4-trimethylpentyl) phosphinic acid (Cyanex 272, also indicated by C272), BTMPP, carboxylic acid functions such as CA-12, SOPPA, TODGA and fluorine-containing functions such as BETI, NTf 2 、PF 6 Etc. The loss of anions and cations in the water phase in the extraction process can be reduced to a great extent due to the hydrophobicity of the anions and cations, and the metal is extracted through an ion association mechanism rather than an ion exchange mechanism, so that the method is beneficial to the treatment of environmental problems, and on the other hand, the extraction performance and selectivity of the method are improved.
Disclosure of Invention
In order to improve the technical problems, the invention provides an ionic liquid, wherein cations in the ionic liquid are selected from phosphonate ion functionalized quaternary ammonium, carboxylic acid ion functionalized quaternary ammonium and/or amide ion functionalized quaternary ammonium, and anions in the ionic liquid are selected from 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507), bis (2, 4-trimethyl amyl) phosphinic acid (C272) and/or sec-octyl phenoxy substituted acetic acid (CA-12).
According to an embodiment of the invention, the cation in the ionic liquid is a phosphate ion functionalized quaternary amine [ N ] 888 DOPE] + In this case, the ionic liquid is any one of the following ionic liquids: [ N ] 888 DOPE][P507]、[N 888 DOPE][C272]、[N 888 DOPE][CA-12]。
According to an embodiment of the invention, the cation in the ionic liquid is a carboxylic acid ion functionalized quaternary ammonium [ N ] 888 COOH] + In this case, the ionic liquid is any one of the following ionic liquids: [ N ] 888 COOH][P507]、[N 888 COOH][C272]、[N 888 COOH][CA-12]。
According to an embodiment of the invention, the isolatingThe cation in the subliquid is amide ion functionalized quaternary ammonium [ N ] 888 CON] + In this case, the ionic liquid is any one of the following ionic liquids: [ N ] 888 CON][P507]、[N 888 CON][C272]、[N 888 CON][CA-12]。
According to an embodiment of the invention, the [ N ] 888 DOPE][C272]Has a structure as shown in formula (I):
the invention also provides a preparation method of the ionic liquid, which comprises the following steps:
(1) Under the auxiliary condition of microwaves, the compound containing the cations reacts with tertiary amine compounds in an organic solvent to prepare an intermediate;
(2) And (3) reacting the intermediate in the step (1) with a compound containing the anions in an organic solvent to obtain the ionic liquid.
According to an embodiment of the present invention, the compound containing the cation may be selected from halogenated phosphonates, halogenated carboxylic acids or halogenated amides, wherein the halogen element is bromine, chlorine or iodine. For example, the compound containing the cation is diethyl 2-bromoethylphosphonate.
According to an embodiment of the invention, the compound containing said anion may be selected from sodium 2-ethylhexyl phosphonate mono-2-ethylhexyl ester, sodium bis (2, 4-trimethylpentyl) phosphinate or sodium sec-octylphenoxy substituted acetate, preferably sodium bis (2, 4-trimethylpentyl) phosphinate.
According to an embodiment of the present invention, the tertiary amine compound may be selected from alkyl tertiary amines, such as trioctylamine.
According to an embodiment of the invention, the molar ratio of the compound containing a cation to the tertiary amine compound is (1-1.2): 1, preferably 1.07:1, 1.1:1.
According to an embodiment of the invention, the molar ratio of the compound containing an anion to the intermediate is (1-1.2): 1, preferably 1:1.
According to an embodiment of the present invention, the organic solvent is a solvent capable of sufficiently dissolving the cation-containing compound and/or the anion-containing compound and/or the intermediate, for example, ethanol, acetonitrile or toluene.
According to an embodiment of the invention, in step (1), the volume molar ratio of the organic solvent to the cation-containing compound is (0.8-1.5) mL:1mmol, for example 1.1mL:1mmol.
According to an embodiment of the invention, in step (1), the temperature of the microwave reaction is 50-80 ℃, preferably 60-70 ℃, and exemplary 60 ℃, 70 ℃. For example, the time for the microwave reaction is 0.5 to 4 hours, for example 1 to 3 hours, and exemplary are 1 hour, 2 hours, 3 hours.
According to an embodiment of the invention, in step (2), the temperature of the reaction is 40 to 70 ℃, preferably 50 to 60 ℃, and exemplary 50 ℃ and 60 ℃. For example, the reaction time is 0.5 to 10 hours, for example 2 to 8 hours, and exemplary are 2 hours, 4 hours, and 6 hours.
According to an embodiment of the invention, in step (2), the volume molar ratio of the organic solvent to the compound containing the anion is (0.8-2) mL:1mmol, for example 1.6mL:1mmol.
According to an embodiment of the present invention, step (2) further includes a process of washing the reaction product after the completion of the reaction. For example, the reaction product is washed with distilled water a plurality of times.
According to an exemplary embodiment of the invention, ionic liquids [ N 888 DOPE][C272]The preparation method of the (C) comprises the following steps:
(1) Under the auxiliary condition of microwaves, 2-bromoethyl phosphonic acid diethyl ester and trioctylamine react in ethanol to prepare an intermediate;
(2) Reacting the intermediate in the step (1) with sodium bis (2, 4-trimethylpentyl) phosphinate in ethanol to obtain the ionic liquid [ N ] 888 DOPE][C272]。
The invention also provides application of the ionic liquid in rare earth ion separation and/or enrichment (or recovery), preferably in heavy rare earth ion separation and/or enrichment (or recovery). For example, lu ions are separated from an enrichment of Tm, yb and Lu ions.
The invention also provides application of the ionic liquid as an extractant, preferably as a rare earth ion extractant, and more preferably as a heavy rare earth ion extractant.
According to an embodiment of the invention, the heavy rare earth ions include, but are not limited to, at least one of TmYb and Lu ions, preferably Lu ions.
The invention also provides an extractant, which contains the ionic liquid. Preferably, the extractant is a rare earth ion extractant; more preferably a heavy rare earth ion extractant.
The invention also provides a method for separating rare earth ions, which comprises the following steps:
mixing the organic phase containing the ionic liquid or the extractant, the diluent and the phase modifier with the feed liquid, oscillating, centrifuging and extracting rare earth ions from the aqueous phase into the organic phase.
According to an embodiment of the invention, the diluent is toluene, kerosene, dichloromethane or chloroform, preferably toluene.
According to an embodiment of the invention, the phase modifier is one of isooctyl alcohol or TBP (tributyl phosphate).
According to an embodiment of the invention, the volume ratio of the diluent to the phase modifier is (5-15): 1, e.g. 10:1.
According to an embodiment of the present invention, the feed solution contains a salting-out agent. Preferably, the salting-out agent is sodium chloride. Preferably, the concentration of the salting-out agent in the feed liquid is 0.5-2mol/L, for example 1mol/L.
According to an embodiment of the invention, the feed solution is a solution containing at least two rare earth ions, for example, a solution containing three rare earth ions of Tm, yb and Lu.
According to an embodiment of the invention, the pH of the feed solution is 1-6, e.g. 2-5, preferably 3.
According to an embodiment of the invention, the molar concentration ratio of the ionic liquid to the total rare earth ions in the feed liquid is (2-5): 1.
According to an embodiment of the invention, the volume ratio of the feed liquid to the organic phase is (0.5-2): 1, for example (1-2): 1, exemplary 1:1.
According to an embodiment of the invention, the concentration of ionic liquid in the organic phase is 0.03-0.05mol/L, for example 0.03mol/L.
According to the embodiment of the invention, the concentration of rare earth ions in the feed liquid is 0.03-0.05 mol/L.
According to an embodiment of the invention, the time of oscillation is 2-60min, for example 5-50min, exemplary 40min.
According to an embodiment of the invention, the temperature of the oscillation is 20-35 ℃, e.g. 25-30 ℃.
According to an embodiment of the invention, the rotational speed of the centrifugation is 3000rpm and the centrifugation time is 3-5min.
The invention also provides a method for enriching rare earth ions, which comprises the following steps: and (3) oscillating and contacting the organic phase containing the rare earth ions obtained by the method for separating the rare earth ions with a hydrochloric acid aqueous solution, and back extracting the rare earth ions from the organic phase into the aqueous phase.
According to an embodiment of the invention, the concentration of the aqueous hydrochloric acid solution is 0.1 to 1.5mol/L, preferably 0.3 to 1mol/L.
According to an embodiment of the invention, the volume ratio of the aqueous hydrochloric acid solution to the organic phase containing rare earth ions is 1 (0.5-1.5), for example 1:1.
The beneficial effects of the invention are that
(1) The novel functional ionic liquid is obtained by combining cations with functional groups and functional anions.
(2) According to the invention, the ionic liquid is used as an extractant, so that heavy metals Tm, yb and Lu of rare earth, especially Lu, can be separated efficiently; the extraction capacity of the synthesized ionic liquid is far higher than that of the precursor; the extractant can achieve extraction balance in a short time by jointly extracting rare earth ions with anions and cations, has good extraction capacity, load capacity and selectivity, and can be back-extracted at lower acidity; the catalyst is stable after repeated use, and has good regeneration performance.
(3) The ionic liquid prepared by the invention has the functional group capable of forming coordination bond with metal ions on cations or anions, the metal ions are extracted through an ion association mechanism instead of an ion exchange mechanism, no cations are exchanged from organic phase, and the mechanism is environment-friendly, and on the other hand, the extraction performance and selectivity of the ionic liquid are improved. The extract formed by this mechanism is in the form of ion pairs in the organic phase, whereas for the ionic association mechanism, the salting-out agent added during extraction, after extraction, the anions of the salting-out agent transfer with the metal ions to the organic phase.
Drawings
FIG. 1 is an infrared spectrum of an ionic liquid prepared in example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the ionic liquid prepared in example 1;
FIG. 3 is a nuclear magnetic resonance carbon spectrum of the ionic liquid prepared in example 1;
fig. 4 is a nuclear magnetic resonance chromatogram of the ionic liquid prepared in example 1.
Detailed Description
The preparation method and application of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
Under the protection of inert gas, 11.0g of diethyl 2-bromoethyl phosphate (A336) is dissolved in 50ml of ethanol and 14.9g of trioctylamine is added, the mixture is heated to 70 ℃ under the assistance of microwaves, the temperature is kept for reaction for 1 hour, and the solvent is evaporated to obtain 23.9g of [ N ] 888 DOPE][Br]Pale yellow liquid with a yield of 95%.
11.7g of sodium bis (2, 4-trimethylpentyl) phosphinate (C272) and 22.4g of [ N 888 DOPE][Br]Dissolved in 60ml ethanol and reacted at 50℃for 6 hours. Washing with distilled water several times, drying in vacuo gave 25.1g of [ N ] as a yellow oil 888 DOPE][C272](having a structure represented by formula (I)) in 83% yield.
[N 888 DOPE][C272]The characterization results of (2) are shown in FIGS. 1-4:
IR(cm -1 )：1240，1163(P＝O)，1027，946(P-O)。
1 H NMR(500MHz,DMSO,ppm)：0.84-0.92(m,33H)，1.02-1.14(m，4H)，1.24(t，30H)，1.26-1.29(d，6H)，1.33-1.47(m，6H)，1.57(dtd，6H)，2.91(m，8H)，3.98(dq，4H)。
13 C NMR(126MHz,DMSO,ppm):14.40,16.63,16.68,24.60,24.64,30.37(CH 3 ),22.53,26.59,28.97,31.64,55.37(CH 2 ),31.40([C272] - P-CH in 2 ),24.57,30.45(CH),52.92(4N-CH 2 ),61.75(O-CH 2 )。 31 P NMR(202MHz,DMSO,ppm)：16.90([N 888 DOPE] + P=o), 47.66 ([ C272)] - P=o).
Application example
The ionic liquid [ N ] prepared in example 1 888 DOPE][C272]Rare earth ions are extracted as an extractant, and a back extraction experiment is carried out:
dissolving ionic liquid in toluene serving as a diluent and uniformly mixing with isooctanol serving as a phase modifier, wherein toluene serving as the diluent is used for reducing the viscosity of an extracting agent, the concentration of the ionic liquid is 0.03-0.05mol/L, the volume ratio of toluene to isooctanol is 10:1, preparing an organic phase, and placing 5ml of the organic phase and 5ml of feed liquid containing rare earth ions into a 15ml centrifuge tube, wherein the feed liquid comprises LuCl 3 Aqueous solution, luCl 3 Concentration range of 0.008-0.01mol/L, or TmCl of the same concentration 3 、YbCl 3 、LuCl 3 ，TmCl 3 Or YbCl 3 Or LuCl 3 The concentration of (C) is in the range of 0.003-0.005mol/L, and the concentration is dissolvedThe centrifuge tube is oscillated in an oscillation mixer for 40min at the temperature of 25 ℃ in the aqueous phase solution of the sodium chloride salting-out agent with the temperature of 1mol/L, and the sodium chloride can ensure the constancy of the ionic strength in the extraction process and improve the extraction efficiency.
After the completion of the shaking, the centrifuge tube was centrifuged at 3000rpm for 5min to separate rare earth ions.
The concentration of rare earth ions in the aqueous phase was determined using ICP-OES and the content of rare earth elements in the organic phase was calculated by mass balance.
The stripping experiments were carried out by contacting 5ml of organic phase loaded with RE (III) with 5ml of aqueous HCl of different concentrations at 25℃for 30min in a shaking mixer.
Extraction efficiency (E), partition ratio (D), separation factor (beta), stripping efficiency (S) is calculated by the following equation:
in the formula, [ M ]] a And [ M ]] t Expressed as initial and equilibrium concentrations, [ M ] of RE (III), respectively, in the aqueous phase] aq，a Represents the concentration of RE (III) [ M ] in the stripping agent when the stripping stage reaches equilibrium] org，t Represents the concentration of RE (III) in the organic phase, D, at equilibrium in the extraction stage 1 And D 2 Is the partition ratio of two RE (III) obtained by a single extraction experiment.
Application example 1-1
[ N ] in example 1 888 DOPE][C272]And intermediates [ N ] thereof 888 DOPE][Br]And C272 as extractant, respectively, with reference to the extraction method of application example 1: the organic phase is prepared by mixing an extractant, toluene and isooctanol, wherein the volume ratio of toluene to isooctanol is 10:1, the concentration of the extractant is 0.05mol/L, and the pH value of feed liquid is=4.5; contains Lu with concentration of 0.01mol/L 3+ And 1mol/L of aqueous phase feed liquid of sodium chloride salting-out agent; mixing 5ml of organic phase and 5ml of aqueous phase feed liquid containing rare earth ions, and respectively carrying out extraction experiments under the same conditions, wherein the extraction experiments show that [ N ] 888 DOPE][Br]With C272 to Lu 3+ The extraction efficiencies of (a) are 2.61% and 11.87%, respectively, and [ N ] 888 DOPE][C272]The extraction efficiency of (2) was 99.94%.
As can be seen from the analysis of the above results, since both cations and anions in the ionic liquid contain extraction functional groups, the cation and anion pair Lu 3+ Is synergistic with Lu 3+ Effective coordination is carried out to form stable complex, thereby improving the extraction capacity of the extractant.
Application examples 1-2 influence of acidity of solution
The pH of the feed solution in application example 1 was gradually and incrementally adjusted from 1 to 5 in the range of 1-5, extractant [ N ] 888 DOPE][C272]The concentration is 0.03mol/L, and the best [ N ] is achieved at pH=3 888 DOPE][C272]For Tm 3+ ,Yb 3+ ,Lu 3+ The extraction rates of (a) were 78.9%,92.6%,94.2%, respectively, and the beta value of Lu/Tm was similar to the trend of change in acidity of aqueous phase, and reached the maximum at ph=3, while the beta value of Lu/Yb was hardly changed.
Application examples 1-3 kinetic study
By changing the contact time of the organic phase and the feed liquid, [ N ] is explored 888 DOPE][C272]Extraction of Tm from chloride Medium 3+ ，Yb 3+ ，Lu 3+ The concentration of the extractant is 0.03mol/L, [ N ] 888 DOPE][C272]The system extraction kinetics is faster, and the extraction time is only 3min [ N ] 888 DOPE][C272]For Tm 3+ ，Yb 3+ ，Lu 3+ The extraction efficiencies of (a) are 64.97%, 80.76% and 83.19%, respectively, and the extraction is basically balanced at 40min, and the extraction efficiencies are 78.01 when the extraction reaches saturation％、92.89％、95.17％。
There is a small error in the experiment, and therefore, the calculated extraction efficiency (E), partition ratio (D), separation factor (β), and stripping efficiency (S) are all within an acceptable range within 1%.
Application examples 1-4 loading of ionic liquid
The extraction load is an important index for measuring the performance of the extractant, and the ionic liquid prepared in example 1 [ A336]][C272]And C272 are respectively identical to one part of LuCl described in application example 1-1 3 The feed liquid is contacted and oscillated for 40min, after the organic phase is separated, the organic phase is extracted with a part of fresh feed liquid, and the extraction operation is repeated for 5 times, thus obtaining [ N ] 888 DOPE][C272]For Lu 3+ Saturation loading of extraction and reaction with [ A336] under the same conditions][C272]Compared with C272, after the above 5 times of repeated extraction experiments, lu in the organic phase 3+ Is substantially unchanged. The concentration of the extractant is 0.05mol.L -1 When [ N ] 888 DOPE][C272]、[A336][C272]And C272 to Lu in the presence of salting-out agent sodium chloride medium 3+ The extraction saturation loadings of (2) were 2.55 g.L, respectively -1 ，2.23g·L -1 ，0.21g·L -1 From the above, the loading of C272 is far lower than N 888 DOPE][C272]And [ A336]][C272]。
Application examples 1-5 extraction and separation of RE (III) from ionic liquids
Research [ N 888 DOPE][C272]、[A336][C272]Extraction of Tm with three C272 extractants in chloride medium 3+ ，Yb 3+ ，Lu 3+ And the partition ratio D and the separation factor beta to compare their extraction performance and selectivity for the enriched heavy rare earths. The extraction performance of the three extractants is [ N ] 888 DOPE][C272]＞[A336][C272]> C272, and the partition ratio is greater as the ionic radius decreases. Selecting a feed liquid with pH=3 and total rare earth ion concentration of 0.009mol/L (the feed liquid contains three ions of Tm, yb and Lu, and the ion concentration is 0.003 mol/L) and an extractant with concentration of 0.03mol/L as the optimal separation conditions, [ N ] 888 DOPE][C272]And [ A336]][C272]Extraction of Tm 3+ The partition ratios of (A) are very close, 3.87 and 3.55 respectively, [ A336]][C272]Yb extraction 3+ And Lu 3+ The partition ratio of (2) is 5.93 and 6.61, and [ N ] 888 DOPE][C272]Yb extraction 3+ And Lu 3+ Up to 13.61 and 18.56. The beta value of Lu/Tm of the three extractants is 4.80,1.86,2.34, [ N ] 888 DOPE][C272]Beta value of (C) is higher than [ A336]][C272]Beta values with C272, lu/Yb are 1.36,1.11,1.46, [ N ] 888 DOPE][C272]Beta value of (C) is higher than [ A336]][C272]。
Table 1 shows [ N ] 888 DOPE][C272]The partition ratio D and the separation factor beta after extracting a plurality of mixed rare earth with the same concentration show [ N ] 888 DOPE][C272]The system tends to extract the nature of heavy rare earth ions with an extractant concentration of 0.03mol/L, a single rare earth metal concentration of 0.001mol/L, and a pH of 3.
TABLE 1
Application examples 1-6 Back extraction experiments
To examine [ N ] 888 DOPE][C272]The stripping performance of the extraction system is 0 to 1.5mol L -1 HCl of different concentrations Lu was extracted from application example 1 3+ Is subjected to a stripping experiment in which Lu 3+ The concentration is 0.01mol/L, and the Lu is difficult to be mixed with deionized water 3+ Back extracted but when the HCl concentration increased to 0.3mol L -1 24% Lu 3+ Is stripped from the organic phase. And when the HCl concentration is from 0.3mol L -1 To 0.5mol L -1 At the time, the stripping rate increases rapidly, so that Lu 3+ Almost complete strip from the organic phase to the aqueous phase, indicating [ N 888 DOPE][C272]The stripping performance of the catalyst is better.
Application examples 1-7 cycle experiments
[ N ] prepared in example 1 888 DOPE][C272]The regeneration and cycle performance test of (2) is as follows:
0.05mol L was added to the vessel -1 N [ N ] of 888 DOPE][C272]1L of organic phase and 0.01mol L of organic phase -1 Lu 3+ 1L of feed liquid is mixed, the feedThe initial pH of the aqueous phase in the liquid was 4.5, and the aqueous phase was separated. 1mol L is used -1 1L of aqueous HCl solution in the organic phase to ensure Lu in the organic phase 3+ All are stripped into the aqueous phase, and the aqueous phase is separated. After stripping, the vessel was charged with a concentration of 0.5mol L -1 1L of NaOH aqueous solution, and oscillating for 30min to remove HCl contained in the organic phase, and separating the organic phase and the aqueous phase; this procedure was repeated 6 times to determine the stability of the extractant.
[N 888 DOPE][C272]After 6 cycles, for Lu 3+ The extraction efficiency of (2) is kept at 100%, and the back extraction rate in each cycle reaches 100%. Indicating [ N ] 888 DOPE][C272]Can be well recycled and regenerated.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (16)
1. A functional ionic liquid is characterized in that the ionic liquid is [ N ] 888 DOPE][C272]；
The [ N ] 888 DOPE][C272]Has a structure as shown in formula (I):
2. the method for preparing the ionic liquid according to claim 1, wherein the method comprises the following steps: (1) Under the auxiliary condition of microwaves, a compound containing cations and a tertiary amine compound react in an organic solvent to prepare an intermediate; (2) Reacting the intermediate in the step (1) with a compound containing anions in an organic solvent to obtain the ionic liquid;
the compound containing cations is selected from halogenated phosphonate, wherein halogen element is bromine, chlorine or iodine; the anion containing compound is selected from sodium bis (2, 4-trimethylpentyl) phosphinate.
3. The process according to claim 2, wherein the tertiary amine compound is selected from the group consisting of alkyl tertiary amines,
the molar ratio of the cation-containing compound to the tertiary amine compound is (1-1.2): 1;
the molar ratio of the anionic-containing compound to the intermediate is (1-1.2): 1.
4. The preparation method according to claim 2, wherein in the step (1), the temperature of the microwave reaction is 50-80 ℃ and the time of the microwave reaction is 0.5-4 hours;
in the step (2), the reaction temperature is 40-70 ℃ and the reaction time is 0.5-10h.
5. Use of the ionic liquid according to claim 1 for rare earth ion separation and/or enrichment.
6. The use according to claim 5, characterized in that it is in heavy rare earth ion separation and/or enrichment.
7. The use according to claim 5, characterized in that the Lu ions are separated from the concentrate of Tm, yb and Lu ions.
8. Use of the ionic liquid of claim 1 as an extractant.
9. The use according to claim 8, characterized in that the use is as rare earth ion extractant.
10. The use according to claim 9, characterized in that the use is as heavy rare earth ion extractant.
11. The use according to claim 10, wherein the heavy rare earth ions are selected from at least one of TmYb and Lu ions.
12. An extractant comprising the ionic liquid of claim 1.
13. The extractant of claim 12, wherein the extractant is a rare earth ion extractant.
14. The extractant of claim 13, wherein the extractant is a heavy rare earth ion extractant.
15. A method of separating rare earth ions, the method comprising the steps of:
mixing an organic phase comprising the ionic liquid of claim 1 or the extractant, diluent, and phase modifier of any one of claims 12-14, and a feed liquid, shaking, centrifuging, and extracting rare earth ions from the aqueous phase into the organic phase.
16. A method for enriching rare earth ions, the method comprising the steps of: the method for separating rare earth ions according to claim 15, wherein the organic phase containing rare earth ions is contacted with an aqueous hydrochloric acid solution in an oscillating manner, and the rare earth ions are back extracted from the organic phase into the aqueous phase.
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