CN114540619A - 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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- CN114540619A CN114540619A CN202011345768.4A CN202011345768A CN114540619A CN 114540619 A CN114540619 A CN 114540619A CN 202011345768 A CN202011345768 A CN 202011345768A CN 114540619 A CN114540619 A CN 114540619A
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- ionic liquid
- rare earth
- extractant
- extraction
- earth ions
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- -1 carboxylic acid ion Chemical class 0.000 claims abstract description 71
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 63
- 150000001768 cations Chemical class 0.000 claims abstract description 30
- 150000001450 anions Chemical class 0.000 claims abstract description 23
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 16
- 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 claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001242 acetic acid derivatives Chemical class 0.000 claims abstract description 5
- HYGWNUKOUCZBND-UHFFFAOYSA-N azanide Chemical compound [NH2-] HYGWNUKOUCZBND-UHFFFAOYSA-N 0.000 claims abstract description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000012074 organic phase Substances 0.000 claims description 33
- 238000000926 separation method Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052765 Lutetium Inorganic materials 0.000 claims description 11
- 239000008346 aqueous phase Substances 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910052775 Thulium Inorganic materials 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 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 4
- 238000002156 mixing Methods 0.000 claims description 4
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- UMJXWRGUKRAFGF-UHFFFAOYSA-N 2,4,4-trimethyl-1-phosphorosooxypentane Chemical compound CC(C)(C)CC(C)COP=O UMJXWRGUKRAFGF-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 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
- 150000001732 carboxylic acid derivatives Chemical class 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229940085991 phosphate ion Drugs 0.000 claims description 2
- 239000004808 2-ethylhexylester Substances 0.000 claims 1
- LGCMATLLTRQLHG-UHFFFAOYSA-N C(C)C(COP(O)(=O)CC)CCCC Chemical group C(C)C(COP(O)(=O)CC)CCCC LGCMATLLTRQLHG-UHFFFAOYSA-N 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 70
- 150000002910 rare earth metals Chemical class 0.000 abstract description 15
- 238000011068 loading method Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 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 3
- 239000000284 extract Substances 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 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
- 239000003795 chemical substances by application Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000002474 experimental method Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- 238000000638 solvent extraction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 5
- 238000005192 partition Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 4
- 229940093635 tributyl phosphate Drugs 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
- 238000005481 NMR spectroscopy Methods 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
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012527 feed solution Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-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
- MQWSHBCKOSWEFJ-UHFFFAOYSA-N CC[P] Chemical compound CC[P] MQWSHBCKOSWEFJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 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
- 239000002253 acid Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004458 analytical method Methods 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
- 238000004090 dissolution Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- WFJTZFAWJFZTFV-UHFFFAOYSA-M sodium;bis(2,4,4-trimethylpentyl)phosphinate Chemical compound [Na+].CC(C)(C)CC(C)CP([O-])(=O)CC(C)CC(C)(C)C WFJTZFAWJFZTFV-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-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
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 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 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
- 238000004679 31P NMR spectroscopy Methods 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
- 101100420946 Caenorhabditis elegans sea-2 gene Proteins 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
- 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 239000003153 chemical reaction reagent Substances 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
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 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
- 239000003814 drug Substances 0.000 description 1
- IOIFRTZBJMZZFO-UHFFFAOYSA-N dysprosium(3+) Chemical compound [Dy+3] IOIFRTZBJMZZFO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000002955 isolation Methods 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
- AEDROEGYZIARPU-UHFFFAOYSA-K lutetium(iii) chloride Chemical compound Cl[Lu](Cl)Cl AEDROEGYZIARPU-UHFFFAOYSA-K 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 239000013316 polymer of intrinsic microporosity Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 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
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- JCQGIZYNVAZYOH-UHFFFAOYSA-M trihexyl(tetradecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC JCQGIZYNVAZYOH-UHFFFAOYSA-M 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
- 238000005406 washing Methods 0.000 description 1
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 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
Images
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
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- 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), di (2,4,4-trimethylpentyl) phosphinic acid (Cyanex272) and/or sec-octylphenoxy 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 extract rare earth ions through the anion and cation, can reach extraction balance in a short time, has good extraction capacity, loading capacity and selectivity, and can perform back extraction at low acidity; the catalyst can still keep stable after being recycled for many times 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 "industrial vitamins" and are widely used in the fields of alloy materials, metallurgy, glass, ceramics, chemical industry, nuclear industry, electronics, agriculture, optics, medicine, and the like. The ion adsorption type rare earth mineral is the most important primary heavy rare earth resource, is 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 lanthanide, and is widely applied to high-end scientific and technological 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 high-end fields, so that lutetium is particularly important for separating other heavy rare earths, but a pure single rare earth compound is difficult to separate due to the similarity of physical and chemical properties of HREE.
The separation of rare earth is carried out by separating out rare earth ions from leaching solution by ammonium bicarbonate or oxalic acid, calcining to prepare mixed rare earth oxide, and producing rare earth metal and alloy by solvent extraction and electrodeposition (Vahidi, E.; ZHao, F. environmental life cycle analysis of rare earth oxides through solution extraction. J environmental management manager 2017,203(Pt 1), 255) 263). 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507) has been the most widely used extractant for the separation of REs (Sato, T.liquid-liquid extraction of raw-earth elements from aqueous acid solutions by acid organophosphorus compounds, hydrometallurgy 1989,22(1-2), 121-. Taking P507 as an example, in the solvent extraction stage, the separation method of heavy rare earth in industry generally divides various rare earths into groups, then separates individual heavy rare earth through the cascade extraction process, lutetium is finally separated from thulium ytterbium lutetium enrichment (Wang, Y.L.; Li, F.J.; ZHao, Z.Y.; Dong, Y.M.; Sun, X.Q.the novel extraction process based on
572for separating the heaven earth from ion-adsorbed disposed. Sep. Purif. technol.2015,151, 303-308). But because the separation coefficient of P507 in heavy rare earth is relatively highSince small and high acidity is required for dissolution, many extractants for separating heavy Rare Earth instead of P507 have been studied, for example Cytec Industries developed a novel extractant Cyanex272 which largely increases the separation coefficient between heavy Rare Earth and has low dissolution acidity but low extraction ability, small amount of extraction load, and easy formation of a third phase (Zhang, X.F.; Li, D.Q.extraction of ray-Earth Ions (III) with Bis (2.4.4-trimethyl-phosphoric acid. Chinese Journal of Applied Chemistry 1993,10, 72-72.). The single extractant is difficult to improve the performance of the extractant comprehensively, and the synergistic extraction is an effective extraction method for separating the rare earth. For example, for mixtures of Cyanex272 and other extractants (e.g., HEHEHEHP, D2EHPA, TBP, sec-octylphenoxy-substituted acetic acid (CA-12), etc.), many synergistic extraction systems have been reported (Zhu, Z.W. Separation of cobalt and zinc synthesized solutions with Cyanex 272.J.Chem.Technol.Biotechnol.2011, 86-81. Zhang, C.; Wang, L.S. Huang, X.W. Yttrium extraction from chlorine solution with synthetic system of 2-ethyl phosphorus acetic acid- (2-ethyl) reactors (2,4, 4-methyl) reactor of 2-ethyl phosphorus synthesis, and sea-2-ethyl phenol synthesis of 2-ethyl cellulose synthesis of reaction of 2-ethyl phenol synthesis of 2-ethyl cellulose synthesis of reaction, sea-reaction of 2, 4-methyl phenol and reaction of 2-reaction of sea-reaction, sea-2-reaction of sea-2-ethyl phenoxy, sea-2, sea-4, sea, m. is; rahbar Kelissami, A.solvent extraction of sodium from nitrate medium by TBP, Cyanex272 and the same mix.J.Radioanal.Nucl.chem.2014).
Ionic Liquids (ILs) are molten salts with melting temperatures below 100 ℃, usually consisting of asymmetric cations and anions, and can be widely used in the fields of electrochemistry, bio-utilization, analysis, solvents and catalysts, engineering, physicochemical, etc. due to their unique physicochemical properties. The low flammability, non-volatility and high thermal stability make its use in solvent extraction environmentally friendly. Furthermore, ILs are characterized by a tunable anionic and cationic structure, which is considered to be a "programmable solvent" because of this tunability, i.e., the ability to attach specific functional groups to the anions and cations of ILs for specific purposes, as required by the actual situation, is known as functionalized ionic liquids (TSILs). The properties of this tunable synthesis of ILs will give them unique behavior in solvent extraction processes compared to the molecular extractant MEs. ILs exhibit higher partition ratios and better selectivity than organic solvents, with increased selectivity allowing for a reduction in separation stages, and increased partition ratios allowing for a reduction in the volume of diluent added during separation, with the possibility of recycling the extractant. There have been many studies on the separation of rare earths using ionic liquids. Studies have reported that ionic liquids prepared from Cyphos IL101 (trihexyl (tetradecyl) phosphonium chloride) successfully separate cobalt (II), neodymium (III) and dysprosium (III) from iron-free leachates in nitric acid (Quijada-Maldonado, E.; Olea, F.; Sep U.V. Ed, R.; Castillo, J.; Cabezas, R.; Merlet, G.; Romero, J.Possiblities and transformers for ionic acids in hydrometallurgy.Sep.purif.Techno.2020, 251.). Guo et al have studied the extraction and separation of the REs (III) in nitrate and chloride media using [ A336] [ P507] or [ A336] [ P204] as an extractant, and the high selectivity and low acid-base consumption thereof are positive factors for industrial applications (Xiong, Y.; Kuang, W.Q.; ZHao, J.M.; Liu, H.Z.Ionic liquid-based synthetic extraction of rare earths with a direct out solution: Tycal ion-association mechanism. Sep.Purif.Tehnol.2017, 179, 349-356). Recently, Ce (III), Eu (III) and Y (III) are selectively recovered from chloride medium leachate by a four-stage cross-flow solvent extraction process using two ionic liquids Primene 81R & D2EHPA IL and Primene 81R & Cyanex 572IL as extractants and successfully applied to actual waste streams in fluorescent lamp waste, and the purity thereof is more than or equal to 99.9%. The Ionic Liquid can also form acid-base coupled Bifunctional Ionic liquids (ABC-BILs) with a molecular extractant TRPO for separating Rare earth elements, which is a new form of synergistic Extraction Using the Ionic Liquid extractant and the molecular extractant (Guo, L.; Chen, J.; Shen, L.; Zhang, J.P.; Zhang, D.L.; Deng, Y.F. high choice Extraction and Separation of ray Earth (III) Using Bifunctional Ionic Liquid extractant, Sustainable Chem. Eng.2014,2(8), 1968-. In recent years of research, ionic liquids have been embedded in PIMs and used in metal ion adsorption separations.
The ionic liquid is used as extractant or diluent for metal separation, the cation is mostly imidazole and some quaternary ammonium or phosphine cations with long-chain alkyl, etc., the anion is phosphate functional group such as EHEHEHP, bis (2,4,4-trimethylpentyl) phosphinic acid (Cyanex272, also can be represented by C272), BTMPP, carboxylic acid functional group such as CA-12, SOPPA, TODGA and fluorine-containing functional group such as BETI, NTf2、PF6And the like. Due to the hydrophobicity of the anions and cations, the loss of the anions and cations in the water phase in the extraction process can be reduced to a great extent, and the metal is extracted through an ion association mechanism rather than an ion exchange mechanism, so that the environmental problem is favorably treated, and the extraction performance and selectivity of the metal are improved.
Disclosure of Invention
In order to improve the above technical problem, the present invention provides an ionic liquid, wherein the cation in the ionic liquid is selected from phosphonate ion functionalized quaternary ammonium, carboxylic acid ion functionalized quaternary ammonium and/or amide ion functionalized quaternary ammonium, and the anion in the ionic liquid is selected from 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507), bis (2,4,4-trimethylpentyl) phosphinic acid (C272) and/or sec-octylphenoxy substituted acetic acid (CA-12).
According to an embodiment of the invention, the cation in the ionic liquid is a phosphate ion functionalized quaternary ammonium [ N ]888DOPE]+When the ionic liquid is any one of the following ionic liquids: [ N ]888DOPE][P507]、[N888DOPE][C272]、[N888DOPE][CA-12]。
According to an embodiment of the invention, the cation in the ionic liquid is a carboxylic acid ion functionalized quaternary ammonium [ N ]888COOH]+When the ionic liquid is any one of the following ionic liquids: [ N ]888COOH][P507]、[N888COOH][C272]、[N888COOH][CA-12]。
According to an embodiment of the invention, the cation in the ionic liquid is an amide ion functionalized quaternary ammonium [ N ]888CON]+When the ionic liquid is any one of the following ionic liquids: [ N ]888CON][P507]、[N888CON][C272]、[N888CON][CA-12]。
According to an embodiment of the present invention, said [ N ]888DOPE][C272]Has a structure shown in formula (I):
the invention also provides a preparation method of the ionic liquid, which comprises the following steps:
(1) under the microwave-assisted condition, reacting the compound containing the cations with a tertiary amine compound in an organic solvent to prepare an intermediate;
(2) and (2) reacting the intermediate in the step (1) with a compound containing the anion in an organic solvent to obtain the ionic liquid.
According to an embodiment of the 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 mono-2-ethylhexyl 2-ethylhexylphosphonate, sodium di (2,4,4-trimethylpentyl) phosphinate or sodium sec-octylphenoxy substituted acetate, preferably sodium di (2,4,4-trimethylpentyl) phosphinate.
According to an embodiment of the invention, the tertiary amine compound may be selected from alkyl tertiary amines, such as trioctylamine.
According to an embodiment of the invention, the molar weight ratio of the compound containing the 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 weight ratio of the compound containing the anion and 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 compound containing the cation and/or the compound containing the anion and/or the intermediate, and is, 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 compound containing the cation is (0.8-1.5) mL:1mmol, for example 1.1mL:1 mmol.
According to an embodiment of the present invention, in step (1), the temperature of the microwave reaction is 50 to 80 ℃, preferably 60 to 70 ℃, exemplary 60 ℃, 70 ℃. For example, the microwave reaction time is 0.5 to 4 hours, such as 1 to 3 hours, exemplary 1 hour, 2 hours, 3 hours.
According to an embodiment of the present invention, in the 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 from 0.5 to 10 hours, such as from 2 to 8 hours, exemplary 2 hours, 4 hours, 6 hours.
According to an embodiment of the present 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:1 mmol.
According to an embodiment of the present invention, the step (2) further includes a process of washing the reaction product after the completion of the reaction. For example, the reaction product is washed several times with distilled water.
According to an exemplary embodiment of the invention, the ionic liquid [ N ]888DOPE][C272]The preparation method comprises the following steps:
(1) under the microwave-assisted condition, reacting 2-bromoethyl diethyl phosphonate with trioctylamine in ethanol to prepare an intermediate;
(2) reacting the intermediate in the step (1) with sodium bis (2,4,4-trimethylpentyl) phosphinate in ethanol to obtain the ionic liquid [ N888DOPE][C272]。
The invention also provides the application of the ionic liquid in rare earth ion separation and/or enrichment (or recovery), preferably the application in heavy rare earth ion separation and/or enrichment (or recovery). For example, Lu ions are separated from a concentrate of Tm, Yb and Lu ions.
The invention also provides application of the ionic liquid as an extracting agent, preferably application as a rare earth ion extracting agent, and more preferably application as a heavy rare earth ion extracting agent.
According to an embodiment of the present 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 extracting agent 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 extracting agent, the diluent and the phase modifier with the feed liquid, oscillating, centrifuging, and extracting the rare earth ions from the aqueous phase to 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 isooctanol or TBP (tributylphosphate).
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 solution is 0.5-2mol/L, such as 1 mol/L.
According to an embodiment of the present invention, the feed liquid 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 in the range of 1 to 6, such as 2 to 5, preferably 3.
According to the 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, e.g. (1-2):1, illustratively 1: 1.
According to an embodiment of the invention, the concentration of ionic liquid in the organic phase is between 0.03 and 0.05mol/L, such as 0.03 mol/L.
According to the embodiment of the invention, the concentration of the 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, such as 5-50min, exemplary 40 min.
According to an embodiment of the invention, the temperature of the shaking is 20-35 deg.C, such as 25-30 deg.C.
According to an embodiment of the invention, the rotation speed of the centrifugation is 3000rpm and the centrifugation time is 3-5 min.
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 in 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 to a water phase.
According to an embodiment of the invention, the concentration of the aqueous hydrochloric acid solution is between 0.1 and 1.5mol/L, preferably between 0.3 and 1 mol/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 invention has the advantages of
(1) The invention combines the cation with functional group and the functional anion to obtain a novel functional ionic liquid.
(2) The invention takes the ionic liquid as an extracting agent, and can efficiently separate the rare earth heavy metals Tm, Yb and Lu, particularly Lu; the extraction capacity of the synthesized ionic liquid is far higher than that of the precursor; the extractant can extract rare earth ions through the anion and cation, can reach extraction balance in a short time, has good extraction capacity, loading capacity and selectivity, and can perform back extraction at low acidity; the catalyst can still keep stable after being recycled for many times and has good regeneration performance.
(3) The cation or anion of the ionic liquid prepared by the invention has a functional group capable of forming a coordination bond with metal ions, and the metal ions are extracted through an ion association mechanism rather than an ion exchange mechanism, so that no cation is exchanged from an organic phase, the mechanism is environment-friendly, and the extraction performance and selectivity of the ionic liquid are improved. The extraction compound formed by this mechanism exists in the organic phase in the form of ion pair, and in the case of ion association mechanism, the salting-out agent is added in the extraction process, and after extraction, the anion of the salting-out agent is transferred to the organic phase with the metal ion.
Drawings
FIG. 1 is an infrared spectrum of an ionic liquid prepared in example 1;
FIG. 2 is a NMR hydrogen spectrum of an ionic liquid prepared in example 1;
FIG. 3 is a NMR carbon spectrum of the ionic liquid prepared in example 1;
FIG. 4 is a NMR phosphorus spectrum of the ionic liquid prepared in example 1.
Detailed Description
The preparation and use 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 only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
Under the protection of inert gas, 11.0g of diethyl 2-bromoethylphosphate (A336) is dissolved in 50ml of ethanol, 14.9g of trioctylamine is added, the mixture is heated to 70 ℃ with the assistance of microwave, the temperature is maintained for reaction for 1 hour, and the solvent is evaporated to obtain 23.9g of [ N ] N888DOPE][Br]A light yellow liquid with a yield of 95%.
11.7g of sodium bis (2,4,4-trimethylpentyl) phosphinate(C272) And 22.4g of [ N ]888DOPE][Br]Dissolved in 60ml of ethanol and reacted at 50 ℃ for 6 hours. Washed with distilled water several times and dried in vacuo to give 25.1g of [ N ] as a yellow oil888DOPE][C272](having a structure as shown in formula (I)), the yield was 83%.
[N888DOPE][C272]The characterization results are shown in FIGS. 1-4:
IR(cm-1)：1240，1163(P＝O)，1027，946(P-O)。
1H 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)。
13C NMR(126MHz,DMSO,ppm):14.40,16.63,16.68,24.60,24.64,30.37(CH3),22.53,26.59,28.97,31.64,55.37(CH2),31.40([C272]-middle P-CH2),24.57,30.45(CH),52.92(4N-CH2),61.75(O-CH2)。31P NMR(202MHz,DMSO,ppm)：16.90([N888DOPE]+Where P ═ O), 47.66([ C272)]-Where P ═ O).
Application example
The ionic liquid [ N ] prepared in example 1888DOPE][C272]Rare earth ions were extracted as extractant, and back extraction experiments:
dissolving ionic liquid in diluent toluene, uniformly mixing the ionic liquid with phase modifier isooctanol, taking the toluene as the diluent to reduce the viscosity of an extracting agent, enabling the concentration of the ionic liquid to be 0.03-0.05mol/L, enabling the volume ratio of the toluene to the isooctanol to be 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 is LuCl3Aqueous solution, LuCl3The concentration range is 0.008-0.01mol/L, or TmCl with the same concentration3、YbCl3、LuCl3，TmCl3Or YbCl3Or LuCl3In the concentration range of0.003-0.005mol/L, and simultaneously dissolving aqueous solution of sodium chloride salting-out agent with concentration of 1mol/L, oscillating the centrifugal tube in an oscillating mixer for 40min at 25 ℃, wherein the sodium chloride can ensure the ionic strength to be constant in the extraction process, and the extraction efficiency is improved.
After completion of the shaking, the 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 method.
The stripping experiments were carried out by contacting 5ml of the organic phase loaded with RE (III) with 5ml of aqueous HCl at different concentrations for 30min at 25 ℃ in a shaking mixer.
The extraction efficiency (E), the distribution ratio (D), the separation factor (beta), and the stripping efficiency (S) are calculated by the following equation:
wherein [ M ]]aAnd [ M]tExpressed as initial and equilibrium concentrations of RE (III) [ M ] in the aqueous phase]aq，aRepresents the RE (III) concentration in the stripping agent at the time of the stage of stripping reaching equilibrium, [ M ]]org，tRepresents the concentration of RE (III) in the organic phase at equilibrium in the extraction stage, D1And D2Is the partition ratio of two re (iii) obtained in a single extraction experiment.
Application examples 1 to 1
[ N ] in example 1888DOPE][C272]And intermediates thereof [ N888DOPE][Br]And C272 as extractant, respectively, with reference to the extraction method of application example 1: the organic phase is prepared by mixing an extracting agent, toluene and isooctanol, wherein the volume ratio of the toluene to the isooctanol is 10:1, the concentration of the extracting agent is 0.05mol/L, and the pH value of feed liquid is 4.5; containing Lu with the concentration of 0.01mol/L3+And 1mol/L of aqueous phase feed liquid of sodium chloride salting-out agent; 5ml of organic phase and 5ml of aqueous phase feed liquid containing rare earth ions are mixed, extraction experiments are respectively carried out under the same conditions, and the extraction experiments show that [ N888DOPE][Br]And C272 to Lu3+The extraction efficiencies of (A) were 2.61% and 11.87%, respectively, and [ N ]888DOPE][C272]The extraction efficiency of (3) was 99.94%.
From the above results, it was found that since both cations and anions in the ionic liquid contain an extraction functional group, the cation and anion pair Lu3+Synergistic effect of (1), with Lu3+Effective coordination is carried out, and a stable complex is formed, so that the extraction capacity of the extractant is improved.
Application examples 1-2 Effect of solution acidity
The pH of the feed liquid in application example 1 was gradually and gradually adjusted from 1 to 5 within the range of 1 to 5, and an extractant [ N ]888DOPE][C272]The concentration was 0.03mol/L and was optimized at pH 3, [ N ]888DOPE][C272]For Tm3+,Yb3+,Lu3+The extraction rates of (1) and (2) are respectively 78.9%, 92.6% and 94.2%, the beta values of Lu/Tm are similar with the change trend of the water phase acidity, the beta values of Lu/Yb reach the maximum at pH 3, and the beta values of Lu/Yb are hardly changed.
Application examples 1-3 kinetic study
By changing the contact time of the organic phase and the feed liquid, the [ N ] is explored888DOPE][C272]Extraction of Tm from chloride Medium3+，Yb3+，Lu3+The extraction kinetics of (1) the extractant concentration is 0.03mol/L, [ N ]888DOPE][C272]The extraction kinetics of the system is fast and is only within 3min (N)888DOPE][C272]For Tm3+，Yb3+，Lu3+The extraction efficiency of (A) is 64.97%, 80.76% and 83.19%, respectively, and the extraction is basically balanced at 40min and reaches the extractionThe extraction efficiencies were 78.01%, 92.89%, and 95.17% respectively by saturation.
Since there are some errors in the experiment, the calculated extraction efficiency (E), distribution ratio (D), separation factor (β), and stripping efficiency (S) have acceptable error ranges within 1%.
Application examples 1-4 Ionic liquid loadings
The extraction loading is an important index for measuring the performance of the extractant, the ionic liquid prepared in example 1, and [ A336]][C272]And C272 with one part of LuCl described in application example 1-1, respectively3Contacting the feed liquid and oscillating for 40min, separating organic phase, extracting the organic phase with a fresh feed liquid, and repeating the extraction for 5 times to obtain [ N ]888DOPE][C272]For Lu3+Saturated loading of extraction and under the same conditions with [ A336]][C272]Lu in the organic phase after 5 repeated extraction experiments as compared with C2723+Is substantially constant. The concentration of the extracting agent is 0.05 mol.L-1When is in [ N ]888DOPE][C272]、[A336][C272]And C272 in the presence of a salting-out agent sodium chloride medium for Lu3+The extraction saturation loading of (A) is 2.55 g.L-1，2.23g·L-1，0.21g·L-1As can be seen from the above, the load amount of C272 is much lower than [ N ]888DOPE][C272]And [ A336]][C272]。
Application examples 1-5 extraction and isolation of RE (III) by Ionic liquids
Study [ N888DOPE][C272]、[A336][C272]Extraction of Tm with three C272 extractants in chloride medium3+，Yb3+，Lu3+The partition ratio D and the separation factor beta are compared to compare the extraction performance and the selectivity of the separation factor D and the separation factor beta on the enrichment of the heavy rare earth. The extraction performance of the three extracting agents is sequentially [ N ]888DOPE][C272]＞[A336][C272]C272 and the distribution ratio is larger as the ionic radius decreases. Selecting feed liquid with pH of 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 0.003mol/L) and extractant with concentration of 0.03mol/L as optimal separation conditions, and [ N ] is selected as the optimal separation conditions888DOPE][C272]And [ A336][C272]Extraction of Tm3+Is very connected withAnd a value of 3.87 and 3.55, [ A336] respectively][C272]Extraction of Yb3+And Lu3+The partition ratio of (1) is 5.93 and 6.61, and [ N ]888DOPE][C272]Extraction of Yb3+And Lu3+Up to a distribution ratio of 13.61 and 18.56. The beta values of Lu/Tm of the three extractants are respectively 4.80, 1.86, 2.34, [ N ]888DOPE][C272]Has a beta value higher than [ A336]][C272]And C272, the beta values of Lu/Yb are 1.36, 1.11, 1.46, [ N ] respectively888DOPE][C272]Has a beta value higher than [ A336]][C272]。
TABLE 1 is [ N ]888DOPE][C272]The distribution ratio D and the separation factor beta after the extraction of a plurality of mixed rare earths with the same concentration show that [ N [ [ N ]888DOPE][C272]The system is prone to the property of extracting 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 strip experiments
To investigate [ N888DOPE][C272]Stripping performance of extraction system, 0 to 1.5mol L-1HCl of different concentrations corresponds to example 1 extracted Lu3+The organic phase of (2) was subjected to a back extraction experiment, wherein, Lu3+The concentration is 0.01mol/L, and Lu is difficult to be mixed with deionized water3+Back-extracted, but when the HCl concentration increased to 0.3mol L-124% Lu in time3+Stripped from the organic phase. When the HCl concentration is from 0.3mol L-1Increased to 0.5mol L-1At that time, the back extraction rate rapidly increases so that Lu3+Almost complete stripping from the organic phase to the aqueous phase, results show [ N ]888DOPE][C272]The back extraction performance of the catalyst is better.
Application example 1-7 cycle experiment
[ N ] prepared in example 1888DOPE][C272]The regeneration and cycle performance test of (1) is as follows:
adding 0.05mol L into the container-1Is [ N ]888DOPE][C272]1L of organic phase and a mixture containing 0.01mol L of-1Lu3+1L of the feed liquid was mixed, the initial pH of the aqueous phase in the feed liquid was 4.5, and the aqueous phase was separated. Using 1mol of L-11L of aqueous HCl solution (g) was added to the organic phase to ensure Lu in the organic phase3+All is back extracted into the water phase, and the water phase is separated. After back extraction, 0.5mol L of alcohol was added to the vessel-11L of NaOH aqueous solution, oscillating for 30min to remove HCl contained in the organic phase, and separating the organic phase from the aqueous phase; this procedure was repeated 6 times to determine the stability of the extractant.
[N888DOPE][C272]After 6 times of circulation, for Lu3+The extraction efficiency is kept at 100%, and the back extraction rate in each circulation reaches 100%. Indicates [ N888DOPE][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, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A functional ionic liquid, characterized in that the cation in the ionic liquid is selected from phosphonate ion functionalized quaternary ammonium, carboxylic acid ion functionalized quaternary ammonium and/or amide ion functionalized quaternary ammonium and the anion in the ionic liquid is selected from mono-2-ethylhexyl 2-ethylphosphonate, bis (2,4,4-trimethylpentyl) phosphinic acid and/or sec-octylphenoxy substituted acetic acid.
2. The ionic liquid of claim 1, wherein the cation in the ionic liquid is a phosphate ion functionalized quaternary ammonium [ N [ ]888DOPE]+When the ionic liquid is any one of the following ionic liquids: [ N ]888DOPE][P507]、[N888DOPE][C272]、[N888DOPE][CA-12]。
Preferably, the cation in the ionic liquid is a carboxylic acid ion functionalized quaternary ammonium [ N [ ]888COOH]+When the ionic liquid is any one of the following ionic liquids: [ N ]888COOH][P507]、[N888COOH][C272]、[N888COOH][CA-12]。
Preferably, the cation in the ionic liquid is amide ion functionalized quaternary ammonium [ N [ ]888CON]+When the ionic liquid is any one of the following ionic liquids: [ N ]888CON][P507]、[N888CON][C272]、[N888CON][CA-12]。
3. The ionic liquid of claim 2, wherein [ N ] is888DOPE][C272]Has a structure shown in formula (I):
4. a process for the preparation of an ionic liquid according to any one of claims 1 to 3, characterised in that it comprises the following steps: (1) under the microwave-assisted condition, reacting the compound containing the cations with a tertiary amine compound in an organic solvent to prepare an intermediate; (2) and (2) reacting the intermediate in the step (1) with a compound containing the anion in an organic solvent to obtain the ionic liquid.
5. The method according to claim 4, wherein the compound containing the cation is selected from a halogenated phosphonate, a halogenated carboxylic acid or a halogenated amide, and wherein the halogen element is bromine, chlorine or iodine.
Preferably, the compound containing the anion is selected from sodium 2-ethylhexyl phosphonate, mono-2-ethylhexyl ester, sodium di (2,4,4-trimethylpentyl) phosphinate or sodium sec-octylphenoxy substituted acetate.
Preferably, the tertiary amine compound is selected from alkyl tertiary amines, such as trioctylamine.
Preferably, the molar weight ratio of the compound containing the cation to the tertiary amine compound is (1-1.2): 1.
Preferably, the molar weight ratio of the compound containing the anion to the intermediate is (1-1.2): 1.
Preferably, in the step (1), the temperature of the microwave reaction is 50-80 ℃, and the time of the microwave reaction is 0.5-4 h.
Preferably, in the step (2), the reaction temperature is 40-70 ℃, and the reaction time is 0.5-10 h.
6. Use of an ionic liquid according to any one of claims 1 to 3 for separation and/or enrichment (or recovery) of rare earth ions, preferably for separation and/or enrichment (or recovery) of heavy rare earth ions. For example, Lu ions are separated from a concentrate of Tm, Yb and Lu ions.
7. Use of an ionic liquid according to any one of claims 1 to 3 as an extractant, preferably as an extractant for rare earth ions, more preferably as an extractant for heavy rare earth ions.
Preferably, the heavy rare earth ions include, but are not limited to, at least one of TmYb and Lu ions, preferably Lu ions.
8. An extractant comprising an ionic liquid according to any one of claims 1 to 3. Preferably, the extractant is a rare earth ion extractant; more preferably a heavy rare earth ion extractant.
9. A method of separating rare earth ions, the method comprising the steps of:
mixing an organic phase containing the ionic liquid of any one of claims 1 to 3 or the extractant, diluent and phase modifier of claim 8, and a feed liquid, shaking, centrifuging, and extracting rare earth ions from the aqueous phase into the organic phase.
10. A method for enriching rare earth ions, comprising the steps of: the method for separating rare earth ions according to claim 9, wherein the organic phase containing rare earth ions obtained by the method for separating rare earth ions is brought into contact with an aqueous hydrochloric acid solution by shaking, thereby back-extracting the rare earth ions from the organic phase into the aqueous phase.
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