CN115433842B - Phosphorus-containing amino acid compound and use thereof for extraction separation of yttrium - Google Patents
Phosphorus-containing amino acid compound and use thereof for extraction separation of yttrium Download PDFInfo
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- CN115433842B CN115433842B CN202110613154.8A CN202110613154A CN115433842B CN 115433842 B CN115433842 B CN 115433842B CN 202110613154 A CN202110613154 A CN 202110613154A CN 115433842 B CN115433842 B CN 115433842B
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- phosphorus
- extraction system
- amino acid
- containing amino
- acid compound
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- -1 amino acid compound Chemical class 0.000 title claims abstract description 132
- 238000000605 extraction Methods 0.000 title claims abstract description 123
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000011574 phosphorus Substances 0.000 title claims abstract description 85
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 85
- 229910052727 yttrium Inorganic materials 0.000 title claims description 46
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 title claims description 46
- 238000000926 separation method Methods 0.000 title abstract description 40
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 12
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 11
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims description 50
- 150000002602 lanthanoids Chemical class 0.000 claims description 42
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 38
- 239000007791 liquid phase Substances 0.000 claims description 28
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 26
- 239000012071 phase Substances 0.000 claims description 24
- 239000003607 modifier Substances 0.000 claims description 17
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 14
- 239000004471 Glycine Substances 0.000 claims description 13
- 239000003085 diluting agent Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000003350 kerosene Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 7
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 7
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 125000005023 xylyl group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
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- 229920005989 resin Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 229940057995 liquid paraffin Drugs 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 21
- 239000012074 organic phase Substances 0.000 description 20
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 19
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 238000007127 saponification reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000002910 rare earth metals Chemical class 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 5
- 150000001242 acetic acid derivatives Chemical class 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 5
- 238000005192 partition Methods 0.000 description 5
- 229910052691 Erbium Inorganic materials 0.000 description 4
- 229910052689 Holmium Inorganic materials 0.000 description 4
- 229910052765 Lutetium Inorganic materials 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 229910052775 Thulium Inorganic materials 0.000 description 4
- 229910052769 Ytterbium Inorganic materials 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical class C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 4
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- JQZSKHZKLNKYQS-UHFFFAOYSA-N OP(O)=O.OP(O)=O.OP(O)=O.P.P Chemical compound OP(O)=O.OP(O)=O.OP(O)=O.P.P JQZSKHZKLNKYQS-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 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 description 3
- ZLMKQJQJURXYLC-UHFFFAOYSA-N bis(2-ethylhexoxy)-oxophosphanium Chemical compound CCCCC(CC)CO[P+](=O)OCC(CC)CCCC ZLMKQJQJURXYLC-UHFFFAOYSA-N 0.000 description 3
- HDIBKVVPMJKRGL-UHFFFAOYSA-N bis(2-ethylhexyl) hydrogen phosphite Chemical compound CCCCC(CC)COP(O)OCC(CC)CCCC HDIBKVVPMJKRGL-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- KUYLHALFMPOMKK-UHFFFAOYSA-N hydroxy-sulfanylidene-bis(2,4,4-trimethylpentyl)-$l^{5}-phosphane Chemical compound CC(C)(C)CC(C)CP(O)(=S)CC(C)CC(C)(C)C KUYLHALFMPOMKK-UHFFFAOYSA-N 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
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- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Chemical class C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 description 1
- GOCVCBDBQYEFQD-UHFFFAOYSA-N 3-[[2-ethylhexoxy(2-ethylhexyl)phosphoryl]oxymethyl]heptane Chemical compound CCCCC(CC)COP(=O)(CC(CC)CCCC)OCC(CC)CCCC GOCVCBDBQYEFQD-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WBLGXIFKKXGJGJ-UHFFFAOYSA-N CC(CCCCCC)(C)OP(O)(=O)C Chemical compound CC(CCCCCC)(C)OP(O)(=O)C WBLGXIFKKXGJGJ-UHFFFAOYSA-N 0.000 description 1
- XOVGHMTUWWTYDF-UHFFFAOYSA-N N-[amino-(2-methylpropylamino)phosphoryl]-2-methylpropan-1-amine Chemical compound P(=O)(NCC(C)C)(NCC(C)C)N XOVGHMTUWWTYDF-UHFFFAOYSA-N 0.000 description 1
- QPLDKTCVZCNIJH-UHFFFAOYSA-N N-diaminophosphoryltridecan-1-amine Chemical compound P(=O)(NCCCCCCCCCCCCC)(N)N QPLDKTCVZCNIJH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- VYRDHRYMAZWQJH-UHFFFAOYSA-N [P].P Chemical compound [P].P VYRDHRYMAZWQJH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- GPTJTTCOVDDHER-UHFFFAOYSA-N cyclononane Chemical compound C1CCCCCCCC1 GPTJTTCOVDDHER-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 150000001940 cyclopentanes Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910021644 lanthanide ion Inorganic materials 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- GRTBAGCGDOYUBE-UHFFFAOYSA-N yttrium(3+) Chemical compound [Y+3] GRTBAGCGDOYUBE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to phosphorus-containing amino acid compounds of the general formula I wherein R 1 and R 2 are each independently selected from C 1～C14 alkyl and the total number of carbon atoms of R 1 and R 2 is 10 or more; r 3 is selected from hydrogen, C 1～C6 alkyl or C 6～C12 aryl; z is C 1～C12 alkylene, R 4 and R 5 are each independently selected from hydrogen, C 1～C10 alkyl, C 3～C10 cycloalkyl and C 6～C12 aryl, or R 4 and R 5 together with the carbon atom to which they are attached form C 3～C10 cycloalkyl. The phosphorus-containing amino acid compound provided by the invention is good in extraction and separation, large in separation coefficient, simple in synthesis method, simple and easily available in raw materials, low in cost and high in industrial application value.
Description
Technical Field
The invention belongs to the field of extraction and separation of yttrium, and relates to a phosphorus-containing amino acid compound and application thereof in extraction and separation of yttrium.
Background
Aiming at the extraction and separation of yttrium, the two-step extraction and separation method of N263-NH 4 SCN-HCl system is adopted in the last 70 th century of China to obtain yttrium oxide products with purity more than 99.99%, but NH 4 SCN and N263 have strong polarity, serious corrosion to equipment and poor operation environment, and the process is gradually eliminated.
At present, an extraction and separation process method which takes naphthenic acid (code NA) as a main extractant is mainly adopted. The naphthenic acid process also exposes problems over long periods of industrial operation: (1) Under the working condition of higher pH value, the high-valence metal ions such as Fe 3+、Th4+ are extremely easy to combine to form solid salt, so that the extractant is emulsified and lost; (2) The slow esterification reaction with alcohol reagents such as isooctanol or methyl heptanol which are phase modifiers, causes the continuous reduction of the effective concentration of the extractant, and needs to be periodically supplemented with fresh extractant and even replaced completely; (3) The separation coefficient of yttrium and light rare earth such as lanthanum is small, and P507 secondary purification is needed, so that the process is tedious; (4) Naphthenic acid is used as a petroleum cracking byproduct, the components of the naphthenic acid are complex, the naphthenic acid is unstable after long-term use, and the extraction of products in each batch is quite different. Meanwhile, with the implementation of national V and VI standards of motor vehicles and the implementation of petroleum deep hydrogenation and desulfurization processes, naphthenic acid sources as petroleum by-products are less and less, so that the price is increased and the petroleum is difficult to buy; meanwhile, naphthenic acid products are poorer and the content of the included small molecular organic acid is higher, so that the service period of the naphthenic acid products is shorter and shorter (from the previous half year to the current 2-3 months) [ Li Deqian, 1995, chemical engineering problems in the rare earth hydrometallurgy industry, chemical progress, 7 (3), 209-213]. Thus, naphthenic acids are increasingly unsuitable, both from a product source and from a product quality perspective, as the primary extractant for separating yttrium.
ZL99118261.8 discloses a liquid-liquid extraction separation process of high-purity yttrium, which adopts a mixture of sec-octyl phenoxy substituted acetic acid (CA 12) and monobasic phosphorus (phosphonic) acid such as P204, P507, cyanex 272, cyanex 302 and the like as an extractant, and methyl heptanol or isoamyl alcohol as an additive for extracting and separating yttrium, so that the problem of emulsification of a naphthenic acid system is solved, but alcohol is easy to carry out slow esterification reaction with sec-octyl phenoxy substituted acetic acid (CA 12), and the effective concentration of the extractant is reduced.
CN200410010737.8 discloses a process for extracting and separating high-purity yttrium oxide by using a mixture of monohydroxy phenoxy substituted acetic acid (CA 12, CA100, etc.) and a salt-based phosphorus (phosphine) acid such as P204, P507, cyanex 272, cyanex 302, etc. as an extractant and TBP as an additive for extracting and separating yttrium. Although the problem of esterification when alcohol is used as an additive is solved, TBP has high water solubility, the proportion of each component of an organic phase is greatly changed after a period of operation, TBP needs to be periodically supplemented, and the organic phase dissolved in a water body seriously pollutes the environment.
Therefore, the search for a novel efficient yttrium separation extractant, which is expected to break through in the aspects, is a focus of long-term attention of rare earth separation workers.
Disclosure of Invention
Through intensive research and experimental verification, a class of phosphorus-containing amino acid compounds which have different extraction rates for yttrium and lanthanide elements and have a large separation coefficient beta Ln/Y of the lanthanide element (Ln) and yttrium are unexpectedly discovered, so that the phosphorus-containing amino acid compounds can be used as an extractant for extracting and separating yttrium. In addition, the phosphorus-containing amino acid compound can be used as an extractant to prepare an extraction system without adding a phase modifier, so that the formula of the extraction system can be simplified, and adverse effects caused by adding the phase modifier are avoided. In addition, the phosphoamino acid compounds also have different extraction rates and separation coefficients for different lanthanides, and thus can also be used to separate different lanthanides. The phosphorus-containing amino acid compound is easy to synthesize, wide in raw material source, stable in components, good in extraction phenomenon and high in separation coefficient.
It is an object of the present invention to provide a class of phosphorus-containing amino acid compounds or salts thereof which can be used for the extractive separation of yttrium.
It is another object of the present invention to provide an extraction system comprising one or more selected from the above-mentioned phosphorus-containing amino acid compounds and salts thereof.
It is another object of the present invention to provide the use of said phosphorus-containing amino acid compound or salt thereof as an extractant for the extractive separation of yttrium.
It is a further object of the present invention to provide the use of said phosphorus-containing amino acid compound or salt thereof as an extractant for separating lanthanoids by extraction.
One aspect of the present invention provides a phosphorus-containing amino acid compound of the following formula I:
Wherein,
R 1 and R 2 are each independently selected from C 1～C14 alkyl groups, and the total number of carbon atoms of R 1 and R 2 is 10 or greater;
R 3 is selected from hydrogen, C 1～C6 alkyl or C 6～C12 aryl;
z is a C 1～C12 alkylene group, preferably a C 1～C4 alkylene group, more preferably a C 1～C2 alkylene group,
R 4 and R 5 are each independently selected from hydrogen, C 1～C10 alkyl, C 3～C10 cycloalkyl and C 6～C12 aryl,
Or R 4 and R 5 together with the carbon atom to which they are attached form a C 3～C10 cycloalkyl group.
In another aspect, the present invention provides an extraction system comprising one or more selected from the group consisting of the above-described phosphorus-containing amino acid compounds and salts thereof.
In another aspect, the invention provides the use of the above-described phosphorus-containing amino acid compound as an extractant for the extractive separation of yttrium.
In another aspect the present invention provides the use of a phosphorus-containing amino acid compound as described above as an extractant for separating lanthanoids by extraction.
Advantageous effects
The phosphorus-containing amino acid compound adopted by the invention not only has good extraction and separation capability on yttrium and lanthanide series elements, but also does not need to use a phase modifier. In addition, the phosphorus-containing amino acid compounds of the present invention have a large difference in separation coefficient for lanthanoids, and can be used for separating lanthanoids. Finally, the synthesis method of the phosphorus-containing amino acid compound is simple, the chemical raw materials used in synthesis are simple and easy to obtain, the cost is low, the components are stable, and therefore the extraction and separation cost of yttrium can be effectively reduced, and the method has high industrial application value.
Detailed Description
The present invention will be described in more detail below, but the present invention is not limited to the following.
(1) Phosphorus-containing amino acid compounds
In one aspect, the present invention provides a phosphorus-containing amino acid compound of formula I:
Wherein,
R 1 and R 2 are each independently selected from C 1～C14 alkyl, preferably C 4～C12 alkyl, more preferably C 6～C10 alkyl, most preferably C 6～C9 alkyl; and the total carbon number of R 1 and R 2 is 10 or more;
R 3 is selected from hydrogen, C 1～C6 alkyl or C 6～C12 aryl;
z is a C 1～C12 alkylene group, preferably a C 1～C4 alkylene group, more preferably a C 1～C2 alkylene group,
R 4 and R 5 are each independently selected from hydrogen, C 1～C10 alkyl, C 3～C10 cycloalkyl and C 6～C12 aryl,
Or R 4 and R 5 together with the carbon atom to which they are attached form a C 3～C10 cycloalkyl group.
In some embodiments, the phosphorus-containing amino acid compound of formula I is a compound of formula II:
Wherein R 1、R2、R3、R4 and R 5 are as defined in formula I.
In the general formulas I and II, R 1 and R 2 are the same or different. Furthermore, R 1 and R 2 are preferably the same alkyl group, more preferably the same C 6～C10 alkyl group; most preferably the same C 6～C9 alkyl groups.
Preferably, the total number of carbon atoms of R 1 and R 2 is an integer between 10 and 24, including but not limited to 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, preferably an integer between 12 and 18.
R 3 is preferably hydrogen, C 1～C4 alkyl or C 6～C10 aryl, more preferably hydrogen, C 1～C2 alkyl or phenyl, benzyl, tolyl, ethylphenyl, xylyl.
Preferably, R 4 is hydrogen and R 5 is selected from hydrogen, C 1～C6 alkyl, C 5～C7 cycloalkyl and C 6～C10 aryl, preferably hydrogen, C 1～C4 alkyl, C 5～C7 cycloalkyl and C 6～C8 aryl; more preferred are hydrogen, C 1～C2 alkyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, tolyl, ethylphenyl, xylyl.
Preferably, the phosphorus-containing amino acid compound is one or more selected from ((di ((2-ethylhexyl) oxy) phosphoryl) methyl) glycine (code PA 1), ((di ((2-ethylhexyl) oxy) phosphoryl) (phenyl) methyl) glycine (code PA 2), ((di ((2-ethylhexyl) oxy) phosphoryl) (phenyl) methyl) phenylalanine (code PA 3).
In the present invention, the salt of the phosphorus-containing amino acid compound of the general formula I is not particularly limited as long as the cation thereof does not adversely affect the extraction of the rare earth element, and for example, it may be an ammonium salt, an alkali metal salt (e.g., lithium salt, sodium salt, potassium salt) or an alkaline earth metal salt (e.g., magnesium salt, calcium salt), preferably an ammonium salt, sodium salt.
The phosphorus-containing amino acid compounds of the present invention can be synthesized analogously according to methods known in the art (e.g., US 4486359, etc.) or described below and in the examples.
For example, the phosphorus-containing amino acid compound of formula I can be synthesized as follows, as shown in equation 1:
Reaction 1
Wherein, the compound II, the compound III and the compound IV are subjected to condensation reaction to obtain the phosphorus-containing amino acid compound with the general formula I,
Wherein R 1、R2、R3、R4、R5 and Z are as defined above.
The carbonyl compound III may be an aliphatic aldehyde (e.g., formaldehyde) or an aromatic aldehyde. Compound II, compound IV may be commercially available products or synthesized according to methods known in the art.
Furthermore, according to the structure of the phosphorus-containing amino acid compound disclosed in the present invention, a person skilled in the art can design a new synthetic route with reference to synthetic methods known in the prior art, and thus, the synthetic method of the phosphorus-containing amino acid compound of the present invention is not limited to the above-described method.
(2) Extraction system
In another aspect, the present invention provides an extraction system comprising one or more selected from the group consisting of the above-described phosphorus-containing amino acid compounds and salts thereof as an extractant. The extraction system may also be referred to as an extraction composition.
The extraction system is preferably a liquid phase extraction system comprising: one or more selected from the group consisting of the phosphorus-containing amino acid compounds of the above general formula I and salts thereof as an extractant; and a diluent. Preferably, the liquid phase extraction system consists essentially of the above components.
The description of the phosphorus-containing amino acid compound of the general formula I or a salt thereof is the same as that described above.
In the present invention, the liquid phase extraction system is mainly composed of organic matter, and thus is sometimes referred to as an organic phase during the extraction process, and the rare earth feed liquid is an aqueous solution, and thus is sometimes referred to as an aqueous phase during the extraction process.
In some embodiments, the diluent may be selected from: c 5～C16 alkanes such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, etc.; aviation kerosene; sulfonated kerosene, liquid paraffin, e.g., light lubricating oil fractions at 250 to 400 ℃ and the like; c 5-16 alicyclic alkanes such as cyclopentane, C 1～C4 alkyl-substituted cyclopentane, cyclohexane, C 1～C4 alkyl-substituted cyclohexane, decalin and the like; c 6～C10 aromatics such as benzene, toluene, xylenes (including ortho-, meta-, para-xylene and mixed xylenes), and the like. Preferably, the diluent may be one or more selected from aviation kerosene, sulfonated kerosene, heptane and xylene. But the present invention is not limited thereto.
In the extraction system, the concentration of the phosphorus-containing amino acid compound or salt thereof may be 0.0001 to 1.0mol/L, preferably 0.01 to 0.5mol/L, for example, 0.05, 0.1, 0.2, 0.3, 0.4mol/L, based on the volume of the liquid-phase extraction system (i.e., organic phase). But the present invention is not limited thereto.
In some embodiments, the liquid phase extraction system may also optionally include auxiliary extractants and/or phase modifiers.
The auxiliary extractant mainly plays an auxiliary extraction role, and can enhance the extraction performance of the phosphorus-containing amino acid compound extractant on lanthanide elements.
The auxiliary extractant can be selected from neutral phosphorus or phosphine extractant, carboxylic acid extractant or salt thereof, acidic phosphorus or phosphine extractant, neutral phosphoramide extractant and mixed extractant of the above extractants in any proportion.
The neutral phosphorus or phosphine extractant may be an alkyl phosphine oxide, alkyl phosphonate or alkyl phosphate. Specifically, the neutral phosphorus or phosphine extractant may be represented by the following formula V:
Wherein R 1、R2 and R 3 are each independently selected from C 1～C12 alkyl and C 1～C12 alkoxy, and the total number of carbon atoms of R 1、R2 and R 3 is 10 or more.
More particularly, the neutral phosphorus or phosphine extractant may be selected from linear trialkylphosphine oxides (Cyanex 923), branched trialkylphosphine oxides (Cyanex 925), trioctylphosphine oxides, dimethylheptyl methylphosphonate, di-2-ethylhexyl 2-methylphosphonate, tributyl phosphate, and the like, but is not limited thereto.
The carboxylic acid extractant or a salt thereof may be selected from the group consisting of sec-octylphenoxy substituted acetic acid (CA-12), sec-nonylphenoxy substituted acetic acid (CA-100), and the like, but is not limited thereto.
The acidic phosphorus or phosphine extractant may be an acidic phosphorus (phosphonate) of the general formula VI or a salt thereof, but is not limited thereto:
Wherein,
Z is O or S;
R 3 and R 4 are each independently selected from C 1-12 alkyl, C 1-12 alkoxy;
Suitable acidic phosphorus (phosphonate) esters of the general formula VI may be selected from: bis (2, 4-trimethylpentyl) thiophosphonic acid (Cyanex 302), bis (2-ethylhexyl) phosphoric acid (P204), 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507), bis (2, 4-trimethylpentyl) phosphonic acid (Cyanex 272), bis (2-ethylhexyl) phosphonic acid (P227 or P229) and mixtures of the above extractants in any proportions. But the present invention is not limited thereto.
In the present invention, the salt of the acidic phosphorus (phosphonate) of the general formula VI is not particularly limited as long as the cation thereof does not adversely affect the extraction of the rare earth element, and for example, it may be an ammonium salt, an alkali metal salt (e.g., lithium salt, sodium salt, potassium salt) or an alkaline earth metal salt (e.g., magnesium salt, calcium salt), preferably a sodium salt. But the present invention is not limited thereto.
The neutral phosphoramide extractant may be a neutral phosphoramide extractant of the following formula VII, but is not limited thereto:
Wherein,
R 1 is C 1～C18 alkyl;
R 2 and R 3 are each independently selected from: c 1～C18 alkyl, C 1～C18 alkylamino, and C 1～C18 alkoxy;
Wherein, the total carbon number of R 1、R2 and R 3 is 14 to 36, preferably 16 to 30, for example 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, etc.
Suitable neutral phosphoramide extractants of formula VII may be selected from: triisooctylphosphoramide, diisooctyloxyphosphamide, isooctyl-diisooctyloxyphosphamide, tris (diisobutyl) phosphoramide, bis (diisobutyl) -isooctylphosphamide, tridecylphosphoramide, dihexyl-decylphosphamide, and the like; and the mixed extractant of the above extractants mixed in any proportion. But the present invention is not limited thereto.
In the liquid phase extraction system, the concentration of the auxiliary extractant may be from 0 to 1.0mol/L, preferably from 0 to 0.5mol/L, for example 0.01mol/L、0.05mol/L、0.10mol/L、0.15mol/L、0.20mol/L、0.25mol/L、0.30mol/L、0.35mol/L、0.40mol/L、0.45mol/L、0.50mol/L, etc., based on the total volume of the liquid phase extraction system (i.e., the organic phase). But the present invention is not limited thereto.
The phase modifier mainly plays a role in improving extraction physical phenomena, and can be one or more selected from C 4～C12 alkanol and tributyl phosphate, di (2-ethylhexyl) phosphonate (2-ethylhexyl) ester and [ (2-ethylhexyl) amino ] methylenephosphonic acid di (2-ethylhexyl) ester, preferably one or more selected from n-octanol, isooctanol, 2-methyl heptanol, mixed alcohol mixed by any proportion of the three alcohols and tributyl phosphate; more preferably isooctyl alcohol or 2-methyl heptanol. But the present invention is not limited thereto.
In the liquid phase extraction system, the concentration of the phase modifier may be 0 to 1.0mol/L, preferably 0 to 0.5mol/L, for example 0.01mol/L、0.05mol/L、0.10mol/L、0.15mol/L、0.20mol/L、0.25mol/L、0.30mol/L、0.35mol/L、0.40mol/L、0.45mol/L、0.50mol/L, etc., based on the total volume of the liquid phase extraction system (organic phase). But the present invention is not limited thereto.
In addition, some of the compounds may function as both auxiliary extractants and phase improvers, such as tributyl phosphate, (2-ethylhexyl) phosphonic acid di (2-ethylhexyl) ester and [ (2-ethylhexyl) amino ] methylenephosphonic acid di (2-ethylhexyl) ester described above, which may be used in accordance with the intended purpose of use. For example, they may be used as auxiliary extractants with or without additional phase modifiers; or they may be used as phase improvers with or without additional auxiliary extractants.
In some embodiments, the liquid phase extraction system is prepared as follows: mixing a phosphorus-containing amino acid compound of the general formula I or a salt thereof with a diluent, optionally an auxiliary extractant and optionally a phase modifier, and optionally, adjusting the saponification degree to obtain the liquid phase extraction system.
The saponification degree refers to the salification degree of an acidic extractant in an extraction system, including a phosphorus-containing amino acid compound of the general formula I and an auxiliary extractant, and can be calculated as follows:
Saponification degree% = molar amount of salified acidic extractant/molar amount of total acidic extractant x 100%.
The saponification degree of the extraction system may be 10 to 90%, preferably 20 to 85%, more preferably 50 to 85%, for example 55%, 60%, 65%, 70%, 75%, 80%, etc. Because the extraction reaction mechanism is a cation exchange mechanism, if the saponification process is not performed, rare earth ions are extracted into an organic phase in the extraction reaction process, and hydrogen ions are replaced into a water phase, so that the acidity of the water phase is increased, and the subsequent extraction reaction is affected. Therefore, it is preferable to adjust the acidic extractant extraction system to a suitable saponification degree prior to extraction.
There is no particular limitation on the method of adjusting the saponification degree. In some embodiments, the phosphorus-containing amino acid compound of formula I and/or the auxiliary extractant are used in the acid form, in which case the saponification treatment may be performed by adding a saponification agent to the liquid phase extraction system. The saponifier may be selected from aqueous ammonia, ammonium carbonate, ammonium bicarbonate, soluble carbonates, bicarbonates and hydroxides of alkali metals or alkaline earth metals, etc., for example sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, sodium hydroxide, potassium hydroxide, etc., preferably aqueous ammonia or sodium hydroxide. In some embodiments, the saponifying agent may be formulated for use in the form of an aqueous solution. In other embodiments, the phosphorus-containing amino acid compound of formula I and/or the auxiliary extractant are used in salt form, in which case the saponification degree can be adjusted by adding a mineral acid to the phosphorus-containing amino acid compound extraction system. The inorganic acid can be hydrochloric acid solution, nitric acid solution or a mixed solution of the hydrochloric acid solution and the nitric acid solution. In still other embodiments, mixtures of the phosphorus-containing amino acid compounds of formula I and/or co-extractants in acid form with the phosphorus-containing amino acid compounds of formula I and/or co-extractants in salt form may be used. In this case, the aqueous solution may be reacted with a saponification agent or an inorganic acid as needed to obtain a suitable saponification degree, or the saponification degree may not be adjusted.
On the basis of using the phosphorus-containing amino acid compound of the general formula I of the present invention or a salt thereof as an extractant, a person skilled in the art can experimentally determine suitable diluents, auxiliary extractants, phase improvers and their amounts, and select suitable saponifying agents and determine suitable saponification degrees, and thus the scope of the present invention is not limited to the above description regarding diluents, auxiliary extractants, phase improvers, saponifying agents and saponification degrees.
Furthermore, the extraction system of the present invention may be a solid phase extraction system.
The solid phase extraction system may be a resin, porous silica spheres, diatomaceous earth, or the like loaded with one or more selected from the group consisting of a phosphorus-containing amino acid compound of formula I and a salt thereof. The solid phase extraction system may be prepared by conventional methods in the art, for example, by loading the phosphorus-containing amino acid compound of formula I or a salt thereof onto a resin, porous silica spheres, diatomaceous earth, by methods such as impregnation, in situ polymerization, chemical bonding, etc. (preferably by impregnation, in situ polymerization, etc.), as disclosed in, for example, reference to cn201910842104. X. But the present invention is not limited thereto.
The solid phase extraction system may also be loaded with an auxiliary extractant. The description of the auxiliary extractant is the same as that described above with respect to the auxiliary extractant and is therefore not repeated here.
The description of the saponification degree in the liquid phase extraction system applies equally to the solid phase extraction system and is therefore not repeated here.
(3) Use of the same
When the phosphorus-containing amino acid compound or the salt thereof is used as an extractant to extract rare earth elements, the prepared extraction system has different extraction rates and distribution ratios for yttrium and lanthanide elements, and particularly the extraction rates and distribution ratios for lanthanide rare earth elements are obviously larger than those for yttrium, so that the phosphorus-containing amino acid compound or the salt thereof can be used for separating yttrium from lanthanide elements by extraction.
Accordingly, in a further aspect the present invention provides the use of a phosphorus-containing amino acid compound as described above or a salt thereof as an extractant for separating yttrium. In other words, the present invention provides the use of the above-described phosphorus-containing amino acid compound or a salt thereof as an extractant for preparing an extraction system for separating yttrium.
Or the present invention provides the use of the above extraction system comprising one or more selected from the above-mentioned phosphorus-containing amino acid compounds or salts thereof as an extractant for separating yttrium.
Furthermore, it has been found during the course of experiments that the phosphorus-containing amino acid compound or salt thereof of the present invention has different extraction rates and partition ratios for different lanthanoids as an extractant, and thus can be used for separating different lanthanoids by extraction. For example, it may be used to group lanthanoids, e.g., into light, medium, heavy rare earth elements, or into groups containing more than two (e.g., two, three, four, etc.) similar lanthanoids, respectively, or to separate out individual lanthanoids.
Accordingly, in another aspect the present invention provides the use of a phosphorus-containing amino acid compound as described above, or a salt thereof, as an extractant for separating lanthanides. In other words, the present invention provides the use of the above-described phosphorus-containing amino acid compound or a salt thereof as an extractant for preparing an extraction system for separating lanthanoid elements.
Or the present invention provides the use of the above extraction system comprising one or more selected from the above-mentioned phosphorus-containing amino acid compounds or salts thereof as an extractant for separating lanthanoid elements.
Terminology
In the present invention, "yttrium separation" refers to separation of yttrium (i.e., trivalent yttrium (III) or trivalent yttrium ion Y 3 +) from other rare earths (i.e., lanthanide elements or trivalent lanthanide ions Ln 3+) by extraction.
In the invention, rare earth elements refer to lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium and scandium, wherein light rare earth elements refer to lanthanum, cerium, praseodymium and neodymium; the medium-heavy rare earth refers to samarium, europium, gadolinium, terbium, dysprosium, holmium, europium, erbium, thulium, ytterbium, lutetium, yttrium and scandium.
The term C 1～C18 alkyl as used herein refers to straight or branched chain alkyl groups containing from 1 to 18 carbon atoms, such as straight or branched chain alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 carbon atoms, including, without limitation, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, neopentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and the like. The meaning of C 1～C14 alkyl, C 1～C12 alkyl, C 1～C10 alkyl, C 1～C6 alkyl, C 1～C4 alkyl, C 2～C9 alkyl, C 2～C8 alkyl, C 4～C12 alkyl, C 6～C10 alkyl, C 6～C9 alkyl, and the like.
The term C 6～C12 aryl as used herein refers to aryl groups containing 6 to 12 carbon atoms inclusive of the number of carbon atoms of the substituent, such as aryl groups having 6, 7, 8, 9, 10, 11 or 12 carbon atoms, including, without limitation, phenyl, alkyl substituted phenyl, phenyl C 1-C4 alkyl, alkyl substituted phenyl C 1-C4 alkyl, and the like. The meanings of C 6～C10 aryl, C 6～C9 aryl and C 6～C8 aryl and so on.
The term C 1～C12 alkoxy as used herein refers to a straight or branched chain alkoxy group containing 1 to 12 carbon atoms, such as straight or branched chain alkoxy groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, including without limitation methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, isobutoxy, n-pentoxy, neopentoxy, isopentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy and the like. The meaning of C 1～C10 alkoxy, C 4～C10 alkoxy, etc. is analogized.
The term C 4～C10 alkanol as used in the present invention refers to straight or branched chain alkanols containing 4 to 10 carbon atoms, such as straight or branched chain alkanols having 4, 5, 6, 7, 8, 9 or 10 carbon atoms, including without limitation n-butanol, t-butanol, isobutanol, n-pentanol, neopentyl alcohol, isoamyl alcohol, hexanol, heptanol, octanol, nonanol, decanol and the like.
The term C 5～C16 alkane as used in the present invention refers to straight or branched chain alkanes containing 5 to 16 carbon atoms, straight or branched chain alkanes having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16 carbon atoms, such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, etc.
The term C 5～C16 alicyclic alkane as used in the present invention refers to a saturated cyclic alkane containing 5 to 16 carbon atoms inclusive of the number of carbon atoms of the substituent which may be monocyclic or bicyclic, for example, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, decalin, etc., and the substituent may be selected from one or more substituents of C 1～C4 alkyl.
The term C 6～C10 aromatic hydrocarbon as used in the present invention refers to aromatic hydrocarbons containing 6 to 10 carbon atoms inclusive of the number of carbon atoms of the substituent, such as benzene and benzene substituted with one or more substituents selected from C 1～C4 alkyl groups, such as benzene, toluene, xylene, etc.
Unless otherwise indicated, numerical values in this disclosure represent approximate measures or limits to include minor deviations from the given value and ranges of embodiments having about the stated value and having the exact value noted. Except in the following detailed description of the final embodiments, all numerical values of parameters (e.g., amounts or conditions) in this document (including the appended claims) should be construed in all cases to be modified by the term "about" whether or not "about" actually appears before the numerical value. "about" means that the recited value allows for slight imprecision (with some approximation to the exact value; approximately or reasonably close to the value; approximated). "about" as used herein at least means variations that can be produced by ordinary methods of measuring and using these parameters if the imprecision provided by "about" is not otherwise understood in the art with this ordinary meaning. For example, "about" may include less than or equal to 15%, less than or equal to 10%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, less than or equal to 1%, less than or equal to 0.5%, less than or equal to 0.1% variation, and in some aspects less than or equal to 0.01% variation.
The present invention has been described in detail above, but the present invention is not limited to the above.
Examples
For further illustrating the aspects of the present invention, specific embodiments of the invention are provided to aid those skilled in the art in understanding and practicing the invention, but the invention is not limited to these embodiments.
Preparation examples Synthesis of phosphorus-containing amino acid Compounds
Reagents and sources:
(1) Bis (2-ethylhexyl) phosphite, bis (2-methylhexyl) phosphite, jet fuel, sulfonated kerosene, methyl heptanol, isooctanol, and TBP were purchased from Shanghai Laiyshi chemical Co.
(2) Reagents such as paraformaldehyde, benzaldehyde, glycine, phenylalanine, triethylamine, potassium hydroxide, methanol, toluene, xylene, heptane and the like were purchased from the company acla Ding Shiji, inc.
(3) Rare earth feed liquid is self-made in a laboratory.
(4) Other reagents (e.g., acids, etc.) are commercially available analytically pure reagents.
The rare earth ion concentrations were all determined using ICP-OES (instrument model: optical-8000, manufacturer: PERKIN ELMER).
Preparation example 1: preparation of ((di ((2-ethylhexyl) oxy) phosphoryl) methyl) glycine (code PA 1)
To a 150mL single neck round bottom flask was added 0.1mol triethylamine and 50mL methanol, heated to 40℃and stirred. Then, 0.11mol of glycine and 0.11mol of paraformaldehyde were added thereto, heated and stirred at 80℃for 4 hours, and 0.1mol of di (2-ethylhexyl) phosphite was added dropwise thereto with a constant pressure titration funnel at this temperature over 10 minutes, and after the completion of the dropwise addition, the temperature was raised to 130℃for reaction for 8 hours. After the reaction was completed, the reaction mixture was cooled to 5℃or lower with ice cubes, and glycine precipitated by crystallization was filtered. The filtrate was distilled under reduced pressure to remove the solvent. The crude product is dissolved by 150mL of ethyl acetate, washed by distilled water and distilled under reduced pressure to obtain the target product.
1H NMR(600MHz,CDCl3)δ:0.89(t,6H),0.95(t,6H),1.22-1.36(m,18H),1.46-1.54(m,1H),2.91-3.15(m,2H),3.23-3.32(m,2H),3.86-4.11(m,4H).
Preparation example 2: preparation of ((di ((2-ethylhexyl) oxy) phosphoryl) (phenyl) methyl) glycine (code PA 2)
To a 150mL single neck round bottom flask was added 0.1mol potassium hydroxide and 50mL methanol, heated to 40℃and stirred to dissolve completely. Then, 0.11mol of glycine and 0.11mol of benzaldehyde were added to the clear solution, and the mixture was stirred at 80℃for 4 hours, at which point 0.1mol of di (2-ethylhexyl) phosphite was added dropwise to the solution in a constant pressure titration funnel over 10 minutes, and after the completion of the addition, the temperature was raised to 130℃for 8 hours. After the reaction was completed, the reaction mixture was cooled to 5℃or lower with ice cubes, and glycine precipitated by crystallization was filtered. Acidifying the filtrate with hydrochloric acid, cooling the turbid liquid to below 5deg.C, filtering to obtain crystallized potassium chloride, and vacuum distilling to remove solvent and residual hydrochloric acid. The crude product is dissolved by 150mL of ethyl acetate, washed by distilled water and distilled under reduced pressure to obtain the target product.
1H NMR(600MHz,CDCl3)δ:0.89(t,6H),0.95(t,6H),1.22-1.46(m,18H),1.75-1.85(m,1H),3.13-3.27(m,2H),3.83-4.10(m,5H),7.31-7.41(m,5H).
Preparation example 3: preparation of ((di ((2-ethylhexyl) oxy) phosphoryl) (phenyl) methyl) phenylalanine (code PA 3)
To a 150mL single neck round bottom flask was added 0.1mol potassium hydroxide and 50mL methanol, heated to 40℃and stirred to dissolve completely. Then, 0.11mol of phenylalanine and 0.11mol of benzaldehyde were added to the clear solution, and the mixture was stirred at 80℃for 4 hours, at which point 0.1mol of di (2-ethylhexyl) phosphite was added dropwise to the solution over 10 minutes using a constant pressure titration funnel, and after the completion of the addition, the temperature was raised to 130℃for 8 hours. After the reaction was completed, the reaction mixture was cooled to 5℃or lower with ice cubes, and the crystallized phenylalanine was filtered. Acidifying the filtrate with hydrochloric acid, cooling the turbid liquid to below 5deg.C, filtering to obtain crystallized potassium chloride, and vacuum distilling to remove solvent and residual hydrochloric acid. The crude product is dissolved by 150mL of ethyl acetate, washed by distilled water and distilled under reduced pressure to obtain the target product.
1H NMR(600MHz,CDCl3)δ:0.89(t,6H),0.95(t,6H),1.22-1.46(m,18H),1.77-1.83(m,1H),2.81-3.06(m,2H),3.32-3.43(m,1H),3.78-4.08(m,5H),7.27-7.38(m,10H).
Extraction examples
The extraction E%, partition ratio D and separation coefficient β Ln/Y of lanthanoid (Ln) from yttrium were calculated as follows:
Wherein [ M ] (aq,init) and [ M ] (aq) are respectively the initial concentration and the equilibrium concentration of the metal ions in the aqueous phase, D Ln is the distribution ratio of the lanthanoid element, and D Y is the distribution ratio of yttrium.
Extraction example 1
Preparing an organic phase: ((2-ethylhexyl) oxy) phosphoryl) methyl) glycine (code PA 1) was mixed with heptane as diluent to make up the organic phase, wherein the concentration of PA1 was 0.1mol/L based on the total volume of the organic phase.
Preparing yttrium-containing rare earth feed liquid: and respectively mixing solutions of yttrium, holmium, erbium, thulium, ytterbium and lutetium, diluting to the required concentration by distilled water, and regulating the pH by dilute hydrochloric acid and sodium hydroxide to prepare yttrium-containing rare earth feed liquid with each rare earth concentration of 0.0025mol/L, wherein the pH is 2.5 and the total concentration is 0.015mol/L.
The organic phase and yttrium-containing rare earth feed liquid are mixed according to the volume ratio of 1:1, mixing, and performing single-stage extraction at room temperature. After the extraction is completed, the extraction rate E%, partition ratio D and separation coefficient β Ln/Y of lanthanoid (Ln) and yttrium are calculated (see Table 1). In the extraction process, the phase separation is rapid, and the phase interface is clear.
TABLE 1
| PA1 system | Y | Ho | Er | Tm | Yb | Lu |
| E％ | 34.62 | 46.48 | 47.47 | 50.85 | 62.09 | 67.89 |
| D | 0.5295 | 0.8685 | 0.9037 | 1.035 | 1.638 | 2.114 |
| βLn/Y | 1.00 | 1.64 | 1.71 | 1.95 | 3.09 | 3.99 |
Extraction example 2
Preparing an organic phase: ((2-ethylhexyl) oxy) phosphoryl) methyl) glycine (code PA 1), TBP or isooctanol as a phase modifier, and heptane as a diluent were mixed to constitute an organic phase, the concentration of PA1 being 0.1mol/L, the concentration of TBP (or isooctanol) being 0.1mol/L, based on the total volume of the organic phase.
Otherwise, the same as in example 1 was conducted.
The extraction results of the above extraction are shown in Table 2.
TABLE 2
| PA1-TBP system | Y | Ho | Er | Tm | Yb | Lu |
| E％ | 27.54 | 35.90 | 37.24 | 39.85 | 55.00 | 62.06 |
| D | 0.3801 | 0.5601 | 0.5934 | 0.6625 | 1.222 | 1.636 |
| βLn/Y | 1.00 | 1.47 | 1.56 | 1.74 | 3.22 | 4.30 |
| PA 1-isooctanol system | Y | Ho | Er | Tm | Yb | Lu |
| E％ | 24.20 | 37.59 | 40.14 | 42.57 | 55.69 | 62.05 |
| D | 0.3193 | 0.6023 | 0.6706 | 0.7413 | 1.257 | 1.635 |
| βLn/Y | 1.00 | 1.89 | 2.10 | 2.32 | 3.94 | 5.12 |
As can be seen from the data in table 2, the addition of the phase modifier TBP or isooctanol to the organic phase resulted in a reverse synergistic effect, resulting in a reduced extraction rate of rare earth from extractant PA1, as compared to the results of example 1. Therefore, the phosphorus-containing amino acid extraction system can avoid the problems of unstable components of the extraction system caused by adding TBP and esterification caused by adding alcohol reagents from the source without adding a phase modifier TBP or isooctanol.
Comparative example 1
The phosphoryl carboxylic acid extractant 3- ((di ((2-ethylhexyl) oxy) phosphoryl) -3-phenylpropionic acid (code P1, its structural formula shown below) was prepared according to the method disclosed in cn201910842104. X.
An extraction experiment was performed in the same manner as in extraction examples 1 and 2, except that P1 was used as an extractant instead of PA1, and the extraction results thereof are shown in Table 3.
TABLE 3 Table 3
| P1 system | Y | Ho | Er | Tm | Yb | Lu |
| E％ | 37.31 | 58.64 | 57.27 | 57.02 | 58.55 | 54.50 |
| D | 0.5952 | 1.418 | 1.340 | 1.327 | 1.413 | 1.198 |
| βLn/Y | 1.00 | 2.38 | 2.25 | 2.23 | 2.37 | 2.01 |
| P1-TBP system | Y | Ho | Er | Tm | Yb | Lu |
| E％ | 37.50 | 60.26 | 60.24 | 61.19 | 64.63 | 61.21 |
| D | 0.6000 | 1.516 | 1.515 | 1.577 | 1.827 | 1.578 |
| βLn/Y | 1.00 | 2.53 | 2.53 | 2.63 | 3.05 | 2.63 |
| P1-isooctanol system | Y | Ho | Er | Tm | Yb | Lu |
| E％ | 37.47 | 60.15 | 60.97 | 60.81 | 64.39 | 61.72 |
| D | 0.5992 | 1.509 | 1.562 | 1.552 | 1.808 | 1.612 |
| βLn/Y | 1.00 | 2.52 | 2.61 | 2.59 | 3.02 | 2.69 |
As can be seen from the data in Table 3, P1 and TBP (or isooctanol) produce a positive synergistic effect, and the extraction rate of organic relative rare earth added with phase modifier is slightly improved. However, TBP has high water solubility, and the TBP dissolved in the water phase needs to be periodically replenished during long-term operation, so that the treatment cost of tail water is increased, and environmental pollution is caused; the alcohol additive is easy to generate esterification reaction with carboxylic acid, so that the effective concentration of an organic phase is reduced, and the extraction separation performance of the alcohol additive is further reduced. Compared with the extractant P1, the extractant used in the application has the advantage that the phase modifier TBP or isooctyl alcohol is not required to be added, so that the problems are avoided from the source.
In terms of separation performance, after TBP is added into the extractant PA1 system, the separation coefficient of part of lanthanide series elements (such as holmium, erbium, thulium and the like) and yttrium is reduced, and the separation coefficient of the other part of lanthanide series elements (such as ytterbium, lutetium and the like) and yttrium is increased; after isooctyl alcohol is added, the separation coefficient of lanthanide and yttrium is increased; and after TBP or isooctanol is added into the extractant P1 system, the separation coefficient of the lanthanide and yttrium is increased, but the average separation coefficient is smaller than that of the extractant PA 1-isooctanol system.
Furthermore, the extraction agent used in the present application has a larger difference in separation coefficient between the lanthanoid elements than the extraction agent P1, and thus can also be used to separate the lanthanoid elements.
Extraction example 3
Preparing an organic phase: ((2-ethylhexyl) oxy) phosphoryl) (phenyl) methyl) glycine (code PA 2) was mixed with toluene as a diluent to make up an organic phase, the PA2 concentration being 0.1mol/L.
Otherwise, the same as in example 1 was conducted.
The extraction rate E%, partition ratio D and separation coefficient beta Ln/Y of lanthanoid (Ln) and yttrium of the above extraction are shown in Table 4.
TABLE 4 Table 4
| PA2 system | Y | Ho | Er | Tm | Yb | Lu |
| E％ | 50.95 | 59.85 | 70.71 | 82.69 | 93.03 | 95.89 |
| D | 1.039 | 1.491 | 2.414 | 4.777 | 13.35 | 23.33 |
| βLn/Y | 1 | 1.44 | 2.32 | 4.60 | 12.85 | 22.46 |
Extraction example 4
Preparing an organic phase: ((2-ethylhexyl) oxy) phosphoryl) (phenyl) methyl) phenylalanine (code PA 3) was mixed with sulfonated kerosene as a diluent to make up an organic phase, the PA3 concentration being 0.1mol/L.
Otherwise, the same as in example 1 was conducted.
The extraction rate E%, partition ratio D and separation coefficient beta Ln/Y of lanthanoid (Ln) and yttrium of the above extraction are shown in Table 5.
TABLE 5
| PA3 system | Y | Ho | Er | Tm | Yb | Lu |
| E％ | 5.70 | 11.77 | 20.13 | 25.37 | 37.73 | 43.81 |
| D | 0.06045 | 0.1334 | 0.2520 | 0.3399 | 0.6059 | 0.7797 |
| βLn/Y | 1 | 2.21 | 4.17 | 5.62 | 10.02 | 12.90 |
Comparative example 2
The phosphoryl carboxylic acid extractants 3- ((di ((2-ethylhexyl) oxy) phosphoryl) propionic acid (P2) and 3- ((di ((2-ethylhexyl) oxy) phosphoryl) butyric acid (P3) were prepared according to the method disclosed in cn201910842104. X.
An extraction experiment was performed in the same manner as in extraction example 4, except that P2 or P3 was used instead of PA3, and the separation properties thereof are shown in Table 6.
TABLE 6
| P2 | Y | Ho | Er | Tm | Yb | Lu |
| E％ | 45.78 | 60.44 | 59.12 | 57.47 | 58.21 | 56.53 |
| D | 0.8443 | 1.528 | 1.446 | 1.351 | 1.393 | 1.300 |
| βLn/Y | 1 | 1.81 | 1.71 | 1.60 | 1.65 | 1.54 |
| P3 | Y | Ho | Er | Tm | Yb | Lu |
| E％ | 45.05 | 60.98 | 60.85 | 59.69 | 61.11 | 60.35 |
| D | 0.8198 | 1.563 | 1.554 | 1.481 | 1.571 | 1.522 |
| βLn/Y | 1 | 1.91 | 1.90 | 1.81 | 1.92 | 1.86 |
Compared with the phosphoryl carboxylic acid extractant P2 and P3 of CN201910842104.X, the phosphorus-containing amino acid extractant used in the application has the advantages of larger separation coefficient of lanthanoid and yttrium as a whole, less separation stages and more concise process. In addition, the extractant used in the present application has a greater difference in separation coefficient between the lanthanoids, and thus can also be used to separate the lanthanoids.
Claims (30)
1. A phosphorus-containing amino acid compound of formula I:
Wherein,
R 1 and R 2 are each independently selected from C 1～C14 alkyl groups, and the total number of carbon atoms of R 1 and R 2 is 10 or greater;
R 3 is selected from hydrogen, C 1～C6 alkyl, and C 6～C12 aryl;
z is a C 1～C12 alkylene group,
R 4 and R 5 are each independently selected from hydrogen, C 1～C10 alkyl, C 3～C10 cycloalkyl and C 6～C12 aryl,
Or R 4 and R 5 together with the carbon atom to which they are attached form a C 3～C10 cycloalkyl group.
2. The phosphorus-containing amino acid compound or a salt thereof as claimed in claim 1, wherein,
R 1 and R 2 are each independently selected from C 4～C12 alkyl;
Z is C 1～C4 alkylene.
3. The phosphorus-containing amino acid compound of claim 2, or a salt thereof, wherein R 1 and R 2 are each independently selected from C 6～C10 alkyl; z is C 1～C2 alkylene.
4. The phosphorus-containing amino acid compound of claim 3, wherein R 1 and R 2 are each independently selected from C 6～C9 alkyl.
5. The phosphorus-containing amino acid compound or a salt thereof according to claim 1, wherein the phosphorus-containing amino acid compound of the general formula I is a compound of the following general formula II:
Wherein R 1、R2、R3、R4 and R 5 are as defined in claim 1.
6. The phosphorus-containing amino acid compound or salt thereof of any one of claims 1-5, wherein R 1 and R 2 are the same alkyl group.
7. The phosphorus-containing amino acid compound or salt thereof of any one of claims 1-3 and 5, wherein R 1 and R 2 are the same C 6～C10 alkyl group.
8. The phosphorus-containing amino acid compound of claim 7, wherein R 1 and R 2 are the same C 6～C9 alkyl group, or a salt thereof.
9. The phosphorus-containing amino acid compound or salt thereof of any one of claims 1-5, wherein the total number of carbon atoms of R 1 and R 2 is an integer between 10 and 24.
10. The phosphorus-containing amino acid compound or salt thereof of any one of claims 1-5, wherein the total number of carbon atoms of R 1 and R 2 is an integer between 12 and 18.
11. The phosphorus-containing amino acid compound or salt thereof of any one of claims 1-5, wherein R 3 is hydrogen, C 1～C4 alkyl, or C 6～C10 aryl; and/or
R 4 is hydrogen and R 5 is selected from hydrogen, C 1～C6 alkyl, C 5～C7 cycloalkyl and C 6～C10 aryl.
12. The phosphorus-containing amino acid compound of claim 11, or a salt thereof, wherein R 5 is selected from the group consisting of hydrogen, C 1～C4 alkyl, C 5～C7 cycloalkyl, and C 6～C8 aryl.
13. The phosphorus-containing amino acid compound or a salt thereof as claimed in any one of claims 1 to 5, wherein R 3 is hydrogen, C 1～C2 alkyl, phenyl, benzyl, tolyl, ethylphenyl, xylyl; and/or
R 4 is hydrogen and R 5 is selected from hydrogen, C 1～C2 alkyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, tolyl, ethylphenyl, xylyl.
14. The phosphorus-containing amino acid compound or a salt thereof according to any one of claims 1 to 5, wherein the phosphorus-containing amino acid compound is one or more selected from ((di ((2-ethylhexyl) oxy) phosphoryl) methyl) glycine, ((di ((2-ethylhexyl) oxy) phosphoryl) (phenyl) methyl) phenylalanine.
15. An extraction system comprising as an extractant one or more selected from the group consisting of the phosphorus-containing amino acid compounds of any one of claims 1 to 14 and salts thereof.
16. The extraction system of claim 15, which is a liquid phase extraction system or a solid phase extraction system.
17. The extraction system of claim 16, wherein the liquid phase extraction system comprises: one or more selected from the group consisting of the phosphorus-containing amino acid compounds of any one of claims 1 to 14 and salts thereof as an extractant; and a diluent;
the solid phase extraction system is selected from the group consisting of resins, porous silica spheres, diatomaceous earth loaded with one or more selected from the group consisting of the phosphorus-containing amino acid compounds and salts thereof according to any one of claims 1 to 14.
18. The extraction system of claim 17, wherein the diluent is selected from the group consisting of: c 5～C16 alkane; aviation kerosene; sulfonated kerosene, liquid paraffin; c 5-16 cycloaliphatic alkanes; c 6～C10 aromatic hydrocarbons.
19. The extraction system of claim 18, wherein the diluent is one or more selected from the group consisting of aviation kerosene, sulfonated kerosene, heptane, and xylene.
20. The extraction system of claim 17, wherein the concentration of the phosphorus-containing amino acid compound or salt thereof in the liquid phase extraction system is from 0.0001 to 1.0mol/L based on the volume of the liquid phase extraction system.
21. The extraction system of claim 20, wherein the concentration of the phosphorus-containing amino acid compound or salt thereof in the liquid phase extraction system is from 0.01 to 0.5mol/L based on the volume of the liquid phase extraction system.
22. The extraction system of claim 17, wherein the liquid phase extraction system further comprises an auxiliary extractant and/or a phase modifier.
23. The extraction system of claim 22, wherein the concentration of the auxiliary extractant in the liquid phase extraction system is from 0 to 1.0mol/L based on the total volume of the liquid phase extraction system.
24. The extraction system of claim 22, wherein the concentration of the auxiliary extractant in the liquid phase extraction system is from 0 to 0.5mol/L based on the total volume of the liquid phase extraction system.
25. The extraction system of claim 22, wherein the concentration of the phase modifier in the liquid phase extraction system is from 0 to 1.0mol/L based on the total volume of the liquid phase extraction system.
26. The extraction system of claim 22, wherein the concentration of the phase modifier in the liquid phase extraction system is from 0 to 0.5mol/L based on the total volume of the liquid phase extraction system.
27. Use of the phosphorus-containing amino acid compound of any of claims 1-14 or a salt thereof as an extractant for separating yttrium.
28. Use of the extraction system of any one of claims 15-26 for separating yttrium.
29. Use of the phosphorus-containing amino acid compound of any of claims 1-14 or a salt thereof as an extractant for separating lanthanoid elements.
30. Use of the extraction system of any one of claims 15-26 for separating lanthanoid elements.
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