CN109706323B - Benzoheterocycles and application thereof - Google Patents
Benzoheterocycles and application thereof Download PDFInfo
- Publication number
- CN109706323B CN109706323B CN201910176843.XA CN201910176843A CN109706323B CN 109706323 B CN109706323 B CN 109706323B CN 201910176843 A CN201910176843 A CN 201910176843A CN 109706323 B CN109706323 B CN 109706323B
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- Prior art keywords
- extractant
- compound
- lithium
- chloride
- separation
- Prior art date
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- 238000000605 extraction Methods 0.000 claims abstract description 92
- 150000001875 compounds Chemical class 0.000 claims abstract description 68
- 238000000926 separation method Methods 0.000 claims abstract description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 34
- 239000012071 phase Substances 0.000 claims description 51
- 239000012074 organic phase Substances 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000008346 aqueous phase Substances 0.000 claims description 22
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 150000002367 halogens Chemical class 0.000 claims description 17
- 239000003607 modifier Substances 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- WHXSMMKQMYFTQS-IGMARMGPSA-N lithium-7 atom Chemical compound [7Li] WHXSMMKQMYFTQS-IGMARMGPSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000003085 diluting agent Substances 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 6
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 5
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 5
- UMMDBKGUDMBUSR-UHFFFAOYSA-M tris-decyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(CCCCCCCCCC)CCCCCCCCCC UMMDBKGUDMBUSR-UHFFFAOYSA-M 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- PSLWZOIUBRXAQW-UHFFFAOYSA-M dimethyl(dioctadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC PSLWZOIUBRXAQW-UHFFFAOYSA-M 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 3
- LFSAPCRASZRSKS-UHFFFAOYSA-N 2-methylcyclohexan-1-one Chemical compound CC1CCCCC1=O LFSAPCRASZRSKS-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 claims description 3
- 229960000228 cetalkonium chloride Drugs 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- LCXAARCEIWRIMU-UHFFFAOYSA-M dibenzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1C[N+](C)(C)CC1=CC=CC=C1 LCXAARCEIWRIMU-UHFFFAOYSA-M 0.000 claims description 3
- 229940117389 dichlorobenzene Drugs 0.000 claims description 3
- UMGXUWVIJIQANV-UHFFFAOYSA-M didecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC UMGXUWVIJIQANV-UHFFFAOYSA-M 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- QLPMKRZYJPNIRP-UHFFFAOYSA-M methyl(trioctyl)azanium;bromide Chemical compound [Br-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC QLPMKRZYJPNIRP-UHFFFAOYSA-M 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 159000000001 potassium salts Chemical class 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims description 3
- SNNIPOQLGBPXPS-UHFFFAOYSA-M tetraoctylazanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC SNNIPOQLGBPXPS-UHFFFAOYSA-M 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 11
- 238000005372 isotope separation Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 7
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000001612 separation test Methods 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- WHXSMMKQMYFTQS-BJUDXGSMSA-N (6Li)Lithium Chemical compound [6Li] WHXSMMKQMYFTQS-BJUDXGSMSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- -1 LiSCN Chemical compound 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- DORMTBIPKNPJPY-UHFFFAOYSA-N acetic acid;iodobenzene Chemical compound CC(O)=O.IC1=CC=CC=C1 DORMTBIPKNPJPY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000005805 hydroxylation reaction Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 229910000497 Amalgam Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XCHARIIIZLLEBL-UHFFFAOYSA-N Medicagenic acid 3-O-beta-D-glucoside Chemical compound C12CC(C)(C)CCC2(C(O)=O)CCC(C2(CCC3C4(C)C(O)=O)C)(C)C1=CCC2C3(C)CC(O)C4OC1OC(CO)C(O)C(O)C1O XCHARIIIZLLEBL-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- DIRRKLFMHQUJCM-UHFFFAOYSA-N (2-aminophenyl)boronic acid Chemical compound NC1=CC=CC=C1B(O)O DIRRKLFMHQUJCM-UHFFFAOYSA-N 0.000 description 1
- DGUWACLYDSWXRZ-UHFFFAOYSA-N (2-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1C=O DGUWACLYDSWXRZ-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- MEQBJJUWDCYIAB-UHFFFAOYSA-N 2-chloropyridin-3-amine Chemical compound NC1=CC=CN=C1Cl MEQBJJUWDCYIAB-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- UPMCDOMOBNMTPH-UHFFFAOYSA-N 6-phenyl-5,6-dihydroimidazo[2,1-b][1,3]thiazole Chemical compound N1=C2SC=CN2CC1C1=CC=CC=C1 UPMCDOMOBNMTPH-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000282346 Meles meles Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 238000005614 Skraup synthesis reaction Methods 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- UHVBHDVQHCETLR-UHFFFAOYSA-N [Cl-].[NH4+].C(C1=CC=CC=C1)C=1C(=C(C=CC1)C)C Chemical compound [Cl-].[NH4+].C(C1=CC=CC=C1)C=1C(=C(C=CC1)C)C UHVBHDVQHCETLR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005347 high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) Methods 0.000 description 1
- JLRMRTRHBRVQMS-UHFFFAOYSA-N hydrogen peroxide;2-methylpropan-2-ol Chemical compound OO.CC(C)(C)O JLRMRTRHBRVQMS-UHFFFAOYSA-N 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QYQXCUGHLJZLMP-UHFFFAOYSA-L methyl(trioctyl)azanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC QYQXCUGHLJZLMP-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- IZCXRHJRUQKMPT-UHFFFAOYSA-N n,n-dioctyloctan-1-amine;methyl hydrogen sulfate Chemical compound COS(O)(=O)=O.CCCCCCCCN(CCCCCCCC)CCCCCCCC IZCXRHJRUQKMPT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- JSKVKBMXPWAGRU-UHFFFAOYSA-M sodium trifluoro-oxido-oxo-lambda6-sulfane Chemical compound FS(=O)([O-])(F)F.[Na+] JSKVKBMXPWAGRU-UHFFFAOYSA-M 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 238000010561 standard procedure Methods 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
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a benzo-heterocycle compound and application thereof. Specifically, the invention provides a compound shown as a formula (I), and an extracting agent formed by the compound has high extraction rate on lithium ions and high separation coefficient on lithium isotopes, and can realize high-efficiency extraction and separation of the lithium isotopes.
Description
Technical Field
The invention belongs to the field of chemical industry. In particular to benzo-heterocyclic compounds and application thereof in lithium isotope extraction separation.
Background
Lithium isotopes (i.e., lithium-7 and lithium-6) are important energy source materials, and the abundance of the two isotopes is 92.48% and 7.52% in natural lithium element, respectively. After separation and concentration, the lithium-7 isotope material (the abundance is more than 99.995%) is indispensable molten salt coolant in a thorium-based molten salt reactor, and meanwhile, the high-abundance lithium-7 isotope is also a pH regulator in a pressurized water reactor. On the other hand, a high abundance of lithium-6 isotopes is an essential fuel in a controlled thermonuclear fusion reactor.
The separation method of lithium isotopes reported in domestic and foreign documents includes: physical methods (such as electromagnetic, molecular distillation, gas diffusion, etc.) and chemical methods (such as electromigration, electrolysis, lithium amalgam exchange, solvent extraction exchange, etc.) (nuclear and radiochemistry, 1991, 13, 1). In isotope separation, it is advantageous to use a physical method for heavy isotopes; for light isotopes, the chemical method is high in efficiency, and the physical method is large in investment and low in efficiency. Lithium isotopes belong to light isotopes, and lithium does not have a suitable gaseous compound, so the physical separation of lithium isotopes is only an exploratory stage. In the chemical method, a gas-liquid chemical exchange method does not exist in the lithium element, but the liquid-solid chemical exchange method is difficult to realize the countercurrent multistage cascade, so that the liquid-liquid chemical exchange method can be only adopted. To date, the method capable of industrially separating lithium isotopes is the lithium amalgam liquid-liquid chemical exchange method (chem. phys,1976,64,1828), but this method requires the use of large amounts of mercury, poses serious hazards to operators and the environment, and cannot meet the increasing demand for products. The invention patent applications CN201210274233.1 and CN201210274356.5 adopt a liquid-solid chemical exchange method, and develop a crown ether polymer separation system, and although the system has a higher single-stage separation coefficient, the liquid-solid separation method is difficult to realize multi-stage cascade enrichment and scale-up production.
The liquid-liquid chemical exchange method is adopted, and the developed extraction separation system comprises the following components: neutral solvent extraction systems (e.g., isoamyl alcohol/LiBr system), ion exchange systems (e.g., hexanoic acid/kerosene system), chelate extraction systems (e.g., Sudan I-TOPO system), etc., but these extraction systems all have a low separation coefficient α (about 1.010) (atomic energy science, 1987, 21, 433). The invention patent applications CN201510952278.3, CN201510952117.4 and CN201510976889.1 report crown ether and aza-crown ether extractants, and the enriched organic phase of the extractant is lithium-6. The invention patents CN103801194 and CN104140379 report multi-aromatic ring extractant, and the enriched substance in the organic phase is lithium-7.
In the prior art, the method also has the defects of serious pollution, low separation coefficient, low extraction rate, slow extraction reaction speed, difficult operation, low back extraction efficiency and the like, and the development of safe, green and efficient compounds for the extraction and separation of lithium isotopes is urgently needed.
Disclosure of Invention
The invention provides a benzo-heterocycle compound which can be used for efficiently and quickly extracting and separating lithium isotopes.
In a first aspect of the invention, there is provided a compound of formula (I),
wherein,
A1is selected from N or CH;
A2is selected from N or CH; and
A1and A2At least one is N;
R1、R2、R3、R4、R5and R6Each independently hydrogen, halogen, nitro, unsubstituted or halogen-substituted C1-8Alkyl radical, C1-8Alkoxy, unsubstituted or halogen-substituted phenyl.
In another preferred embodiment, R1、R2、R3、R4、R5And R6Each independently hydrogen, halogen, unsubstituted or halogen-substituted C1-8An alkyl group.
In another preferred embodiment, R1、R2、R3、R4、R5And R6Each independently hydrogen, halogen or halogen substituted C1-8An alkyl group.
In another preferred embodiment, R1、R2、R3、R4、R5And R6Each independently is hydrogen, halogen or-CF3。
In another preferred embodiment, the halogen is fluorine, chlorine or bromine.
In another preferred embodiment, R1、R2And R3Is hydrogen.
In another preferred embodiment, R4、R5And R6Each independently hydrogen, halogen or halogen substituted C1-8An alkyl group.
In another preferred embodiment, R4、R5And R6Each independently is hydrogen, halogen or-CF3。
In another preferred embodiment, R1、R2And R3Is hydrogen, and R4、R5And R6Each independently hydrogen, halogen or halogen substituted C1-8An alkyl group.
In another preferred embodiment, the compound is selected from:
in another preferred embodiment, the compound is selected from:
in a second aspect of the invention, there is provided an extractant comprising a compound of formula (I) as described in the first aspect of the invention and a diluent.
In another preferred embodiment, the diluent is selected from the group consisting of: pentanol, octanone, chloroform, petroleum ether, carbon tetrachloride, nitrobenzene, heptane, octane, kerosene, cyclohexane, n-hexane, dodecane, toluene, xylene, dichlorobenzene, trichlorobenzene, diethylbenzene, bromobenzene, anisole, nitromethane, 2-methylcyclohexanone, chlorobenzene, methylisobutylketone, diphenyl ether, and combinations thereof.
In another preferred embodiment, the diluent is selected from the group consisting of: trichlorobenzene, chloroform, methyl isobutyl ketone, octanone, and combinations thereof.
In another preferred embodiment, the molar concentration of the compound of formula (I) in the extractant is 0.01 to 2.5mol/L, preferably 0.05 to 1.5mol/L, more preferably 0.08 to 1mol/L, and most preferably 0.8 to 0.5 mol/L.
In another preferred embodiment, the extractant further comprises a modifier selected from the group consisting of: tetraoctylammonium bromide, tetraoctylammonium chloride, decaalkyltrimethylammonium chloride, benzyldimethylbenzylammonium chloride, tridecylmethylammonium chloride, dioctadecyldimethylammonium bromide, hexadecyldimethylbenzylammonium chloride, trioctylmethylammonium sulfate, trioctylmethylammonium carbonate, didecyldimethylammonium bromide, trinonylmethylammonium chloride, trioctylmethylammonium bromide, trioctylmethylammonium chloride, hexadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, and combinations thereof.
In another preferred embodiment, the modifier is selected from the group consisting of: benzyl dimethyl phenyl ammonium chloride, trioctylmethyl ammonium chloride, methyl isobutyl ketone, tridecyl methyl ammonium chloride, trioctyl methyl ammonium sulfate, and combinations thereof.
In another preferred embodiment, the concentration of the modifier in the extractant is 0.01-1mol/L, preferably 0.05-0.5mol/L, more preferably 0.08-0.3 mol/L.
In a third aspect of the invention, there is provided the use of an extractant according to the second aspect of the invention for the extractive separation of lithium isotopes.
In a fourth aspect of the present invention, there is provided a lithium isotope extraction separation method, including the steps of:
(1) contacting and extracting an extractant according to the second aspect of the present invention with an aqueous phase containing lithium ions to obtain an organic phase enriched in lithium-7 isotopes;
(2) and (2) carrying out back extraction treatment on the organic phase obtained in the step (1) by using a back extractant, and collecting a water phase, thereby obtaining a product which is enriched with the lithium-7 isotope after separation.
In another preferred embodiment, the lithium ions are from Li2SO4、Li2CO3、LiNO3、LiCl、LiBr、 LiSCN、LiClO4、LiI、Li3PO4、CF3COOLi、CCl3COOLi, LiOH, or a combination thereof.
In another preferred embodiment, the lithium ions are from Li2SO4LiCl, LiOH, LiI, or combinations thereof.
In another preferred embodiment, in step (1), the molar concentration of the lithium ions in the aqueous phase is 0.01 to 3mol/L, preferably 0.05 to 2mol/L, more preferably 0.1 to 1mol/L, and most preferably 0.1 to 0.5 mol/L.
In another preferred embodiment, in step (1), the volume ratio of the extractant to the aqueous phase containing lithium ions is 0.1-10:1, preferably 0.5-8:1, more preferably 1-6:1, most preferably 2-5: 1.
In another preferred embodiment, in step (1), the aqueous phase further comprises a base.
In another preferred embodiment, the base is selected from: NaOH, KOH, LiOH, and combinations thereof.
In another preferred embodiment, the base is ammonia.
In another preferred embodiment, the concentration of the base in the aqueous phase is 0.5 to 10mol/L, preferably 1 to 8mol/L, more preferably 2 to 5 mol/L.
In another preferred embodiment, in step (1), the extraction time is 1-3min, preferably 1-2 min.
In another preferred embodiment, the stripping agent is water or an aqueous solution of an inorganic salt, wherein the inorganic salt is selected from the group consisting of: sodium salts, ammonium salts, potassium salts, and combinations thereof.
In another preferred embodiment, the sodium salt is selected from: NaCl, NaBr, NaI, Na2SO4、NaNO3And combinations thereof.
In another preferred embodiment, the ammonium salt is selected from: NH (NH)4Cl、(NH4)2SO4、NH4NO3And combinations thereof.
In another preferred embodiment, the potassium salt is selected from: KCl, K2SO4And combinations thereof.
In another preferred embodiment, the molar concentration of the inorganic salt in the stripping agent is 0.01-1mol/L, preferably 0.1-0.5mol/L, and more preferably 0.2-0.3 mol/L.
In another preferred embodiment, in step (2), the volume ratio of the stripping agent to the organic phase obtained in step (1) is 0.1-10:1, preferably 0.5-5:1, more preferably 1-3:1, most preferably 1-2: 1.
In another preferred embodiment, the time for the back extraction is 1-3min, preferably 1-2 min.
In another preferred embodiment, said step (2) is repeated 2-4 times, preferably 2-3 times.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Detailed Description
The inventor of the invention has long and intensive research and unexpectedly found a benzo-heterocyclic compound which can be used as an organic extractant to extract and separate lithium isotopes. Surprisingly, the benzo-heterocycle compound is used as an organic extractant to extract and separate lithium isotopes in a water phase, so that the two phases are separated quickly, the single extraction efficiency is high (the one-time extraction rate of lithium ions reaches 53-70%), and the isotope separation coefficient can reach 1.023-1.029. On the basis of this, the present invention has been completed.
Definition of
As used herein, the term "alkyl" includes straight or branched chain alkyl groups. E.g. C1-8The alkyl group means a straight-chain or branched alkyl group having 1 to 8 carbon atoms (preferably, 1 to 6, more preferably, 1 to 4), such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, etc.
As used herein, the term "C1-8Alkoxy "means a straight or branched chain alkoxy group having 1 to 8 carbon atoms (preferably, 1 to 6, more preferably, 1 to 4); for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy and the like.
A compound of formula (I)
A compound of formula (I):
wherein,
A1is selected from N or CH;
A2is selected from N or CH; and
A1and A2At least one is N;
R1、R2、R3、R4、R5and R6Each independently hydrogen, halogen, nitro, unsubstituted or halogen-substituted C1-8Alkyl radical, C1-8Alkoxy, unsubstituted or halogen-substituted phenyl.
In another preferred embodiment, R1、R2、R3、R4、R5And R6Each independently hydrogen, halogen, unsubstitutedOr halogen-substituted C1-8An alkyl group.
Preparation of Compounds of formula (I)
The compounds of the present invention may be prepared by standard methods known in the art or by known methods analogous thereto. The general process for preparing the compounds of the invention is illustrated below. The starting materials and reagents described in the following experimental reaction schemes are generally commercially available.
(1) When said compound is: a. the1Is a CH group and A2When it is an N atom, the general synthesis method is as follows:
in the above reaction route, the first step is to perform group protection by using a conventional amine protection method. The second reaction step is a Pd-catalyzed coupling reaction (reference: U.S. patent application No. US 20080214818). The third step is Pd catalyzed hydroxylation reaction to finally synthesize the D-type compound.
Among them, another preparation route of compound C is also referred to in the literature: chem.2013, 78, 1311-.
(2) When said compound is: a. the1Is a N atom and A2When it is a CH group, the general synthesis method is as follows:
the synthesis method mainly comprises a first step of Skraup reaction (Badger et al, Australian J.chem. 1963,16,814, 828; N.Wahren, Tetrahedron,1964,20,2773) and a second step of Pd-catalyzed hydroxylation reaction, and finally, the G-type compound is synthesized and prepared.
Among others, other methods for the preparation of compound F are also referred to in the literature: chem, 2008,73, 5558-;
(3) when said compound is: a. the1Is a N atom and A2Is an N atomThe general synthesis method is as follows:
the first two steps of the synthesis method can refer to the reaction conditions in chem.Commun, 2007,2506-2508, and the fourth step adopts Pd-catalyzed hydroxylation reaction to finally prepare and synthesize the L-type compound.
Extracting agent
The extractant of the present invention comprises a compound of formula (I) as described above together with a diluent.
The diluent is typically a conventional organic solvent and is added to improve the characteristics of the extraction system, such as solubility, density, viscosity, extractability, prevention of emulsification, and the like.
In another preferred embodiment, the diluent is selected from the group consisting of: pentanol, octanone, chloroform, petroleum ether, carbon tetrachloride, nitrobenzene, heptane, octane, kerosene, cyclohexane, n-hexane, dodecane, toluene, xylene, dichlorobenzene, trichlorobenzene, diethylbenzene, bromobenzene, anisole, nitromethane, 2-methylcyclohexanone, chlorobenzene, methylisobutylketone, diphenyl ether, and combinations thereof.
In another preferred embodiment, the molar concentration of the compound of formula (I) in the extractant is 0.01 to 2.5mol/L, preferably 0.05 to 1.5mol/L, more preferably 0.08 to 1mol/L, and most preferably 0.8 to 0.5 mol/L.
In another preferred embodiment, the extractant further comprises a modifier selected from the group consisting of: tetraoctylammonium bromide, tetraoctylammonium chloride, decaalkyltrimethylammonium chloride, benzyldimethylbenzylammonium chloride, tridecylmethylammonium chloride, dioctadecyldimethylammonium bromide, hexadecyldimethylbenzylammonium chloride, trioctylmethylammonium sulfate, trioctylmethylammonium carbonate, didecyldimethylammonium bromide, trinonylmethylammonium chloride, trioctylmethylammonium bromide, trioctylmethylammonium chloride, hexadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, and combinations thereof.
In another preferred embodiment, the concentration of the modifier in the extractant is 0.01-1mol/L, preferably 0.05-0.5mol/L, more preferably 0.08-0.3 mol/L.
Extraction separation of lithium isotopes
The extracting agent provided by the invention has the application of extracting and separating lithium isotopes.
In the chemical exchange method for liquid-liquid separation of lithium isotopes, the isotope exchange reaction between two liquid phases can be expressed as:
wherein A and B represent different lithium ion coordination environments in two phases, for example, A represents an aqueous phase and B represents an extractant organic phase in the invention.
The extraction rate is the percentage of the total amount of lithium ions extracted into the organic phase to the total amount of lithium ions in the two phases, and represents the complete degree of lithium ion extraction.
The effect of single-stage separation of lithium isotopes is expressed by the separation coefficient (α value), i.e. the quotient of the ratio of the abundance of lithium isotopes in the B phase and the ratio of the abundance of lithium isotopes in the a phase:
the separation coefficient indicates the degree to which two substances are separated in a certain unit separation operation or a certain separation process. Its size reflects the ease with which the two components can be separated. The separation coefficient is equal to 1, so that the separation cannot be realized; the greater the separation coefficient deviates from 1, the easier it is to be separated.
Most isotope separation methods have separation coefficients close to 1, so another parameter representing the isotope separation effect is the enrichment coefficient ∈:
a small increase in the enrichment factor epsilon (. apprxeq.alpha. -1) during separation can have a significant impact on isotope separation operations, such as the energy consumption of the separation being inversely proportional to the square of epsilon, the equilibrium time of the separation being inversely proportional to the square of epsilon, the volume of the separation equipment being inversely proportional to the square of epsilon, and the number of separation equipment being inversely proportional to epsilon. It can be seen that a small increase in the value of the separation coefficient α can have a large positive effect on the separation work.
The invention also provides a lithium isotope extraction separation method, which comprises the following steps:
(1) contacting and extracting an extractant according to the second aspect of the present invention with an aqueous phase containing lithium ions to obtain an organic phase enriched in lithium-7 isotopes;
(2) and (2) carrying out back extraction treatment on the organic phase obtained in the step (1) by using a back extractant, and collecting a water phase, thereby obtaining a product which is enriched with the lithium-7 isotope after separation.
In another preferred embodiment, the lithium ions are from Li2SO4、Li2CO3、LiNO3、LiCl、LiBr、 LiSCN、LiClO4、LiI、Li3PO4、CF3COOLi、CCl3COOLi, LiOH, or a combination thereof.
In another preferred embodiment, in step (1), the molar concentration of the lithium ions in the aqueous phase is 0.01 to 3mol/L, preferably 0.05 to 2mol/L, more preferably 0.1 to 1mol/L, and most preferably 0.1 to 0.5 mol/L.
In another preferred embodiment, in step (1), the aqueous phase further comprises a base.
In another preferred embodiment, the base is selected from: NaOH, KOH, LiOH, and combinations thereof.
In another preferred embodiment, in step (1), the extraction time is 1-3min, preferably 1-2 min.
In another preferred embodiment, the stripping agent is water or an aqueous solution of an inorganic salt, wherein the inorganic salt is selected from the group consisting of: sodium salts, ammonium salts, potassium salts, and combinations thereof.
The invention has the main advantages that:
(1) the invention provides a benzo-heterocyclic compound, which has a simple preparation method, and provides an extracting agent containing the compound, wherein the extracting agent can be used for efficiently extracting and separating lithium isotopes.
(2) The extracting agent has strong capability of extracting lithium (the one-time extraction rate reaches 53-70%), high extraction speed (the extraction oscillation time is about 1 minute), and high separation coefficient of the extracted and separated lithium isotope (the separation coefficient reaches 1.023-1.029).
(3) The extraction method provided by the invention is simple and convenient to operate, easy in back extraction and high in efficiency, and the lithium back extraction rate can reach 99.5% if the back extraction is carried out for 2 times; meanwhile, the concentration of the stripping agent is low (0.20-0.3 mol/L), the dosage of the reagent is small, and the extraction agent is easy to recycle.
(4) The extraction separation method provided by the invention is mercury-free, green and environment-friendly, reduces the cost of lithium isotope separation, and has high economic benefit.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
The molecular structure of the compound is determined by a nuclear magnetic resonance apparatus, a mass spectrometer and an infrared spectrometer,1h NMR was measured by 300 or 400MHz, Bruker NMR, with TMS as internal standard. ESI-MS was determined using a Perkin-Elmer Mariner mass spectrometer.
Example 1
Method for synthesizing compound D1:
the first step is as follows: 650mg (A1, 5mmol,1.0equiv.) of the commercially available compound 2-chloro-3-aminopyridine is dissolved in 10mL of triethylamine, 1mL (15mmol,3.0equiv.) of acetyl chloride is added under the protection of nitrogen, the mixture is stirred for 3h at room temperature and then 1mL (15mmol,3.0equiv.) of acetyl chloride is added, the reaction is continued for 15h at room temperature, and the TLC detection of the raw materials is almost completed. 50mL of water and 50mL of ethyl acetate are added for liquid separation and extraction, the aqueous phase after liquid separation is extracted twice by 50mL of ethyl acetate, the combined organic phase is washed twice by 50mL of water, and the solvent is evaporated after drying to obtain 701mg of yellow oily matter B1, the yield is 82%, and the yellow oily matter B1 can be directly used for the next reaction.
The second step is that: 700mg (3.89mmol,1.0equiv) of the above oily substance, 750mg (5mmol,1.28equiv.) of a commercially available compound, 2-formylphenylboronic acid, K2CO3 1.38g(10mmol,2.57equiv.)，Pd(PPh3)4250mg (0.25mmol,6 mol%) are dissolved in 10mL DMSO and 2mL water, heated to 110 ℃ and the reaction mixture gradually turns black from yellow, after about 1h the reaction is detected by TLC essentially completely, cooled, 30mL water and 50mL ethyl acetate are added, filtration and extraction by liquid separation are carried out, the aqueous phase is extracted twice with 50mL dichloromethane, the combined organic phases are washed twice with 50mL water, the solvent is evaporated after drying, and column chromatography (PE: EA ═ 4:1) is carried out to isolate compound C1, 340mg of grey solid, 49% yield. Nuclear magnetic resonance spectrogram data:1H NMR(400MHz,CDCl3)δ9.32 (s,1H),9.15(d,J＝8.2Hz,1H),9.00(dd,J＝4.3,1.5Hz,1H),8.45(dd,J＝8.2, 1.5Hz,1H),8.05(d,J＝7.9Hz,1H),7.99–7.88(m,1H),7.86–7.75(m,1H),7.67 (dd,J＝8.2,4.3Hz,1H).13C NMR(101MHz,CDCl3) δ 154.31,149.40,141.19, 139.23,137.26,133.40,131.48,129.10,128.28,127.88,123.74,123.30. infrared spectral data: IR (thin film): vmax3050,1589,1387cm-1Mass spectrometry data: MS (ESI) M/z 181(M + H)+).
The third step: to a 100mL stopcock were added 1.9g (10.6mmol,1.0equiv.) of Compound C1, 400mg (1.67mmol,15 mol%) of palladium acetate, 4.6g (14.3mmol,1.35equiv.), acetonitrile 40mL, and 10mL of acetic anhydride. After sealing, the mixture was heated to 160 ℃. After 14h of reaction, cooling, detecting by TLC to complete the reaction, adding 4M NaOH solution to neutralize to near neutrality, adding 100mL of dichloromethane for extraction, extracting the aqueous phase after liquid separation twice with 50mL of dichloromethane, evaporating most of the solvent from the organic phase to obtain black oily matter, dissolving the oily matter in 20mL of ethanol and 5mL of water, adding 2g of NaOH, and stirring at room temperature overnight. The next day, addNeutralizing with 3M hydrochloric acid solution, extracting with 100mL dichloromethane, extracting the separated aqueous phase twice with 50mL dichloromethane, evaporating most of the solvent from the organic phase, separating by column chromatography (PE: EA ═ 4:1), and recrystallizing with ethyl acetate and petroleum ether to obtain compound D1 as a yellow solid 800mg with a yield of 39%. Nuclear magnetic resonance spectrogram data:1H NMR(400MHz,CDCl3)δ13.84 (s,1H),9.14(s,1H),8.71(dd,J＝4.6,1.5Hz,1H),8.38(dd,J＝8.3,1.5Hz,1H), 7.68–7.53(m,2H),7.45(dd,J＝7.8,0.7Hz,1H),7.30(dd,J＝8.0,0.9Hz,1H). 13C NMR(101MHz,CDCl3) δ 158.03,155.28,145.96,143.12,138.24,137.51, 130.85,129.37,122.67,118.17,117.53,117.26. infrared spectral data: IR (thin film): vmax 2645,1588,1447cm-1Mass spectrometry data: MS (ESI) M/z 197(M + H)+).
Example 2
Synthesis of compound G1:
the first step is as follows: 8.5g of compound E1, 15mL of glycerol, 15mL of nitrobenzene, 15mL of concentrated sulfuric acid and 10mL of ice water were added to a reaction flask, and the mixture was heated to 160 ℃ for reaction for 24 hours. After cooling to room temperature, 4M NaOH was added for neutralization, the viscous liquid was extracted four times with dichloromethane and water, the organic phases were combined and washed twice with water, the solvent was evaporated after drying, and compound F1 was isolated by column chromatography in 3.82g as a solid in 35% yield.
The second step is that: to a sealed tube were added 0.180g (1.0mmol) of compound F1, 0.676g (2.0mmol) of iodobenzene acetate, 0.012g of palladium acetate (0.042mmol), and added 5mL of acetonitrile and 0.4mL of acetic anhydride, and the mixture was heated to 165 ℃ and stirred for reaction for 18 h. Acetonitrile was distilled off, 0.2G of sodium hydroxide and 10mL of methanol were added, hydrolysis, neutralization and extraction with dichloromethane gave an organic layer, which was washed with saturated brine, dried over anhydrous magnesium sulfate and subjected to column chromatography to give 0.102G of compound G1 in 52% yield.1H NMR (300MHz, chloroform-d) δ 13.74(s, 1H),9.28(s,1H),9.05(d, J ═ 6.0Hz,1H),8.46(dd, J ═ 7.9,1.8Hz,1H), 7.81 to 7.69(M,3H),7.30 to 7.25(M,1H). MS(ESI):m/z 197(M+H+).
Example 3
Synthesis of compound G2:
the first step is as follows: 10.6g of Compound E2, 15mL of glycerol, 15mL of nitrobenzene, 15mL of concentrated sulfuric acid, and 10mL of ice-water were added to a reaction flask, and the mixture was heated to 160 ℃ for reaction for 24 hours. After cooling to room temperature, 4M NaOH was added for neutralization, the viscous liquid was extracted four times with dichloromethane and water, the organic phases were combined and washed twice with water, the solvent was evaporated after drying, and compound F2 was isolated by column chromatography in 5.74g as a solid in 45% yield.
The second step is that: 0.43g of compound F2, 1.35g of iodobenzene acetate, 0.025g of palladium acetate, 10mL of acetonitrile and 0.8mL of acetic anhydride were added to the tube, mixed and heated to 165 ℃ and the reaction was stirred for 20 hours. Acetonitrile was distilled off, 0.5G of sodium hydroxide and 15mL of methanol were added, hydrolysis, neutralization, extraction with dichloromethane to give an organic layer, washing with saturated brine, drying the organic layer over anhydrous magnesium sulfate, and column chromatography to give 0.21G of compound G1 in 45% yield. MS (ESI) M/z 231(M + H)+).
Example 4
Method for synthesizing compound L1:
the first step is as follows: a reaction flask was charged with 1.85g (9mmol) of commercially available compound H1, 1.73g (10mmol) of commercially available compound 2-aminobenzeneboronic acid, 0.61g of tetrakis (triphenylphosphine) palladium, 4.24g (40mmol) of sodium carbonate, and 50ml of toluene, 20ml of ethanol, and 20ml of water, followed by mixing, stirring, and heating under reflux for 30 hours. Extraction, washing and column chromatography gave compound I1, 1.71g, 87% yield.
The second step is that: 0.60g of compound I1 and 250 mL of 1mol/L sodium hydroxide methanol solution are added into a reaction flask, and the mixture is stirred and heated to 70 ℃ for reaction for 6 h. The methanol is evaporated, 2mol/L hydrochloric acid is added for neutralization, ethyl acetate is added for extraction, and the product J1 is obtained after purification and evaporation to dryness, 0.51g and the yield is 92%.
The third step: 1.0g of compound J1, 30ml of dichloromethane and 0.1g of palladium on carbon were hydrogenated at ordinary temperature and pressure for 24 hours. Filtration and column chromatography gave compound K1, 0.83g, 90% yield.
In the fourth step, 0.90g of compound K1, 3.70g of iodobenzene acetate, 0.080g of palladium acetate, 25mL of acetonitrile and 6mL of acetic anhydride were added to the tube, mixed and heated to 160 ℃ and reacted for 48 hours with stirring. Distilling off acetonitrile, extracting, and carrying out column chromatography to obtain an unhydrolyzed solid compound. To the compound, 2g of sodium hydroxide and 40mL of methanol were added, hydrolyzed for 4 hours, neutralized, extracted with ethyl acetate to give an organic layer, washed with saturated brine, dried over anhydrous magnesium sulfate, and subjected to column chromatography to give compound L1, 0.41g, 42% yield.1H NMR (300MHz, chloroform-d) δ 12.92(s,1H), 9.11-9.13 (M,2H),8.37(d, J ═ 6.0Hz,1H),7.98(t, J ═ 9.0Hz,1H),7.91(dd, J ═ 9.0Hz, J ═ 6.0Hz,1H),7.50(d, J ═ 8.1Hz,1H)+).
Example 5
Synthesis of compounds M1 and N1:
to a reaction flask were added 0.41g (2.1mmol) of Compound L1, 10mL of dichloromethane, 4mL of water, 1.44g (6mmol) of sodium trifluorosulfinate, and slowly dropwise added 1.384g of t-butanol hydroperoxide (10mmol), and the reaction was stirred at room temperature. TLC detection after almost complete reaction of the starting material, extraction with dichloromethane twice, washing of the organic phase with water, drying over anhydrous magnesium sulfate and column chromatography of PE: EA (10:1) gave 0.12g (22%) of compound M1 and 0.22g (40%) of compound N1.
Compound M1:1h NMR (400MHz, chloroform-d) δ 13.97(s,1H),9.19(d, J ═ 8.0Hz, 1H),9.16(d, J ═ 4.0Hz,1H),8.39(d, J ═ 8.7Hz,1H),8.19(d, J ═ 8.6Hz,1H), 7.98(dd, J ═ 8.4,4.7Hz,1H).19F NMR (376MHz, chloroform-d) delta-62.2. MS (ESI) M/z 266(M + H)+).
Chemical combinationSubstance N1:1H NMR(300MHz,Chloroform-d)δ13.57(s,1H),9.25–9.19(m, 2H),8.29(d,J＝8.5Hz,1H),8.08–7.97(m,1H),7.49(d,J＝8.5Hz,1H).19f NMR (282MHz, chloroform-d) delta-57.90. MS (ESI) M/z 266(M + H)+).
7Li/6Li ratio test method
Measuring two phases of the extraction process by inductively coupled plasma mass spectrometer (HR-ICP-MS, Thermo Fisher, Scientific Electron 2)7Li/6Ratio of Li, thereby calculating the coefficient of separation of single-stage lithium isotope (. alpha.value)
Method for testing concentration of lithium element
The concentration of lithium ions in both phases was measured by an atomic absorption spectrometer (Thermo Fisher, iCE3000) to calculate the extraction rate (E%) of lithium ions.
Example 6
Extraction separation test
The extractant comprises the following components: 0.20mol/L of Compound D1; the diluent is trichlorobenzene; the modifier is added into the mixture, and the concentration of the modifier is 0.20mol/L of trioctyl ammonium methyl sulfate. Composition of aqueous phase containing lithium: 0.08mol/L LiCl; 2.5mol/L NaOH. Phase ratio (volume ratio of organic phase to aqueous phase): 4:1.
Adding the extracted organic phase and the extracted water phase into a separating funnel, oscillating for 1 minute, standing for layering, and collecting the two phases to be respectively used as the organic phase and the water phase after extraction and separation.
And (3) performing back extraction on the organic phase by using 0.30mol/L ammonium chloride solution (back extraction agent) for 2 times compared with 1:1, wherein the back extraction rate of lithium ions is 99.4%, and products enriched with lithium-7 in the organic phase are completely transferred into a back extraction water phase, so that the extraction agent can be recycled.
Respectively measuring the lithium isotope abundance in the two-phase solution after extraction and separation, and calculating the isotope separation coefficient alpha value to be 1.023; the concentration of lithium ions in the two-phase solution was measured, respectively, and the primary extraction rate of lithium ions was calculated to be 53%.
Example 7
Extraction separation test
The extractant comprises the following components: 0.16mol/L of compound G1; the diluent is chloroform; the modifier is 0.16mol/L tridecyl methyl ammonium chloride. The composition of the water phase is as follows: 0.03mol/L LiOH; 4.0mol/L KOH. Phase ratio (volume ratio of organic phase to aqueous phase): 5:1.
Adding the extracted organic phase and the extracted water phase into a separating funnel, oscillating for 1 minute, standing for layering, and collecting the two phases to be used as the extracted organic phase and the extracted water phase respectively.
And (3) performing back extraction on the organic phase by using 0.25mol/L sodium chloride solution (back extraction agent) for 2 times compared with 1:1, wherein the back extraction rate of lithium ions is 99.3%, and products enriched with lithium-7 in the organic phase are completely transferred into a back extraction water phase, so that the extraction agent can be recycled.
Respectively measuring the lithium isotope abundance in the two-phase solution after extraction and separation, and calculating the isotope separation coefficient alpha value to be 1.026; the concentration of lithium ions in the two-phase solution was measured, respectively, and the primary extraction rate of lithium ions was calculated to be 56%.
Example 8
Extraction separation test
The extractant comprises the following components: 0.10mol/L of compound G2; the diluent is methyl isobutyl ketone; the modifier is added into the mixture, and the concentration of the modifier is 0.20mol/L dioctadecyl dimethyl ammonium bromide. The composition of the water phase is as follows: 0.05mol/L Li2SO4(ii) a 5.0mol/L NaOH. Phase ratio (volume ratio of organic phase to aqueous phase): 4:1.
Adding the extracted organic phase and the extracted water phase into a separating funnel, oscillating for 1 minute, standing for layering, and collecting the two phases to be respectively used as the organic phase and the water phase after extraction and separation.
And (3) performing back extraction on the organic phase by using 0.30mol/L ammonium sulfate solution (back extraction agent) for 2 times compared with 1:1, wherein the back extraction rate of lithium ions is 99.5%, and products enriched with lithium-7 in the organic phase are completely transferred into a back extraction water phase, so that the extraction agent can be recycled.
Respectively measuring the lithium isotope abundance in the two-phase solution after extraction and separation, and calculating the isotope separation coefficient alpha value to be 1.025; the concentrations of lithium ions in the two-phase solutions were measured, respectively, and the primary extraction rate of lithium ions was calculated to be 70%.
Example 9
Extraction separation test
The extractant comprises the following components: 0.10mol/L of Compound L1; the diluent is chloroform; the modifier is added into the solution, and the concentration of the modifier is 0.10mol/L of trioctylmethylammonium chloride. The composition of the water phase is as follows: 0.04mol/L LiI; 5.0mol/L NaOH. Phase ratio (volume ratio of organic phase to aqueous phase): 5:1.
Adding the extracted organic phase and the extracted water phase into a separating funnel, oscillating for 1 minute, standing for layering, and collecting the two phases to be respectively used as the organic phase and the water phase after extraction and separation.
And (3) performing back extraction on the organic phase by using 0.20mol/L sodium sulfate solution (back extraction agent) for 2 times compared with 1:1, wherein the back extraction rate of lithium ions is 99.3%, and products enriched with lithium-7 in the organic phase are completely transferred into a back extraction water phase, so that the extraction agent can be recycled.
Respectively measuring the abundance of lithium isotopes in the two-phase solution after extraction and separation, and calculating the value of an isotope separation coefficient alpha to be 1.029; the concentration of lithium ions in the two-phase solution was measured, respectively, and the primary extraction rate of lithium ions was calculated to be 66%.
Example 10
Extraction separation test
The extractant comprises the following components: 0.04mol/L of compound M1 and 0.04mol/L of compound N1; the diluent is octanone; the modifier is added into the mixture and is 0.08mol/L benzyl dimethyl benzene ammonium chloride. The composition of the water phase is as follows: 0.04mol/L LiI; 5.0mol/L NaOH. Phase ratio (volume ratio of organic phase to aqueous phase): 6:1.
Adding the extracted organic phase and the extracted water phase into a separating funnel, oscillating for 1 minute, standing for layering, and collecting the two phases to be respectively used as the organic phase and the water phase after extraction and separation.
And (3) performing back extraction on the organic phase by using 0.25mol/L ammonium nitrate solution (back extraction agent) for 2 times compared with 1:1, wherein the back extraction rate of lithium ions is 99.4%, completely transferring the product enriched with lithium-7 in the organic phase into a back extraction water phase, and recycling the extraction agent.
Respectively measuring the lithium isotope abundance in the two-phase solution after extraction and separation, and calculating the isotope separation coefficient alpha value to be 1.025; the concentration of lithium ions in the two-phase solution was measured, respectively, and the primary extraction rate of lithium ions was calculated to be 58%.
In conclusion, the benzo-heterocyclic compound can be used as an extracting agent to efficiently separate lithium isotopes, two phases are separated quickly, the single extraction efficiency is high (the one-time extraction rate of lithium ions reaches 53-70%), the separation coefficient alpha value of the lithium isotopes can reach 1.023-1.029, the extraction method is high in back extraction efficiency, and the extracting agent can be recycled.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (16)
1. An extractant for the extractive separation of lithium isotopes, characterized in that the extractant comprises a compound of formula (I), a diluent and a modifier;
wherein,
A1is selected from N or CH;
A2is selected from N or CH;
A1and A2At least one is N; and
R1、R2、R3、R4、R5and R6Each independently hydrogen, halogen, nitro, unsubstituted or halogen-substituted C1-8Alkyl radical, C1-8Alkoxy, unsubstituted or halogen-substituted phenyl; and is
The modifier is selected from the following group: tetraoctylammonium bromide, tetraoctylammonium chloride, decaalkyltrimethylammonium chloride, benzyldimethylbenzylammonium chloride, tridecylmethylammonium chloride, dioctadecyldimethylammonium bromide, hexadecyldimethylbenzylammonium chloride, trioctylmethylammonium sulfate, trioctylmethylammonium carbonate, didecyldimethylammonium bromide, trinonylmethylammonium chloride, trioctylmethylammonium bromide, trioctylmethylammonium chloride, hexadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, and combinations thereof.
2. The extractant of claim 1, wherein the extractant is in the form of a mixture of two or more of the following compoundsIn, R1、R2、R3、R4、R5And R6Each independently hydrogen, halogen or halogen substituted C1-8An alkyl group.
3. The extractant of claim 1 wherein R is1、R2、R3、R4、R5And R6Each independently is hydrogen, halogen or-CF3。
4. The extractant of claim 1 wherein R is1、R2And R3Is hydrogen.
5. An extractant according to claim 1, wherein the compound of formula (I) is selected from:
6. the extractant of claim 1 wherein the compound of formula (I) is
7. The extractant of claim 1 wherein the diluent is selected from the group consisting of: pentanol, octanone, chloroform, petroleum ether, carbon tetrachloride, nitrobenzene, heptane, octane, kerosene, cyclohexane, n-hexane, dodecane, toluene, xylene, dichlorobenzene, trichlorobenzene, diethylbenzene, bromobenzene, anisole, nitromethane, 2-methylcyclohexanone, chlorobenzene, methylisobutylketone, diphenyl ether, and combinations thereof.
8. The extractant of claim 1, wherein the molar concentration of the compound of formula (I) in the extractant is 0.01 to 2.5 mol/L.
9. The extractant of claim 8, wherein the molar concentration of the compound of formula (I) in the extractant is from 0.05 to 1.5 mol/L.
10. The extractant of claim 1 wherein the concentration of the modifier in the extractant is from 0.01 to 1 mol/L.
11. The extractant of claim 10 wherein the concentration of the modifier in the extractant is from 0.05 to 0.5 mol/L.
12. A lithium isotope extraction separation method, characterized by comprising the steps of:
(1) contacting and extracting an extractant according to any one of claims 1 to 11 with an aqueous phase containing lithium ions to obtain an organic phase enriched in lithium-7 isotopes;
(2) and (2) carrying out back extraction treatment on the organic phase obtained in the step (1) by using a back extractant, and collecting a water phase, thereby obtaining a product which is enriched with the lithium-7 isotope after separation.
13. The method of claim 12, wherein in step (1), the molar concentration of the lithium ions in the aqueous phase is 0.01 to 3 mol/L.
14. The method of claim 12, wherein in step (1), the aqueous phase further comprises a base.
15. The method of claim 12, wherein the stripping agent is water or an aqueous solution of an inorganic salt selected from the group consisting of: sodium salts, ammonium salts, potassium salts, and combinations thereof.
16. The use of a compound for preparing an extractant for the extractive separation of lithium isotopes, wherein the compound is
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