CN115367775A - Method for preparing fluorosulfonate from fluorosulfonate - Google Patents
Method for preparing fluorosulfonate from fluorosulfonate Download PDFInfo
- Publication number
- CN115367775A CN115367775A CN202210995292.1A CN202210995292A CN115367775A CN 115367775 A CN115367775 A CN 115367775A CN 202210995292 A CN202210995292 A CN 202210995292A CN 115367775 A CN115367775 A CN 115367775A
- Authority
- CN
- China
- Prior art keywords
- fluorosulfonate
- alkali metal
- reaction
- solvent
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 53
- -1 alkali metal salt Chemical class 0.000 claims abstract description 112
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 74
- 239000002904 solvent Substances 0.000 claims abstract description 48
- 238000001914 filtration Methods 0.000 claims abstract description 30
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims description 23
- 230000008025 crystallization Effects 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 150000001768 cations Chemical class 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 239000003880 polar aprotic solvent Substances 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- 150000005678 chain carbonates Chemical class 0.000 claims description 6
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 6
- 150000008282 halocarbons Chemical class 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 5
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 150000004292 cyclic ethers Chemical class 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229910001414 potassium ion Inorganic materials 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 4
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 4
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 24
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 8
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
- CHHOPPGAFVFXFS-UHFFFAOYSA-M [Li+].[O-]S(F)(=O)=O Chemical compound [Li+].[O-]S(F)(=O)=O CHHOPPGAFVFXFS-UHFFFAOYSA-M 0.000 description 20
- 229910052744 lithium Inorganic materials 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 15
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- XCXLEIPEAAEYTF-UHFFFAOYSA-M sodium fluorosulfate Chemical compound [Na+].[O-]S(F)(=O)=O XCXLEIPEAAEYTF-UHFFFAOYSA-M 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- 239000011356 non-aqueous organic solvent Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- HRXDYOKVWGTDPD-UHFFFAOYSA-N ctk4b9193 Chemical compound [NH4+].[O-]S(F)(=O)=O HRXDYOKVWGTDPD-UHFFFAOYSA-N 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- VXJAYNWISQFORV-UHFFFAOYSA-M potassium fluorosulfate Chemical compound [K+].[O-]S(F)(=O)=O VXJAYNWISQFORV-UHFFFAOYSA-M 0.000 description 4
- 150000004684 trihydrates Chemical class 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- KRRYGFCJUCTWMH-UHFFFAOYSA-N fluorosulfonyloxyethane Chemical compound CCOS(F)(=O)=O KRRYGFCJUCTWMH-UHFFFAOYSA-N 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 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
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- SUPUVLWGKPVHBQ-UHFFFAOYSA-M lithium sulfite Chemical compound [Li+].OS([O-])=O SUPUVLWGKPVHBQ-UHFFFAOYSA-M 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229940039748 oxalate Drugs 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-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
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- LBYHMOFGGBTKJY-UHFFFAOYSA-N 1-fluorosulfonyloxybutane Chemical compound CCCCOS(F)(=O)=O LBYHMOFGGBTKJY-UHFFFAOYSA-N 0.000 description 1
- ZLKOPADYUGFXSN-UHFFFAOYSA-N 2-fluorosulfonyloxy-2-methylpropane Chemical compound CC(C)(C)OS(F)(=O)=O ZLKOPADYUGFXSN-UHFFFAOYSA-N 0.000 description 1
- FKRDYPAKVOATQY-UHFFFAOYSA-N 2-fluorosulfonyloxypropane Chemical compound CC(C)OS(F)(=O)=O FKRDYPAKVOATQY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- BDIBYQORZHGDIR-UHFFFAOYSA-N fluorosulfonyloxybenzene Chemical compound FS(=O)(=O)OC1=CC=CC=C1 BDIBYQORZHGDIR-UHFFFAOYSA-N 0.000 description 1
- QPEUVQOIQCTLBQ-UHFFFAOYSA-N fluorosulfonyloxymethylbenzene Chemical compound FS(=O)(=O)OCC1=CC=CC=C1 QPEUVQOIQCTLBQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- MBXNQZHITVCSLJ-UHFFFAOYSA-N methyl fluorosulfonate Chemical compound COS(F)(=O)=O MBXNQZHITVCSLJ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- FUGINSUSTSZAEY-UHFFFAOYSA-M potassium;ethyl sulfate Chemical compound [K+].CCOS([O-])(=O)=O FUGINSUSTSZAEY-UHFFFAOYSA-M 0.000 description 1
- WBGWGHYJIFOATF-UHFFFAOYSA-M potassium;methyl sulfate Chemical compound [K+].COS([O-])(=O)=O WBGWGHYJIFOATF-UHFFFAOYSA-M 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- RRLOOYQHUHGIRJ-UHFFFAOYSA-M sodium;ethyl sulfate Chemical compound [Na+].CCOS([O-])(=O)=O RRLOOYQHUHGIRJ-UHFFFAOYSA-M 0.000 description 1
- DZXBHDRHRFLQCJ-UHFFFAOYSA-M sodium;methyl sulfate Chemical compound [Na+].COS([O-])(=O)=O DZXBHDRHRFLQCJ-UHFFFAOYSA-M 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/45—Compounds containing sulfur and halogen, with or without oxygen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D13/00—Compounds of sodium or potassium not provided for elsewhere
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a method for preparing fluorosulfonate from fluorosulfonate, which comprises the following steps: (1) Mixing fluorosulfonate, alkali metal salt and organic solvent for reaction, and performing solid-liquid separation to obtain a reaction solution; (2) And (2) concentrating the reaction liquid obtained in the step (1), adding a poor solvent, crystallizing and filtering to obtain the fluorosulfonate. The method provided by the invention simplifies the operation process, reduces the generation of byproducts, improves the yield and purity of the target product, and simultaneously reduces the requirements on production conditions, thereby being beneficial to large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of lithium secondary batteries, relates to an electrolyte of a lithium secondary battery, and particularly relates to a method for preparing fluorosulfonate by adopting fluorosulfonate.
Background
Nonaqueous electrolyte secondary batteries such as lithium secondary batteries are put into practical use in fields ranging from power supplies for consumer use such as mobile phones and notebook personal computers to power supplies for driving vehicles such as automobiles and large-sized power supplies for stationary use. In recent years, the market has been increasingly demanding on the performance of nonaqueous electrolyte secondary batteries, and in particular, lithium secondary batteries are required to be continuously improved in high levels of high capacity, high output, high-temperature storage characteristics, and cycle characteristics.
In particular, in the case of using a lithium secondary battery as a power source for an electric vehicle, the lithium secondary battery is required to have high output characteristics and input characteristics because the electric vehicle requires a large amount of energy at the time of starting and accelerating the vehicle and also the high energy generated at the time of decelerating the vehicle must be efficiently regenerated. Currently, a nonaqueous electrolyte for a lithium secondary battery is required to have a low internal resistance, a high capacity retention rate after a durability test such as a high-temperature storage test or a cycle test, and excellent input/output performance and impedance characteristics even after the durability test.
Fluorosulfonate salts are excellent as a kind of excellent non-aqueous electrolyte for lithium secondary batteries to solve the above problems. In the prior art, the preparation method of fluorosulfonate mainly comprises the following three methods: (1) Reacting fluorosulfonic acid or sulfur trioxide with lithium halide in anhydrous hydrofluoric acid to obtain fluorosulfonic acid salt; (2) a method of reacting fluorosulfonic acid with lithium carboxylate or lithium halide; (3) Ammonium fluorosulfonate and aqueous lithium hydroxide solutions are mixed to obtain trihydrate of fluorosulfonate. However, the sulfur trioxide, fluorosulfonic acid and other substances used in these reactions are highly corrosive, and corrosive sulfuric acid and hydrogen fluoride are generated, which not only causes corrosion of equipment and environmental pollution, but also makes it difficult to operate in the actual production process. In the method (3), after the synthesis of the ammonium salt, the lithium salt must be subjected to cation exchange, which is a complicated operation and easily introduces ammonia to be desorbed.
Therefore, how to provide a preparation method of fluorosulfonate, which simplifies the operation process, reduces the generation of by-products, improves the yield and purity of target products, and reduces the requirements for production conditions, thereby facilitating large-scale production and application and becoming a problem to be solved by technical personnel in the field at present.
Disclosure of Invention
In view of the disadvantages of the prior art, the present invention aims to provide a method for preparing fluorosulfonate from fluorosulfonate, wherein fluorosulfonate and specific alkali metal salt are reacted in a polar aprotic solvent, so as to prepare fluorosulfonate with high purity in a mild condition at a high yield.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing fluorosulfonate from fluorosulfonate, which comprises the following steps:
(1) Mixing fluorosulfonate, alkali metal salt and organic solvent for reaction, and performing solid-liquid separation to obtain a reaction solution;
(2) And (2) concentrating the reaction liquid obtained in the step (1), adding a poor solvent, crystallizing and filtering to obtain the fluorosulfonate.
Wherein the structural formula of the fluorosulfonate ester in the step (1) is as follows:
in the structural formula, R is selected from any one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl or benzyl.
The alkali metal salt in the step (1) includes any one of halogenated alkali metal salt, alkali metal carbonate, alkali metal bicarbonate, alkali metal phosphate, alkali metal carboxylate, alkali metal sulfate, alkali metal sulfite, alkali metal bisulfite, alkali metal oxalate, alkali metal oxide, alkali metal hydride, alkali metal hydroxide or alkali metal alkoxide, and the cation in the alkali metal salt is selected from any one of lithium ion, sodium ion or potassium ion.
The organic solvent in the step (1) is a polar aprotic solvent, and comprises any one of chain carbonate, cyclic carbonate, chain carboxylate, chain ether, cyclic ether or chain nitrile solvent.
The poor solvent in the step (2) is a poor solvent of fluorosulfonate.
The invention takes the fluorosulfonate and the specific alkali metal salt as raw materials, and can prepare the fluorosulfonate by simple chemical reaction in a polar aprotic solvent, thereby simplifying the operation process, reducing the generation of byproducts, improving the yield and purity of the target product, and simultaneously reducing the requirements on production conditions, and being beneficial to large-scale production and application.
Compared with the method for preparing the fluorosulfonate by reacting fluorosulfonic acid or sulfur trioxide with lithium halide in anhydrous hydrofluoric acid, the method does not use raw materials such as fluorosulfonic acid and sulfur trioxide which are easy to generate corrosive substances, reduces the risk and environmental pollution in the production process, and reduces the requirements on reaction equipment.
Compared with the method adopting the reaction of the fluorosulfonic acid and the lithium carboxylate or the lithium halide, the method avoids the product adsorption caused by the existence of the carboxylic acid in the by-product, and further improves the purity of the product.
Compared with the method for preparing the trihydrate of the fluorosulfonate by mixing the ammonium fluorosulfonate and the aqueous solution of lithium hydroxide, the method provided by the invention can be used for efficiently preparing the fluorosulfonate with high yield and high purity under mild conditions through simple conventional operation, does not need to carry out complicated purification steps, and is beneficial to industrial production.
Preferably, the mixing in step (1) is carried out in a specific manner: the alkali metal salt and the organic solvent are mixed, and the temperature is adjusted to 0 to 80 ℃ and then the fluorosulfonate ester is added dropwise, and for example, the temperature can be adjusted to 0 ℃, 5 ℃,10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Preferably, the molar ratio of cation to fluorosulfonate ester in the alkali metal salt of step (1) is (1-5): 1, and can be, for example, 1.
Preferably, in step (1), the mass ratio of the organic solvent to the fluorosulfonate ester is (2 to 15): 1, and may be, for example, 2.
Preferably, the reaction temperature in step (1) is 0 to 80 ℃, for example, 0 ℃, 5 ℃,10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but not limited to the enumerated values, and other non-enumerated values in the numerical range are equally applicable.
Preferably, the reaction time in step (1) is 2-24h, such as 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the temperature is adjusted to 0-25 ℃ after the reaction in step (1) is completed, and may be, for example, 0 ℃,2 ℃, 4 ℃, 6 ℃,8 ℃,10 ℃, 12 ℃, 14 ℃, 16 ℃, 18 ℃, 20 ℃, 22 ℃, 24 ℃ or 25 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the solid-liquid separation of step (1) comprises filtration and/or centrifugation.
Preferably, the concentration in step (2) comprises concentration under reduced pressure, and the absolute pressure of the concentration under reduced pressure is 1 to 5000Pa, and may be, for example, 1Pa, 10Pa, 100Pa, 500Pa, 1000Pa, 1500Pa, 2000Pa, 2500Pa, 3000Pa, 3500Pa, 4000Pa, 4500Pa or 5000Pa, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the poor solvent of step (2) comprises a hydrocarbon solvent and/or a halogenated hydrocarbon solvent.
Preferably, the temperature during the crystallization in step (2) is also reduced to 0 to 25 ℃, for example, 0 ℃, 5 ℃,10 ℃, 15 ℃, 20 ℃ or 25 ℃, and more preferably 0 to 10 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the filtration in step (2) is followed by drying, and the drying temperature is 20-120 ℃, for example, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃,80 ℃, 90 ℃,100 ℃, 110 ℃ or 120 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) Mixing alkali metal salt and an organic solvent, adjusting the temperature to 0-80 ℃, then dropwise adding fluorosulfonate, reacting at the temperature of 0-80 ℃ for 2-24 hours after dropwise adding, adjusting the temperature to 0-25 ℃ after the reaction, and filtering and/or centrifuging to obtain a reaction solution; the molar ratio of cations in the alkali metal salt to fluorosulfonate ester is (1-5) to 1, and the mass ratio of the organic solvent to fluorosulfonate ester is (2-15) to 1; the fluorosulfonate ester has the following structural formula:
in the structural formula, R is selected from any one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl or benzyl; the cation in the alkali metal salt is selected from any one of lithium ion, sodium ion or potassium ion; the organic solvent is a polar aprotic solvent and comprises any one of chain carbonate, cyclic carbonate, chain carboxylate, chain ether, cyclic ether or chain nitrile solvent;
(2) Carrying out reduced pressure concentration on the reaction liquid obtained in the step (1) at the absolute pressure of 1-5000Pa, adding a poor solvent, cooling to 0-25 ℃, crystallizing, filtering, and drying at 20-120 ℃ to obtain fluorosulfonate; the poor solvent is a poor solvent of the fluorosulfonate, and comprises a hydrocarbon solvent and/or a halogenated hydrocarbon solvent.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention takes the fluorosulfonate and the specific alkali metal salt as raw materials, and can prepare the fluorosulfonate by simple chemical reaction in a polar aprotic solvent, thereby simplifying the operation process, reducing the generation of byproducts, achieving the highest yield of the target product of 93.3 percent and the highest purity of 99.9 percent, and simultaneously reducing the requirements of production conditions, and being beneficial to large-scale production and application;
(2) Compared with the method for preparing the fluorosulfonate by reacting fluorosulfonic acid or sulfur trioxide with lithium halide in anhydrous hydrofluoric acid, the method does not use raw materials such as fluorosulfonic acid and sulfur trioxide which are easy to generate corrosive substances, reduces the risk and the pollution to the environment in the production process, and reduces the requirement on reaction equipment;
(3) Compared with the method adopting the reaction of the fluorosulfonic acid and the lithium carboxylate or the lithium halide, the method avoids the product adsorption caused by the existence of the carboxylic acid in the by-product, and further improves the purity of the product;
(4) Compared with the method for obtaining the trihydrate of the fluorosulfonate by mixing the ammonium fluorosulfonate and the lithium hydroxide aqueous solution, the method provided by the invention realizes high-yield and high-purity fluorosulfonate efficiently by simple conventional operation under mild conditions, does not need complicated purification steps, and is beneficial to industrial production.
Detailed Description
The embodiments of the present invention are described in detail below, but the present invention is not limited to the embodiments below, and can be implemented by arbitrarily changing them.
The present invention relates to a process for producing a fluorosulfonate salt, which comprises a step of reacting a fluorosulfonate ester with an alkali metal salt in an organic solvent, wherein after completion of the reaction, the obtained reaction solution is concentrated, a poor solvent is added thereto, the resulting product is crystallized and filtered, and the resulting filter cake is dried to obtain a fluorosulfonate salt solid.
Step one, alkali metal salt and fluorosulfonate ester reaction
The alkali metal salt used in the present invention is not particularly limited, and includes any one of a halogenated alkali metal salt, an alkali metal carbonate, an alkali metal bicarbonate, an alkali metal phosphate, an alkali metal carboxylate, an alkali metal sulfate, an alkali metal sulfite, an alkali metal bisulfite, an alkali metal oxalate, an alkali metal oxide, an alkali metal hydride, an alkali metal hydroxide, or an alkali metal alkoxide, and a cation in the alkali metal salt is selected from any one of a lithium ion, a sodium ion, or a potassium ion. Specific examples include the following:
1) Halogenated alkali metal salts
Lithium fluoride, lithium chloride, lithium bromide, sodium fluoride, sodium chloride, sodium bromide, potassium fluoride, potassium chloride, potassium bromide, and the like;
2) Alkali metal carbonate
Lithium carbonate, sodium carbonate, potassium carbonate, and the like;
3) Alkali metal bicarbonate salts
Lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, and the like;
4) Alkali metal phosphate salt
Lithium phosphate, sodium phosphate, potassium phosphate, etc.;
5) Alkali metal salt of carboxylic acid
Lithium acetate, sodium acetate, potassium acetate, lithium formate, sodium formate, potassium formate, and the like;
6) Alkali metal salts of sulfuric acid
Lithium sulfate, sodium methyl sulfate, sodium ethyl sulfate, potassium methyl sulfate, potassium ethyl sulfate, and the like;
7) Alkali Metal sulfite
Lithium sulfite, sodium sulfite, potassium sulfite, etc.;
8) Alkali metal bisulfite
Lithium bisulfite, sodium bisulfite, potassium bisulfite, and the like;
9) Alkali metal salt of oxalic acid
Lithium oxalate, sodium oxalate, potassium oxalate, etc.;
10 Oxides of alkali metals)
Lithium oxide, sodium oxide, potassium oxide, and the like;
11 Hydrides of alkali metals
Sodium hydride, potassium hydride, lithium hydride;
12 ) hydroxides of alkali metals
Lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like;
13 Alcoholates of alkali metals
Sodium methoxide, sodium ethoxide, lithium methoxide, lithium ethoxide, potassium methoxide, potassium ethoxide, and the like.
Among the above-mentioned alkali metal salts, alkali metal carbonates, alkali metal bicarbonates, alkali metal halides, alkali metal oxides, alkali metal hydroxides, alkali metal hydrides, alkali metal carboxylates, or alkali metal alcoholates are preferred from the viewpoint of ease of reaction and easier availability of high-purity products.
The alkali metal salts may be used alone or in combination, and are preferably used alone so as not to complicate the operation.
The alkali metal salt used in the reaction of the present invention may be a commercially available product as it is, may be used after purification, or may be used after production from another compound. The purity is not particularly limited, and an alkali metal salt having a purity of 99% or more is preferred.
The fluorosulfonate ester used in the reaction of the present invention may be used as it is or after purification, and has the following structural formula:
in the structural formula, R is selected from any one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl or benzyl. The purity of the fluorosulfonate ester is not particularly limited, but in view of the convenience of product purification, the fluorosulfonate ester having a purity of 99% or more is preferable.
In the reaction step of the present invention, the feed molar ratio of the cation in the alkali metal salt to the fluorosulfonate ester is not particularly limited, and from the viewpoint of the raw material cost, it is preferable that the feed molar ratio does not deviate significantly from 1.
In the reaction step of the present invention, when the feed amount of the fluorosulfonate ester is increased relative to the cation in the alkali metal salt, there is a possibility that a part of the acidic substance in the obtained fluorosulfonate salt remains, and the quality and performance of the obtained fluorosulfonate salt are deteriorated. Therefore, the lower limit of the feed molar ratio of the cation in the alkali metal salt to the fluorosulfonate ester is preferably 1 time or more, more preferably 1.02 time or more, and still more preferably 1.05 time or more; the upper limit value is preferably 4 times or less, more preferably 3 times or less, and still more preferably 2.4 times or less. When the feed molar ratio of the cation in the alkali metal salt to the fluorosulfonate ester is adjusted to the above range, a highly pure fluorosulfonate ester can be produced in a high yield without going through a complicated purification step.
In the reaction step of the present invention, a nonaqueous organic solvent is selected, and a solvent having a boiling point of 300 ℃ or lower, more preferably 200 ℃ or lower, and still more preferably 160 ℃ or lower is selected in order to effectively remove the solvent residue.
The nonaqueous organic solvent used in the reaction step of the present invention is preferably a polar organic solvent, and more preferably a polar aprotic organic solvent including a chain carbonate, a cyclic carbonate, a chain carboxylate, a chain ether, a cyclic ether, or a chain nitrile solvent.
Among the above solvents, preferred are chain carbonates such as dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate; cyclic carbonates such as ethylene carbonate, propylene carbonate, vinylene carbonate, and fluorinated ethylene carbonate; chain carboxylates such as ethyl acetate, methyl acetate, n-butyl acetate, isopropyl acetate, etc.; chain nitriles such as acetonitrile and propionitrile; chain ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether; more preferred are dimethyl carbonate, diethyl carbonate, ethyl acetate, n-butyl acetate, acetonitrile, and ethylene glycol dimethyl ether.
The above-mentioned nonaqueous organic solvents may be used alone or in combination, and are preferably used alone in order not to complicate the operation.
The mass ratio of the nonaqueous organic solvent used in the present invention to the fluorosulfonate ester is not particularly limited, but is preferably 100 times or less, more preferably 50 times or less, and still more preferably 25 times or less. The mass ratio of the nonaqueous organic solvent used in the reaction to the fluorosulfonate ester is preferably 2 times or more, and more preferably 3 times or more. Within the above range, the preparation efficiency is excellent, and fluorosulfonate is not excessively precipitated, resulting in unnecessary yield loss.
The temperature in the reaction step of the present invention is not particularly limited, but is preferably 100 ℃ or lower, more preferably 80 ℃ or lower, and still more preferably 60 ℃ or lower. The temperature at which the reaction is carried out is preferably-20 ℃ or higher, more preferably-10 ℃ or higher, and still more preferably 0 ℃ or higher. When the temperature at the start of the reaction step of the present invention is within the above range, unexpected side reactions are less likely to occur, and the reaction rate is not too low.
In the reaction step of the present invention, the order of charging into the reaction system is not particularly limited, and solid alkali metal salt may be charged into the stirred fluorosulfonate solution, or liquid fluorosulfonate may be added dropwise to a mixture of the stirred alkali metal salt and a nonaqueous organic solvent. The fluorosulfonate ester to be added dropwise may be added dropwise after dilution without using a solvent or after dilution with a solvent. In order to avoid complicating the operation, it is preferable to add the liquid fluorosulfonate dropwise to the mixture of the alkali metal salt and the nonaqueous organic solvent under stirring in the order of addition, and the temperature of the dropwise addition is selected to be-10 ℃ or higher, 100 ℃ or lower, preferably-5 ℃ or higher, 80 ℃ or lower, and more preferably 0 to 80 ℃.
The charging time in the reaction step of the present invention is not particularly limited, but is preferably 24 hours or less, more preferably 12 hours or less, and further preferably 10 hours or less. The charging time in the reaction step of the present invention is preferably 30min or more, more preferably 1h or more, and still more preferably 2h or more. By setting the charging time in the reaction step of the present invention within the above range, a relatively good reaction effect can be obtained and a relatively high efficiency can be obtained.
The gas atmosphere in the reaction step of the present invention is not particularly limited, and is preferably protected with an inert gas such as dry nitrogen and/or argon.
The equipment material used in the reaction step of the present invention is not particularly limited as long as it is a material that can be used for production of general chemicals, but a material that is resistant to acid and alkali corrosion other than glass is preferable in consideration of durability of equipment use, corrosiveness of raw materials, and generation of hydrogen fluoride due to hydrolysis of fluorosulfonate.
When the alkali metal salt is used in excess in the reaction step, the excess alkali metal salt may remain as an insoluble component. In this case, the method for removing the excess alkali metal salt insoluble component is not particularly limited, and a method of filtering under reduced pressure, pressure filtration, centrifugal filtration or the like, standing, centrifugal sedimentation, and then taking out the supernatant can be used. Further, these methods may be combined or the same method may be repeated.
Step two, concentrating, crystallizing and drying process
The method for concentrating the fluorosulfonate solution after the reaction step and after the solid-liquid separation is not particularly limited, and it may be atmospheric distillation concentration or vacuum distillation concentration, but if the concentration temperature is too high, an unexpected side reaction may occur, and vacuum concentration tends to have higher concentration efficiency, and it is preferably vacuum distillation concentration at 80 ℃ or lower, and more preferably vacuum concentration at 60 ℃ or lower. The lower limit of the degree of vacuum is not limited, but is preferably 5000Pa or less, more preferably 1000Pa or less, in view of the degree of vacuum that can be easily achieved; the upper limit of the degree of vacuum is not limited, but is preferably 1Pa or more, more preferably 10Pa or more, and still more preferably 20Pa or more, in consideration of the limit of the degree of vacuum measurement and the degree of vacuum system equipment that can be practically achieved.
The yield of the product is reduced due to a large amount of the solvent remained after concentration, and the upper limit of the concentration residue of the reaction solvent is selected as follows: the amount of the fluorosulfonate ester to be charged is preferably 5 times or less, more preferably 3 times or less, and still more preferably 2 times or less, based on the weight of the fluorosulfonate ester to be charged. On the other hand, when the residual amount is too small, a viscous slurry state is formed, and therefore, stirring becomes difficult. Therefore, the lower limit of the concentration-remaining amount of the reaction solvent is preferably 0.5 times or more, more preferably 1 time or more, the weight of the charged fluorosulfonate ester.
In the crystallization process of the present invention, a poor solvent is added, and a hydrocarbon solvent and/or a halogenated hydrocarbon solvent is particularly preferred, and specific examples thereof include: hydrocarbons such as toluene, n-hexane, n-heptane, petroleum ether, cyclohexane, etc.; and halogenated hydrocarbons such as dichloromethane, dichloroethane, tetrachloroethane, and chloroform.
Among the above solvents, toluene, cyclohexane, methylene chloride, dichloroethane, and tetrachloroethane are preferable.
The poor solvents may be used alone or in combination, and are preferably used alone so as not to complicate the operation.
The weight ratio of the poor solvent to the fluorosulfonate ester used in the present invention is not particularly limited, but is preferably 50 times or less, more preferably 25 times or less, and still more preferably 10 times or less. The weight ratio of the poor solvent used in the crystallization step to the fluorosulfonate ester is preferably 2 times or more, and more preferably 3 times or more. Within the range, the method can ensure that the crystallization has higher yield and better crystallization purification effect, and obtain the fluorosulfonate with better quality and performance.
The temperature at the time of crystallization by adding the poor solvent in the present invention is not particularly limited, but is preferably 100 ℃ or lower, more preferably 80 ℃ or lower, and still more preferably 60 ℃ or lower. The temperature at the time of crystallization by adding the poor solvent is preferably 0 ℃ or higher, more preferably 10 ℃ or higher, and still more preferably 20 ℃ or higher. When the temperature for crystallization by adding the poor solvent is within the above range, the fluorosulfonate salt is not precipitated in a large amount because the crystallization temperature is too low.
The charging time in the crystallization step by adding a poor solvent is not limited, but is preferably 6 hours or less, more preferably 4 hours or less, and further preferably 2 hours or less. In the present invention, the charging time in the poor solvent-added crystallization step is preferably 1min or more, more preferably 10min or more, and still more preferably 30min or more. By setting the charging time in the reaction step of the present invention within the above range, a relatively good crystal purification effect can be obtained and a relatively high efficiency can be obtained.
In the crystallization step using the poor solvent of the present invention, the solid-liquid separation method is not particularly limited, and the crystallized fluorosulfonate salt can be obtained by filtration such as reduced pressure filtration, or centrifugal filtration.
In the present invention, the temperature at the time of solid-liquid separation in the crystallization step by adding a poor solvent is not particularly limited, but is preferably 40 ℃ or lower, more preferably 25 ℃ or lower, and still more preferably 20 ℃ or lower in order to increase the crystal yield. On the other hand, if the yield of the recovered crystals is excessively increased, the crystallization effect is deteriorated and the quality of the obtained fluorosulfonate salt is liable to be deteriorated, and it is preferably-20 ℃ or higher, more preferably-10 ℃ or higher, and still more preferably 0 ℃ or higher.
The fluorosulfonate salt obtained through the above-mentioned step is preferably removed by drying under reduced pressure because the organic solvent used in the above-mentioned step remains. Too high a temperature may cause thermal decomposition of the fluorosulfonate salt, and too low a temperature may result in insufficient removal. The temperature for removal is preferably 100 ℃ or lower, more preferably 80 ℃ or lower, and still more preferably 60 ℃ or lower. Further, it is preferably 0 ℃ or higher, more preferably 10 ℃ or higher, and further preferably 20 ℃ or higher. The longer the drying time, the better the removal effect, but at the same time, the production efficiency is lowered, and the drying time is preferably 30min or more, more preferably 1h or more, and further preferably 2h or more. The time for drying and removing is preferably 24 hours or less, more preferably 18 hours or less, and further preferably 12 hours or less.
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The present embodiment provides a lithium fluorosulfonate and a preparation method thereof, the preparation method including the steps of:
(1) Replacing a 500mL reaction vessel with nitrogen for 3 times, sequentially adding 16.2g (0.22 mol) of lithium carbonate, 1.8g (0.10 mol) of pure water and 228.0g of ethylene glycol dimethyl ether into the reaction vessel, adjusting the temperature to 25 ℃, dropwise adding 25.6g (0.20 mol) of ethyl fluorosulfonate, keeping the temperature at 70 ℃ for 2 hours after the dropwise adding is finished until the reaction is complete, wherein the reaction formula is shown as (A), and filtering to remove insoluble substances after the reaction is finished to obtain a reaction solution;
(2) And (2) concentrating the reaction liquid obtained in the step (1) under the absolute pressure of 1000Pa and the temperature of 35 +/-5 ℃ under reduced pressure until the mass of the reaction liquid is 45.5g, adding 84.0g of dried 1, 2-dichloroethane, cooling to 0 ℃ for crystallization, filtering to obtain a lithium fluorosulfonate wet product, and drying at the temperature of 100 ℃ to obtain 19.8g of high-purity lithium fluorosulfonate.
The lithium fluorosulfonate obtained in this example was found to have a yield of 93.4%, a measured purity of 99.5%, a sulfate group of 67ppm, and an acid value of 56ppm (in terms of HF).
Example 2
The implementation provides sodium fluorosulfonate and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) Replacing a 250mL reaction container with nitrogen for 3 times, sequentially adding 25.2g (0.3 mol) of sodium bicarbonate and 128.0g of acetonitrile into the reaction container, adjusting the temperature to 0 ℃, dropwise adding 25.6g (0.20 mol) of ethyl fluorosulfonate, keeping the temperature at 5 ℃ after dropwise adding is finished for 24 hours till the reaction is complete, wherein the reaction formula is shown as (B), and filtering to remove insoluble substances after the reaction is finished to obtain a reaction solution;
(2) And (2) carrying out reduced pressure concentration on the reaction liquid obtained in the step (1) at the absolute pressure of 100Pa and the temperature of 25 +/-5 ℃ until the mass of the reaction liquid is 54.3g, adding 96.0g of dried dichloromethane, cooling to 10 ℃ for crystallization, filtering to obtain a sodium fluorosulfonate wet product, and drying at the temperature of 20 ℃ to obtain 21.8g of high-purity sodium fluorosulfonate.
The sodium fluorosulfonate obtained in this example was found to have a yield of 89.3%, a detected purity of 99.7%, a sulfate group of 76ppm, and an acid number of 65ppm (in terms of HF).
Example 3
The implementation provides potassium fluorosulfonate and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) Replacing a 250mL reaction container with nitrogen for 3 times, sequentially adding 6.2g (0.11 mol) of potassium hydroxide and 31.2g of ethylene glycol dimethyl ether into the reaction container, adjusting the temperature to 5 ℃, dropwise adding 15.6g (0.10 mol) of tert-butyl fluorosulfonate, continuously preserving the temperature at 25 ℃ for 5 hours after dropwise adding is finished until the reaction is complete, wherein the reaction formula is shown as (C), and filtering to remove insoluble substances after the reaction is finished to obtain a reaction solution;
(2) And (2) concentrating the reaction liquid obtained in the step (1) under the absolute pressure of 500Pa at the temperature of 35 +/-5 ℃ under reduced pressure until the mass of the reaction liquid is 30.3g, adding 54.0g of dried cyclohexane, cooling to 0 ℃ for crystallization, filtering to obtain a wet potassium fluorosulfonate product, and drying at 40 ℃ to obtain 12.7g of high-purity potassium fluorosulfonate.
The potassium fluorosulfonate obtained in this example was found to have a yield of 91.9%, a purity of 99.5%, a sulfate group of 78ppm, and an acid value of 55ppm (in terms of HF).
Example 4
The present embodiment provides a lithium fluorosulfonate and a preparation method thereof, the preparation method including the steps of:
(1) Replacing 500mL of reaction vessel with nitrogen for 3 times, sequentially adding 10.2g (0.24 mol) of lithium chloride and 91.2g of tetrahydrofuran into the reaction vessel, adjusting the temperature to 45 ℃, dropwise adding 22.8g (0.20 mol) of methyl fluorosulfonate, continuously preserving the temperature at 55 ℃ for 2 hours after dropwise adding is finished until the reaction is complete, wherein the reaction formula is shown as (E), adjusting the temperature to 20 ℃ after the reaction is finished, and filtering to remove insoluble substances to obtain a reaction solution;
(2) And (2) carrying out reduced pressure concentration on the reaction liquid obtained in the step (1) at absolute pressure of 4500Pa and 55 +/-5 ℃ until the mass of the reaction liquid is 45.4g, adding 84.0g of dried dichloroethane, cooling to 0 ℃ for crystallization, filtering to obtain a lithium fluorosulfonate wet product, and drying at 50 ℃ to obtain 18.8g of high-purity lithium fluorosulfonate.
The lithium fluorosulfonate obtained in this example was found to have a yield of 88.7%, a measured purity of 99.4%, a sulfate group of 118ppm, and an acid value of 75ppm (in terms of HF).
Example 5
The implementation provides sodium fluorosulfonate and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) Replacing 250mL of a reaction vessel for 3 times by using nitrogen, sequentially adding 8.4g (0.21 mol) of sodium hydrogen (60% content) and 97.6g of ethylene glycol diethyl ether into the reaction vessel, adjusting the temperature to 15 ℃, then dropwise adding 28.4g (0.20 mol) of isopropyl fluorosulfonate, continuously preserving the temperature at 50 ℃ for 2 hours after dropwise adding is finished until the reaction is complete, wherein the reaction formula is shown as (E), adjusting the temperature to 20 ℃ after the reaction is finished, and filtering to remove insoluble substances to obtain a reaction solution;
(2) And (2) carrying out reduced pressure concentration on the reaction liquid obtained in the step (1) at the absolute pressure of 300Pa and the temperature of 25 +/-5 ℃ until the mass of the reaction liquid is 56.4g, adding 96.0g of dried dichloromethane, cooling to 0 ℃ for crystallization, filtering to obtain a sodium fluorosulfonate wet product, and drying at the temperature of 30 ℃ to obtain 22.0g of high-purity sodium fluorosulfonate.
The sodium fluorosulfonate obtained in this example was found to have a yield of 90.0%, a detected purity of 99.4%, a sulfate group of 118ppm, and an acid number of 75ppm (as HF).
Example 6
The present embodiment provides a lithium fluorosulfonate and a preparation method thereof, the preparation method including the steps of:
(1) Replacing 500mL of a reaction container by nitrogen for 3 times, sequentially adding 26.4g (0.4 mol) of lithium acetate and 234g of diethyl carbonate into the reaction container, adjusting the temperature to 80 ℃, dropwise adding 31.2g (0.20 mol) of n-butyl fluorosulfonate, keeping the temperature at 80 ℃ for 8 hours after dropwise adding is finished until the reaction is complete, wherein the reaction formula is shown as (F), adjusting the temperature to 20 ℃ after the reaction is finished, and filtering to remove insoluble substances to obtain a reaction solution;
(2) And (2) concentrating the reaction liquid obtained in the step (1) under the reduced pressure of 200Pa and at the temperature of 45 +/-5 ℃ until the mass of the reaction liquid is 54.6g, adding 85.0g of dried n-heptane, cooling to 0 ℃ for crystallization, filtering to obtain a lithium fluorosulfonate wet product, and drying at the temperature of 80 ℃ to obtain 18.9g of high-purity lithium fluorosulfonate.
The lithium fluorosulfonate obtained in this example was found to have a yield of 89.2%, a measured purity of 99.5%, a sulfate group of 98ppm, and an acid value of 65ppm (in terms of HF).
Example 7
The present embodiment provides a lithium fluorosulfonate and a preparation method thereof, the preparation method including the steps of:
(1) Replacing a 250mL reaction vessel for 3 times by using nitrogen, sequentially adding 3.3G (0.11 mol) of lithium oxide and 97.6G of diethylene glycol dimethyl ether into the reaction vessel, adjusting the temperature to 5 ℃, dropwise adding 35.2G (0.20 mol) of phenyl fluorosulfonate, continuously keeping the temperature at 5 ℃ for 10 hours after dropwise adding is finished until the reaction is complete, wherein the reaction formula is shown as (G), adjusting the temperature to 20 ℃ after the reaction is finished, and filtering to remove insoluble substances to obtain a reaction solution;
(2) And (2) carrying out reduced pressure concentration on the reaction liquid obtained in the step (1) at the absolute pressure of 50Pa and the temperature of 85 +/-5 ℃ until the mass of the reaction liquid is 57.6g, adding 88.0g of dried xylene, cooling to 0 ℃ for crystallization, filtering to obtain a lithium fluorosulfonate wet product, and drying at the temperature of 120 ℃ to obtain 17.7g of high-purity lithium fluorosulfonate.
The lithium fluorosulfonate obtained in this example was found to have a yield of 83.5%, a detected purity of 99.7%, a sulfate group of 45ppm, and an acid value of 34ppm (in terms of HF).
Example 8
The implementation provides lithium fluorosulfonate and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) Replacing 250mL of a reaction container with nitrogen for 3 times, sequentially adding 8.0g (0.21 mol) of lithium methoxide and 97.6g of ethyl methyl carbonate into the reaction container, adjusting the temperature to 5 ℃, then dropwise adding 38.0g (0.20 mol) of benzyl fluorosulfonate, continuing to keep the temperature at 5 ℃ for 10 hours after dropwise adding is finished until the reaction is complete, wherein the reaction formula is shown as (H), adjusting the temperature to 20 ℃ after the reaction is finished, and filtering to remove insoluble substances to obtain a reaction solution;
(2) And (2) carrying out reduced pressure concentration on the reaction liquid obtained in the step (1) at the absolute pressure of 20Pa and the temperature of 65 +/-5 ℃ until the mass of the reaction liquid is 53.6g, adding 96.0g of dried toluene, cooling to 0 ℃ for crystallization, filtering to obtain a lithium fluorosulfonate wet product, and drying at the temperature of 80 ℃ to obtain 18.1g of high-purity lithium fluorosulfonate.
The lithium fluorosulfonate obtained in this example was found to have a yield of 85.4%, a detected purity of 99.6%, a sulfate group of 275ppm, and an acid value of 44ppm (as HF).
Therefore, the invention takes the fluorosulfonate and the specific alkali metal salt as raw materials, and can prepare the fluorosulfonate by simple chemical reaction in a polar aprotic solvent, thereby simplifying the operation process, reducing the generation of by-products, enabling the yield of the target product to be as high as 93.3 percent and the purity to be as high as 99.9 percent, and simultaneously reducing the requirements on production conditions, thereby being beneficial to large-scale production and application.
In addition, compared with the method for preparing the fluorosulfonate by reacting fluorosulfonic acid or sulfur trioxide with lithium halide in anhydrous hydrofluoric acid, the method does not use raw materials such as fluorosulfonic acid and sulfur trioxide which are easy to generate corrosive substances, so that the risk and the pollution to the environment in the production process are reduced, and the requirement on reaction equipment is reduced; compared with the method adopting the reaction of the fluorosulfonic acid and the lithium carboxylate or the lithium halide, the method avoids the product adsorption caused by the existence of the carboxylic acid in the by-product, and further improves the purity of the product; compared with the method for obtaining the trihydrate of the fluorosulfonate by mixing the ammonium fluorosulfonate and the lithium hydroxide aqueous solution, the method provided by the invention realizes high-yield and high-purity fluorosulfonate efficiently by simple conventional operation under mild conditions, does not need complicated purification steps, and is beneficial to industrial production.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and should not be construed as limiting the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing fluorosulfonate from fluorosulfonate, said method comprising the steps of:
(1) Mixing fluorosulfonate, alkali metal salt and organic solvent for reaction, and performing solid-liquid separation to obtain a reaction solution;
(2) Concentrating the reaction liquid obtained in the step (1), adding a poor solvent, crystallizing and filtering to obtain fluorosulfonate;
wherein the structural formula of the fluorosulfonate ester in the step (1) is as follows:
in the structural formula, R is selected from any one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl or benzyl;
the alkali metal salt in the step (1) comprises any one of halogenated alkali metal salt, alkali metal carbonate, alkali metal bicarbonate, alkali metal phosphate, alkali metal carboxylate, alkali metal sulfate, alkali metal sulfite, alkali metal bisulfite, alkali metal oxalate, alkali metal oxide, alkali metal hydride, alkali metal hydroxide or alkali metal alcoholate, and the cation in the alkali metal salt is selected from any one of lithium ion, sodium ion or potassium ion;
the organic solvent in the step (1) is a polar aprotic solvent, and comprises any one of chain carbonate, cyclic carbonate, chain carboxylate, chain ether, cyclic ether or chain nitrile solvent;
the poor solvent in the step (2) is a poor solvent of fluorosulfonate.
2. The method according to claim 1, wherein the mixing in step (1) is carried out in a specific manner: firstly, mixing alkali metal salt and organic solvent, adjusting the temperature to 0-80 ℃, and then dropwise adding fluorosulfonate.
3. The method according to claim 1, wherein the molar ratio of the cation to the fluorosulfonate ester in the alkali metal salt in step (1) is (1-5): 1, and the mass ratio of the organic solvent to the fluorosulfonate ester is (2-15): 1.
4. The method of claim 1, wherein the reaction of step (1) is carried out at a temperature of 0 to 80 ℃ for a time of 2 to 24 hours.
5. The method according to claim 1, wherein the temperature is adjusted to 0 to 25 ℃ after the reaction of step (1) is completed.
6. The method of claim 1, wherein the solid-liquid separation of step (1) comprises filtration and/or centrifugation.
7. The method of claim 1, wherein the concentrating of step (2) comprises concentrating under reduced pressure, and the absolute pressure of the concentrating under reduced pressure is 1 to 5000Pa.
8. The method according to claim 1, wherein the poor solvent of step (2) comprises a hydrocarbon solvent and/or a halogenated hydrocarbon solvent.
9. The method according to claim 1, wherein the temperature is also reduced to 0-25 ℃ in the crystallization process in the step (2);
and (3) drying the filtered mixture in the step (2), wherein the drying temperature is 20-120 ℃.
10. The method according to any one of claims 1 to 9, wherein the preparation method comprises the steps of:
(1) Mixing alkali metal salt and an organic solvent, adjusting the temperature to 0-80 ℃, then dropwise adding fluorosulfonate, reacting at the temperature of 0-80 ℃ for 2-24 hours after dropwise adding, adjusting the temperature to 0-25 ℃ after the reaction, and filtering and/or centrifuging to obtain a reaction solution; the molar ratio of cations in the alkali metal salt to fluorosulfonate ester is (1-5) to 1, and the mass ratio of the organic solvent to fluorosulfonate ester is (2-15) to 1; the fluorosulfonate ester has the following structural formula:
in the structural formula, R is selected from any one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl or benzyl; the cation in the alkali metal salt is selected from any one of lithium ion, sodium ion or potassium ion; the organic solvent is a polar aprotic solvent and comprises any one of chain carbonate, cyclic carbonate, chain carboxylate, chain ether, cyclic ether or chain nitrile solvent;
(2) Carrying out reduced pressure concentration on the reaction liquid obtained in the step (1) at the absolute pressure of 1-5000Pa, adding a poor solvent, cooling to 0-25 ℃, crystallizing, filtering, and drying at 20-120 ℃ to obtain fluorosulfonate; the poor solvent is a poor solvent of the fluorosulfonate, and comprises a hydrocarbon solvent and/or a halogenated hydrocarbon solvent.
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