CN117263146A - Continuous production device system and production method for liquid difluoro sulfonyl imide salt - Google Patents
Continuous production device system and production method for liquid difluoro sulfonyl imide salt Download PDFInfo
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- CN117263146A CN117263146A CN202311567806.4A CN202311567806A CN117263146A CN 117263146 A CN117263146 A CN 117263146A CN 202311567806 A CN202311567806 A CN 202311567806A CN 117263146 A CN117263146 A CN 117263146A
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- 239000007788 liquid Substances 0.000 title claims abstract description 78
- 150000003839 salts Chemical class 0.000 title claims abstract description 57
- 238000010924 continuous production Methods 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 146
- -1 bis-fluorosulfonyl imide salt Chemical class 0.000 claims abstract description 105
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000000926 separation method Methods 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 35
- 238000001704 evaporation Methods 0.000 claims abstract description 31
- 230000008020 evaporation Effects 0.000 claims abstract description 31
- 239000010409 thin film Substances 0.000 claims abstract description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000460 chlorine Substances 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 15
- 239000010408 film Substances 0.000 claims description 49
- 239000012043 crude product Substances 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 40
- 238000010790 dilution Methods 0.000 claims description 35
- 239000012895 dilution Substances 0.000 claims description 35
- 238000001914 filtration Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- 150000003949 imides Chemical class 0.000 claims description 26
- 238000011282 treatment Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000003860 storage Methods 0.000 claims description 19
- 238000011084 recovery Methods 0.000 claims description 16
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 11
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 9
- XPVRBHCXMWRJEY-UHFFFAOYSA-N difluoro(imino)-$l^{4}-sulfane Chemical compound FS(F)=N XPVRBHCXMWRJEY-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid group Chemical group C(CCCCC(=O)O)(=O)O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 8
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 claims description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical group CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 8
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 8
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical group CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical group O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000011552 falling film Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical class FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 3
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical group OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 238000007790 scraping Methods 0.000 claims 4
- 230000014759 maintenance of location Effects 0.000 claims 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 description 40
- 229910010941 LiFSI Inorganic materials 0.000 description 29
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 29
- 239000000047 product Substances 0.000 description 25
- 230000001105 regulatory effect Effects 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- 229910021201 NaFSI Inorganic materials 0.000 description 14
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 235000011056 potassium acetate Nutrition 0.000 description 6
- PNDUWCHQCLZPAH-UHFFFAOYSA-M lithium;hexanoate Chemical compound [Li+].CCCCCC([O-])=O PNDUWCHQCLZPAH-UHFFFAOYSA-M 0.000 description 5
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-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
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- BUPUAXFATBDCHV-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Li+].O.O.[Li+].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Li+].O.O.[Li+].[Li+] BUPUAXFATBDCHV-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a continuous production device system and a production method of liquid bis-fluorosulfonyl imide salt, wherein the continuous production device system adopts a micro-channel flow reaction device to replace a conventional reaction kettle, and simultaneously realizes continuous production of bis-fluorosulfonyl imide salt products by matching with equipment such as a flash evaporation separation device, a thin film evaporation device, a thinning device and the like, and has good economy, high production efficiency and safe and controllable process. The method adopts high-purity difluoro sulfonimide and dry metal salt as raw materials, and the difluoro sulfonimide salt product prepared by matching with a continuous production device system has high purity, water content less than or equal to 15ppm, acid value less than or equal to 35ppm, hazen color number less than 30, free chlorine content less than 1ppm, sulfate radical content less than 20ppm, and fluoro sulfonate radical content less than 400ppm, and meets the application standard in electrolyte.
Description
Technical Field
The invention belongs to the technical field of fluoride battery electrolytes, and relates to a continuous production device system and a production method of liquid bis-fluorosulfonyl imide salt.
Background
Metal salts of bis (fluorosulfonyl) imide, molecular formula MN (SO) 2 F) 2 Abbreviated MFSI. Is a stable electrolyte with excellent thermal stability and high conductivity, has been proved to have wide application in the fields of catalysis, electrolytes and fluoridation reagents, and particularly lithium salt (LiFSI) has been proved to be particularly suitable for batteries and supercapacitors.
The synthesis method of LiFSI disclosed in EP2415757, US2011034716 and the like comprises the following steps: synthesizing HClSI, then reacting with fluoro metal salt MFX to prepare corresponding difluoro sulfonimide salt intermediate, and then reacting with lithium hydroxide LiOH or lithium carbonate Li 2 CO 3 Cation exchange is carried out to prepare LiFSI; the defect is that the cation exchange is difficult to continue to complete after reaching equilibrium, and the unreacted complete intermediate is difficult to completely separate from LiFSI, so that a high-quality product cannot be obtained.
Currently, methods for preparing MFSI using bis-fluorosulfonyl imide (HFSI) with metal salts are disclosed. CN104925765a and CN108002355 both disclose a method for preparing LiFSI from bis-fluorosulfonyl imide with lithium hydroxide, lithium carbonate, lithium bicarbonate in an organic solvent. CN106365132a discloses a process for preparing LiFSI under pressurized conditions from HFSI and lithium fluoride; CN106241757a discloses a process for preparing LiFSI by reacting HFSI with lithium chloride. Such direct preparation of LiFSI using inorganic lithium salt requires complicated purification treatments to improve the quality of the product since water or small strong acid (e.g., hydrogen chloride, hydrogen fluoride, etc.) is generated during the reaction. Arkema discloses a LiFeSI crystallization purification method, which adopts a limit method of high vacuum film distillation, but the purity of the purified product is only 99.80%, the impurity content is still higher, and the water content in a typical embodiment is 40ppm, the free chlorine content is 22ppm, and the sulfate radical content is 7ppm. CN110697668 and CN109721037a disclose that high purity HFSI is used as a raw material, a nonaqueous reaction system is adopted, and the residue of byproducts is precisely controlled by poor solvent crystallization, and multiple means are required to combine to obtain the high purity LiFSI effect.
In summary, the process for preparing MFSI in the prior art has the defects of complicated process, difficult product separation, difficult batch reaction operation, high energy consumption, large pollution and the like. Moreover, due to the defects of the preparation process, a crude product is needed to be obtained firstly, then the crude product is recrystallized to obtain a finished product, and the finished product is dissolved again to be configured into electrolyte later, so that the great waste of resources is caused, and the efficiency is low. Therefore, developing a process system and a production method for producing bisfluorosulfonyl imide salt rapidly, in high yield, with high selectivity, safely and continuously is a problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a continuous production device system and a production method of liquid difluoro sulfonyl imide salt, which are used for solving the industrial problems of complicated preparation flow, high production cost, large difference of batch quality in gap operation and high impurity content of water generated products in the reaction in the prior art; the purity of the liquid difluoro sulfonyl imide salt prepared by the continuous production device system and the production method provided by the invention reaches the application level of battery level.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a continuous production plant system for liquid bis-fluorosulfonyl imide salts, the continuous production plant system comprising a feed system, a continuous flow reaction system, and a purification system connected in sequence;
The feeding system comprises a bisfluorosulfonyl imide feeding unit and a metal salt feeding unit which are connected in parallel;
the continuous flow reaction system comprises at least three microchannel flow reaction devices; the micro-channel flow reaction devices are arranged in series;
the difluoro sulfimide feeding unit and the metal salt feeding unit are respectively and independently connected with the micro-channel flow reaction device;
the purification system comprises a flash separation device, at least one thin film evaporation device, a dilution device, a first filtering device and a heat exchange device which are connected in sequence;
the microchannel flow reactor is connected to the flash separation device.
The invention adopts high-purity difluoro sulfimide and metal salt as raw materials, and the prepared MFSI has high purity and high selectivity by carrying out salt formation reaction in a micro-channel flow reaction device, and the product meets the application standard in electrolyte; meanwhile, the micro-channel flow reaction device is matched with equipment such as a flash evaporation separation device, a thin film evaporation device, a dilution device and the like to realize continuous production of MFSI liquid salt, so that the method is good in economy, high in production efficiency and safe and controllable in process.
As a preferable technical scheme of the invention, the difluoro sulfonimide feeding unit comprises a difluoro sulfonimide storage device and a first preheating device which are sequentially connected.
Preferably, a bisfluorosulfonyl imide delivery pump is arranged between the bisfluorosulfonyl imide storage device and the first preheating device.
Preferably, the first preheating device is connected with the micro-channel flow reaction device, and a first back pressure valve and a first mass flowmeter are sequentially arranged on the connected pipeline.
Preferably, the metal salt feeding unit comprises a metal salt storage device, a drying device, a premixing device and a second preheating device which are connected in sequence.
In the invention, the drying device comprises a dryer and a vibration hopper of a positive pressure airtight belt weighing module below the dryer.
Preferably, a metal salt solution delivery pump is arranged between the premixing device and the second preheating device.
Preferably, the second preheating device is connected with the micro-channel flow reaction device, and a second back pressure valve, a second mass flowmeter and a first stop valve are sequentially arranged on the connected pipeline.
Preferably, the premixing device is connected with the flash separation device, and a third mass flowmeter is arranged on a connected pipeline.
According to a preferred technical scheme of the invention, the material of the micro-channel flow reaction device comprises silicon carbide (SiC).
Preferably, the diameter of the channel of the microchannel flow reaction device is 0.1-5 mm, for example, 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm or 4.5mm, etc., but not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the channel structure of the microchannel flow reaction device comprises any one or a combination of at least two of heart type, zigzag type, thorn type, baffle type or Y type.
It is worth to say that, compared with the sandwich structure design of the micro-channel flow reaction device, the heat exchange efficiency of the kettle type reactor is improved by about 1000 times, and compared with the kettle type mechanical stirring mass transfer efficiency, the channel design of the internal heart-shaped structure, the baffle plate structure and the like is improved by about 100 times, and the efficient mass transfer and heat transfer completed in the micro-channel can realize the rapid high-selectivity high-yield preparation of the MFSI.
The holding volume of the microchannel flow reaction device is preferably 7 to 70mL, and may be, for example, 10mL, 15mL, 20mL, 25mL, 30mL, 35mL, 40mL, 45mL, 50mL or 60mL, etc., but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, a third back pressure valve is arranged between the microchannel flow reactor and the flash separation device.
As a preferable technical scheme of the invention, the thin film evaporation device comprises a vertical type scratch film evaporator or a horizontal type scratch film evaporator.
Preferably, the purification system comprises a flash separation device, a vertical wiped film evaporator, a horizontal wiped film evaporator, a thin-film evaporator, a first filtering device and a heat exchange device which are sequentially connected.
Preferably, the thinning device comprises a falling film thinning tower.
Preferably, the dilution device is an external circulating pump.
Preferably, a stirring device is arranged between the dilution opening device and the first filtering device.
Preferably, the filter element of the first filter device comprises any one or a combination of at least two of ceramic, polytetrafluoroethylene (PTFE), expanded Polytetrafluoroethylene (EPTF), polyethylene (HDPE), polyvinylidene fluoride (PVDF), or silicon carbide, wherein the combination is typically but not limited to: a combination of ceramic and PTFE, a combination of EPTF and PTFE, a combination of HDPE and PVDF, or a combination of SiC and PVDF, etc.
Preferably, the pore size of the first filter means comprises any one or a combination of at least two of 0.45 μm, 1 μm or 5 μm, wherein the combination is typically but not limited to: a combination of 0.45 μm and 1 μm, a combination of 1 μm and 5 μm, or a combination of 0.45 μm, 1 μm and 5 μm, etc.
Preferably, the heat exchange device further comprises a second filtering device and a difluoro sulfonimide salt storage device which are connected in sequence.
Preferably, the filter element material of the second filter device comprises any one or a combination of at least two of ceramic, polytetrafluoroethylene (PTFE), expanded Polytetrafluoroethylene (EPTF), polyethylene (HDPE), polyvinylidene fluoride (PVDF), or silicon carbide, wherein the combination is typically but not limited to: a combination of ceramic and PTFE, a combination of EPTF and PTFE, a combination of HDPE and PVDF, or a combination of SiC and PVDF, etc.
Preferably, the pore size of the second filter means comprises any one or a combination of at least two of 0.22 μm, 0.45 μm or 1 μm, wherein the combination is typically but not limited to: a combination of 0.22 μm and 0.45 μm, a combination of 0.45 μm and 1 μm, or a combination of 0.22 μm, 0.45 μm and 1 μm, etc.
In the invention, the first filter device and the second filter device are both precise filter devices.
As a preferred technical scheme of the invention, the continuous flow reaction system further comprises a difluoro sulfimide recovery device.
Preferably, the inlet of the bis-fluorosulfonyl imide recovery unit is connected to the thin film evaporation unit.
Preferably, the outlet of the bisfluorosulfonyl imide recovery device is connected with the first preheating device, and a bisfluorosulfonyl imide recovery pump is arranged on a connected pipeline.
In a second aspect, the present invention provides a process for the continuous production of liquid bis-fluorosulfonyl imide salt using the continuous production apparatus system of the first aspect, the process comprising the steps of:
(1) Delivering the difluoro sulfonimide into a continuous flow reaction system through a difluoro sulfonimide feeding unit, simultaneously delivering metal salt and acid solvent into the continuous flow reaction system through a metal salt feeding unit, and preparing a difluoro sulfonimide salt crude product through a salifying reaction;
(2) And (3) carrying out gas-liquid separation on the crude product of the difluoro sulfonimide salt obtained in the step (1) through a flash evaporation separation device to obtain a gas-phase acid solvent and a liquid-phase difluoro sulfonimide salt crude product, then carrying out deacidification treatment on the liquid-phase difluoro sulfonimide salt crude product through at least one thin film evaporation device, and then sequentially diluting through a dilution device, filtering through a first filtering device and exchanging heat through a heat exchange device to obtain the high-purity liquid difluoro sulfonimide salt.
The invention adopts acid solvent and metal salt to prepare preset liquid, and then the preset liquid is continuously reacted with high-purity HFSI to prepare MFSI. The neutral metal salt, the organic metal salt and the high-valence metal salt are adopted to avoid the production of water in the MFSI synthesis process, and the purity of the obtained MFSI organic solution reaches the battery level application level.
The method provided by the invention overcomes the defects of complex preparation flow of MFSI salt forming procedures, need of multiple means such as crystallization, ion adsorption and the like to purify the MFSI product and incapability of continuous production, has simple process flow design, is suitable for industrial conversion in continuous production, has high yield and purity of the obtained product, higher solvent utilization rate, low three wastes and low energy consumption, is a production method for safely, environmentally-friendly and low-cost continuous preparation of high-purity MFSI, and has good economic benefit.
As a preferred embodiment of the present invention, the metal salt in step (1) has the general formula M + n X n- And n.gtoreq.1, for example, may be 1, 2 or 3, etc., but is not limited toOther values not recited within the numerical range are equally applicable.
Wherein the M + n X n- Wherein M comprises an alkali metal; the M is + n X n- Wherein X comprises any one of F, cl, br, sulfuric acid group, phosphoric acid group, formic acid group, acetic acid group, propionic acid group, butyric acid group, valeric acid group, caproic acid group or adipic acid group.
Preferably, the alkali metal comprises any one of Li, na, K, rb or Cs.
Preferably, the acid solvent of step (1) comprises any one or a combination of at least two of anhydrous hydrofluoric acid, concentrated sulfuric acid, fuming sulfuric acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, adipic acid, trifluoroacetic acid, benzoic acid, phenylacetic acid, toluenesulfonic acid, oxalic acid or citric acid, wherein the combination is typically but not limited to: a combination of anhydrous hydrofluoric acid and concentrated sulfuric acid, a combination of fuming sulfuric acid and acetic acid, or a combination of valeric acid and adipic acid, and the like.
In the invention, the water content of the acid solvent is less than 200ppm, and the acid solvent is selected as the super-dry acid solvent.
It is worth to say that the acid solvent used in the reaction is removed from the reaction system in time through a flash separation device, no new solvent is introduced, and the reaction byproducts are few.
Preferably, the mass ratio of the metal salt and the acid solvent in the step (1) is 55:45-10:90, for example, 50:50, 40:60, 30:70, 20:80 or 15:85, etc., but the method is not limited to the listed values, and other non-listed values in the numerical range are equally applicable.
In the present invention, the sum of the mass of the metal salt and the mass of the acid solvent is 100%.
Preferably, the purity of the bisfluorosulfonyl imide in step (1) is > 99.9%, for example, 99.91%, 99.93%, 99.95%, 99.97% or 99.98%, etc., but not limited to the recited values, other non-recited values in the range of values are equally applicable.
Preferably, in the bisfluorosulfonyl imide in the step (1), the mass content of free chlorine is less than 1ppm, the mass content of sulfate radical is less than 30ppm, and the mass content of fluorosulfonate radical is less than 500ppm.
Preferably, the molar ratio of the bis-fluorosulfonyl imide to the metal salt in the step (1) is (0.80-1.50): 1, for example, 0.85:1, 0.90:1, 0.95:1, 1.00:1, 1.10:1, 1.20:1, 1.30:1, 1.40:1, or 1.45:1, etc., but not limited to the recited values, other non-recited values in the numerical range are equally applicable.
Preferably, the continuous flow reaction system of step (1) comprises a first microchannel flow reaction device, a second microchannel flow reaction device and a third microchannel flow reaction device connected in series in sequence.
The temperature of the first microchannel flow reactor is preferably 60 to 110 ℃, and may be 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, or the like, for example, but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the temperature of the second microchannel flow reactor is 85 to 135 ℃, for example, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
Preferably, the temperature of the third microchannel flow reactor is 95 to 150 ℃, for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
Preferably, the pressures of the first microchannel flow reaction device, the second microchannel flow reaction device and the third microchannel flow reaction device are all 0.25 to 1.2Mpa G, for example, 0.3Mpa G, 0.5Mpa G, 0.7Mpa G, 0.9Mpa G, 1Mpa G or 1.1Mpa G, etc., but the present invention is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the total residence time of the material in the continuous flow reaction system is 5-20 min, for example, 7min, 10min, 12min, 15min, 17min or 19min, etc., but the material is not limited to the listed values, and other values not listed in the numerical range are equally applicable.
In the present invention, the residence time of the material in each microchannel flow reactor is the same.
The method is remarkable in that the pressure drop of the serial reaction devices of the micro-channel flow reaction devices is maintained to be 0.25-1.2 MPaG, the total residence time of the reaction is 5-20 min at the reaction temperature of 60-150 ℃, and the single pass conversion rate can reach 93.2% -99.7%.
As a preferred embodiment of the present invention, the step (1) of delivering the raw material to the continuous flow reaction system specifically includes:
(a) Preheating the bisfluorosulfonyl imide by a first preheating device and then conveying the bisfluorosulfonyl imide to a continuous flow reaction system;
(b) Drying the metal salt by a drying device, conveying the metal salt to a premixing device, conveying an acid solvent to the premixing device for mixing, preheating the obtained metal salt mixed solution by a second preheating device, and conveying the preheated metal salt mixed solution to a continuous flow reaction system;
wherein, the step (a) and the step (b) are not sequenced.
Preferably, the temperature of the first preheating device in the step (a) is 60 to 110 ℃, for example, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, or the like, but the temperature is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the moisture of the metal salt after drying in the step (b) is not more than 120ppm, for example, 110ppm, 100ppm, 90ppm, 80ppm, 70ppm or 60ppm, etc., but the present invention is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the temperature of the second preheating device in the step (b) is 60 to 110 ℃, for example, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, or the like, but the temperature is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
In a preferred embodiment of the present invention, the temperature of the flash separation device in the step (2) is 95 to 150 ℃, and for example, it may be 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
In the present invention, the pressure of the flash separation device comprises normal pressure or micro-positive pressure.
Preferably, the at least one thin film evaporation device in the step (2) comprises a vertical type wiped film evaporator and a horizontal type wiped film evaporator which are sequentially connected in series.
In the invention, the gas-phase acid solvent obtained after separation by the flash separation device is reused in the premixing device; the difluoro sulfimide raw material deacidified by the vertical type wiped film evaporator and the horizontal type wiped film evaporator is reused in a difluoro sulfimide recovery device.
The invention is worth to explain, adopt flash evaporation + vertical thin film evaporation + three series connection deacidification apparatuses of horizontal thin film evaporation, will react and produce and use acid solvent and excessive raw materials HFSI discharge the system together in time, have reduced the acid value of the supplies, has raised the selectivity of the reaction, the light component acid solvent that is continuously recycled returns to the premixing device and continues to use in time, has raised the utilization factor of the acid solvent and shortened the reaction time, have reduced the emergence of the side reaction.
Preferably, the temperature of the vertical wiped film evaporator is 120 to 150 ℃, for example 122 ℃, 125 ℃, 127 ℃, 130 ℃, 132 ℃, 135 ℃, 140 ℃, 142 ℃, 145 ℃, 147 ℃ or the like, but the temperature is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the pressure of the vertical wiped film evaporator is 5 to 15kPaA, for example, 7kPaA, 9kPaA, 10kPaA, 12kPaA or 14kPaA, etc., but the present invention is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the residence time of the material in the vertical wiped film evaporator is 25-35 min, for example, 27min, 29min, 30min, 32min or 34min, etc., but the residence time is not limited to the listed values, and other values not listed in the numerical range are applicable.
Preferably, the temperature of the horizontal wiped film evaporator is 120 to 150 ℃, for example 122 ℃, 125 ℃, 127 ℃, 130 ℃, 132 ℃, 135 ℃, 140 ℃, 142 ℃, 145 ℃, 147 ℃ or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
Preferably, the pressure of the horizontal wiped film evaporator is 500 to 1000PaA, for example, 600PaA, 700PaA, 800PaA, 900PaA or 950PaA, etc., but not limited to the listed values, and other values not listed in the numerical range are applicable.
Preferably, the residence time of the material in the horizontal wiped film evaporator is 60-300 min, for example, 80min, 100min, 120min, 150min, 180min, 200min, 220min, 250min or 280min, etc., but the material is not limited to the listed values, and other non-listed values in the numerical range are applicable.
Preferably, in the step (2), the carbonate compound flows through the dilution device.
According to the invention, the product and the electrolyte solvent are fully dissolved by carrying out mixing operation on the external circulating pump of the dilution opening device.
Preferably, the carbonate compound includes any one or a combination of at least two of methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC) or Ethylene Carbonate (EC), wherein the combination is typically but not limited to: a combination of EMC and DMC, a combination of DMC and DEC or a combination of DEC and EC, etc.
Preferably, the temperature of the dilution device in the step (2) is-15 to 5 ℃, for example, -12 ℃, -10 ℃, -8 ℃, -5 ℃, -3 ℃, -1 ℃, 0 ℃, 1 ℃ or 3 ℃, etc., but the temperature is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the residence time of the material in the lean opening device in the step (2) is 30-180 min, for example, 50min, 80min, 100min, 120min, 140min, 150min, 160min or 170min, etc., but the residence time is not limited to the listed values, and other non-listed values in the numerical range are applicable.
Preferably, the diluting device for diluting the material in the step (2) further comprises: the solution is stirred by a stirring device for 0.5 to 2 hours, for example, 0.7 hours, 0.9 hours, 1 hour, 1.2 hours, 1.5 hours, 1.7 hours or 1.9 hours, etc., but the solution is not limited to the listed values, and other values not listed in the numerical range are applicable.
Preferably, the temperature of the heat exchange device in the step (2) is-15 ℃ to-45 ℃, for example, -17 ℃, -20 ℃, -22 ℃, -25 ℃, -27 ℃, -30 ℃, -32 ℃, -35 ℃, -37 ℃, -40 ℃ or-42 ℃, etc., but the heat exchange device is not limited to the recited values, and other non-recited values in the numerical range are applicable.
Preferably, the heat exchange device of the step (2) further comprises: filtered by a second filter device.
In a preferred embodiment of the present invention, the impurity metal ion content in the liquid bis (fluorosulfonyl) imide salt is less than 1ppm by mass, and for example, it may be 0.9ppm, 0.8ppm, 0.7ppm, 0.5ppm, 0.4ppm or 0.2ppm, etc., but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
In the invention, except M metal, the mass content of other metal ion impurities is less than 1ppm.
Preferably, the moisture of the liquid bis-fluorosulfonyl imide salt is not more than 15ppm, for example, 14ppm, 12ppm, 10ppm, 8ppm, 6ppm or 5ppm, etc., but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the acid value of the liquid bis-fluorosulfonyl imide salt is not more than 35ppm, and for example, it may be 32ppm, 30ppm, 25ppm, 20ppm, 15ppm, or 10ppm, etc., but not limited to the recited values, other values not recited in the numerical range are equally applicable.
In the present invention, the acid value of the liquid bis-fluorosulfonyl imide salt is calculated as HF.
Preferably, the liquid bis-fluorosulfonyl imide salt has a Hazen color number < 30, which may be 28, 25, 20, 15, 10 or 5, for example, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the liquid bis-fluorosulfonyl imide salt has a free chlorine content of < 1ppm, a sulfate content of < 20ppm, and a fluorosulfonate content of < 400ppm.
The liquid difluoro sulfimide salt product prepared by the invention accords with the application standard in the electrolyte.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the following beneficial effects:
(1) The continuous production device system adopts the micro-channel flow reaction device to replace a conventional reaction kettle, and simultaneously realizes continuous production of MFSI liquid salt by matching with equipment such as a flash evaporation separation device, a thin film evaporation device, a thinning device and the like, and has good economy, high production efficiency and safe and controllable process;
(2) The continuous production device system further adopts a three-stage series deacidification mode of flash evaporation, vertical thin film evaporation and horizontal thin film evaporation, the deacidification is more thorough, the acid value of the prepared molten MFSI is low, the chromaticity value of the MFSI solution after dilution is lower than 30, and the product quality is high; after the dilution is finished, the solubility of impurities in the carbonate solvent is reduced by adopting a low-temperature filtering mode, and the purity of liquid salt is improved by matching with a precision filter;
(3) The method adopts high-purity HFSI and dry metal salt as raw materials, and is matched with a continuous production device system to prepare MFSI with high purity, water content less than or equal to 15ppm, acid value less than or equal to 35ppm, hazen color number less than 30, free chlorine content less than 1ppm, sulfate radical content less than 20ppm, and fluorosulfonate radical content less than 400ppm, so that the method meets the application standard in electrolyte;
(4) The method adopts acid solvent as metal salt to dilute mobile phase, and flash evaporation is carried out with byproduct acid after continuous reaction, so that no new solvent is introduced, reaction byproducts are less, MFSI selectivity is high, and MFSI liquid salt purity is high.
Drawings
FIG. 1 is a schematic view showing the construction of a system of a continuous production apparatus for liquid bis-fluorosulfonyl imide salt provided in example 1;
FIG. 2 is a schematic diagram showing the construction of a system of a continuous production apparatus for liquid bis-fluorosulfonyl imide salt provided in example 2;
the device comprises a 1-drying device, a 2-premixing device, a 3-metal salt solution delivery pump, a 4-second preheating device, a 5-difluoro-sulfonimide delivery pump, a 6-first preheating device, a 7-first micro-channel flow reaction device, an 8-second micro-channel flow reaction device, a 9-third micro-channel flow reaction device, a 10-flash separation device, an 11-vertical wiped film evaporator, a 12-horizontal wiped film evaporator, a 13-thinning device, a 14-first filtering device, a 15-heat exchange device, a 16-second filtering device, a 17-difluoro-sulfonimide salt storage device, a 18-difluoro-sulfonimide recovery device, a 19-difluoro-sulfonimide recovery pump, a 20-first back pressure valve, a 21-first mass flowmeter, a 22-second back pressure valve, a 23-second mass flowmeter, a 24-first stop valve, a 25-third back pressure valve, a 26-circulating pump, a 27-stirring device and a 28-third mass flowmeter.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The microchannel flow reaction devices in the following examples and comparative examples were purchased from Corning microchannel reactor technology Co., ltd (G1-SiC). The first micro-channel flow reaction device, the second micro-channel flow reaction device and the third micro-channel flow reaction device all comprise a reaction module group consisting of 2 reaction modules (the channel structure is thorn-shaped and heart-shaped) which are connected in series.
Example 1
The embodiment provides a continuous production device system of liquid bis-fluorosulfonyl imide salt, as shown in fig. 1, wherein the continuous production device system comprises a feeding system, a continuous flow reaction system and a purification system which are sequentially connected;
the continuous flow reaction system comprises a first micro-channel flow reaction device 7, a second micro-channel flow reaction device 8 and a third micro-channel flow reaction device 9 which are sequentially connected in series; the first micro-channel flow reaction device 7 is made of SiC, the channel diameter is 1-1.2 mm, and the holding volume is 10mL; the second micro-channel flow reaction device 8 is made of SiC, the channel diameter is 1-1.2 mm, and the holding volume is 10mL; the third micro-channel flow reaction device 9 is made of SiC, the channel diameter is 1 mm-1.2 mm, and the holding volume is 10mL;
The feeding system comprises a bisfluorosulfonyl imide feeding unit and a metal salt feeding unit which are connected in parallel; the bisfluorosulfonyl imide feed unit and the metal salt feed unit are each independently connected to the first microchannel flow reactor 7;
the bisfluorosulfonyl imide feeding unit comprises a bisfluorosulfonyl imide storage device and a first preheating device 6 which are sequentially connected; a bisfluorosulfonyl imide delivery pump 5 is arranged between the bisfluorosulfonyl imide storage device and the first preheating device 6; the first preheating device 6 is connected with the first micro-channel flow reaction device 7, and a first back pressure valve 20 and a first mass flowmeter 21 are sequentially arranged on the connected pipeline;
the metal salt feeding unit comprises a metal salt storage device, a drying device 1, a premixing device 2 and a second preheating device 4 which are connected in sequence; a metal salt solution delivery pump 3 is arranged between the premixing device 2 and the second preheating device 4; the second preheating device 4 is connected with the first micro-channel flow reaction device 7, and a second back pressure valve 22, a second mass flowmeter 23 and a first stop valve 24 are sequentially arranged on the connected pipeline;
the purification system comprises a flash separation device 10, a vertical type wiped film evaporator 11, a horizontal type wiped film evaporator 12, a thin-film opening device 13, a first filtering device 14 and a heat exchange device 15 which are connected in sequence; the third micro-channel flow reaction device 9 is connected with the flash separation device 10, and a third back pressure valve 25 is arranged on a connected pipeline;
The thinning device 13 is a falling film thinning tower; the dilution device 13 is externally provided with a circulating pump 26; a stirring device 27 is arranged between the thinning device 13 and the first filtering device 14; the heat exchange device 15 further comprises a second filtering device 16 and a difluoro sulfonimide salt storage device 17 which are sequentially connected;
the filter element of the first filter device 14 is made of ceramic, and the aperture is 5 mu m; the second filter device 16 is a ceramic filter element with a pore size of 1 μm and 0.45 μm connected in series.
Example 2
The embodiment provides a continuous production device system of liquid bis-fluorosulfonyl imide salt, as shown in fig. 2, and further comprises the following devices on the basis of the continuous production device system provided in the embodiment 1;
the premixing device 2 is connected with the flash separation device 10, and a third mass flowmeter 28 is arranged on a connected pipeline;
the continuous flow reaction system further includes a bis-fluorosulfonyl imide recovery unit 18; the inlets of the bisfluorosulfonyl imide recovery device 18 are respectively and independently connected with the vertical wiped film evaporator 11 and the horizontal wiped film evaporator 12; the outlet of the bisfluorosulfonyl imide recovery device 18 is connected with the first preheating device 6, and a bisfluorosulfonyl imide recovery pump 19 is arranged on a connected pipeline.
Example 3
This example provides a continuous production apparatus system for a liquid bis-fluorosulfonyl imide salt, and the conditions are the same as those in example 1 except that the horizontal wiped film evaporator 12 is not provided.
Comparative example 1
This comparative example provides a continuous production apparatus system for liquid bis-fluorosulfonyl imide salt, and the same conditions as those of example 1 are applied except that the continuous flow reaction system is provided with only the first microchannel flow reaction apparatus 7, and the second microchannel flow reaction apparatus 8 and the third microchannel flow reaction apparatus 9 are not provided.
Preparation example 1
The present preparation example provides a method for continuously producing a liquid bis-fluorosulfonyl imide salt, using the continuous production apparatus system provided in example 1, wherein the apparatus in the continuous production apparatus system is replaced with high-purity nitrogen for 1h to form an inert atmosphere, the method comprising the steps of:
(1) After the HFSI is preheated to 80 ℃ by the first preheating device 6, the first back pressure valve 20 and the first mass flowmeter 21 are regulated and controlled to pump into the first micro-channel flow reaction device 7 at a flow rate of 100 g/min;
the purity of the HFSI is more than 99.9 percent, the mass content of free chlorine is less than 1ppm, the mass content of sulfate radical is less than 30ppm, and the mass content of fluorosulfonate radical is less than 500ppm;
(2) Drying 2068g LiF in a drying device 1 at 150 ℃ for 8h till the water content reaches 80ppm, then conveying 1034g of the dried LiF to a premixing device 2 through a metal salt solution conveying pump 3 by a vibrating hopper under the drying device 1, simultaneously introducing 5170g of anhydrous hydrofluoric acid solvent into the premixing device 2, stirring and mixing for 2.5h in the premixing device 2 at room temperature to obtain 6205g of LiHF 2 A solution; thereafter, the first shut-off valve 24 is opened, and the resultant LiHF is then used 2 After the solution is preheated to 80 ℃ by the second preheating device 4, regulating and controlling the second back pressure valve 22 and the second mass flowmeter 23 to pump into the first micro-channel flow reaction device 7 at a flow rate of 103-104 g/min;
wherein the molar ratio of the HFSI in step (1) to the LiF in step (2) is 0.83:1;
(3) Setting the temperature of the first micro-channel flow reaction device 7 to be 80 ℃, setting the temperature of the second micro-channel flow reaction device 8 to be 100 ℃, setting the temperature of the third micro-channel flow reaction device 9 to be 140 ℃, regulating and controlling the third back pressure valve 25 to adjust the pressure before the valve to be 1.1-1.2 MpaG, and preparing a LiFSI crude product through salification reaction;
(4) After gas-liquid separation is carried out on the LiFSI crude product obtained in the step (3) in a flash evaporation separation device 10 with the temperature of 140 ℃, the liquid-phase LiFSI crude product enters a vertical wiped film evaporator 11, is subjected to first deacidification treatment for 30min at the temperature of 140 ℃ and the pressure of 10-12 kPaA, then enters a horizontal wiped film evaporator 12, and is subjected to second deacidification treatment for 150min at the temperature of 140 ℃ and the pressure of 1 kPaA;
(5) The molten LiFSI crude product after the second deacidification treatment in the step (4) enters a dilution opening device 13 with the temperature of minus 15 ℃ at a constant speed through a flow limiting orifice plate at a speed of 86g/min, an external circulating pump 26 of the dilution opening device 13 is opened, and meanwhile, an EMC solvent with the temperature of minus 15 ℃ flows into the dilution opening device 13 at a flow speed of 200g/min to prepare a liquid 30% LiFSI/EMC crude product;
(6) And (3) the liquid 30% LiFSI/EMC crude product obtained in the step (5) enters a stirring device 27 in an overflow mode to be stirred for 1h, and then is filtered by a first filtering device 14, subjected to heat exchange by a heat exchange device 15 with the temperature of minus 25 ℃ and filtered by a second filtering device 16, and the obtained liquid 30% LiFSI/EMC product is stored in a difluoro sulfonimide salt storage device 17.
Preparation example 2
The present preparation example provides a method for continuously producing a liquid bis-fluorosulfonyl imide salt, using the continuous production apparatus system provided in example 1, wherein the apparatus in the continuous production apparatus system is replaced with high-purity nitrogen for 1h to form an inert atmosphere, the method comprising the steps of:
(1) After the HFSI is preheated to 110 ℃ by the first preheating device 6, the first back pressure valve 20 and the first mass flowmeter 21 are regulated and controlled to pump into the first micro-channel flow reaction device 7 at a flow rate of 100 g/min;
The purity of the HFSI is more than 99.9 percent, the mass content of free chlorine is less than 1ppm, the mass content of sulfate radical is less than 30ppm, and the mass content of fluorosulfonate radical is less than 500ppm;
(2) Drying 4kg of lithium phosphate dihydrate at 140 ℃ for 8 hours in a drying device 1 to 20ppm of water, and then drying the dried Li 3 PO 4 Delivering the mixture to a premixing device 2 through a metal salt solution delivery pump 3 by a vibration hopper under a drying device 1, simultaneously introducing 20kg of phosphoric acid solvent into the premixing device 2, heating to 80 ℃ for melting, and then stirring and mixing in the premixing device 2 for 4 hours to obtain Li 3 PO 4 A solution; after that, the first stop valve 24 is opened, and the obtained Li 3 PO 4 After the solution is preheated to 110 ℃ by the second preheating device 4, the second back pressure valve 22 and the second mass flowmeter 23 are regulated and controlled to pump into the first micro-channel flow reaction device 7 at a flow rate of 380 g/min;
wherein the HFSI of step (1) and the Li of step (2) 3 PO 4 The molar ratio of (2) is 1.27:1;
(3) Setting the temperature of the first micro-channel flow reaction device 7 to be 110 ℃, setting the temperature of the second micro-channel flow reaction device 8 to be 130 ℃, setting the temperature of the third micro-channel flow reaction device 9 to be 150 ℃, regulating the pressure in front of the valve to be 0.3MpaG by regulating the third back pressure valve 25, and preparing a LiFSI crude product through salification reaction;
(4) After carrying out gas-liquid separation on the LiFSI crude product obtained in the step (3) in a flash evaporation separation device 10 with the temperature of 150 ℃, enabling the liquid-phase LiFSI crude product to enter a vertical wiped film evaporator 11, carrying out first deacidification treatment for 25min at the temperature of 150 ℃ and the pressure of 10-12 kPaA, and then entering a horizontal wiped film evaporator 12, and carrying out second deacidification treatment for 200min at the temperature of 150 ℃ and the pressure of 1 kPaA;
(5) The molten LiFSI crude product after the second deacidification treatment in the step (4) enters a dilution opening device 13 with the temperature of minus 15 ℃ at a constant speed through a flow limiting orifice plate at a speed of 160g/min, an external circulating pump 26 of the dilution opening device 13 is opened, and meanwhile, an EMC solvent with the temperature of minus 15 ℃ flows into the dilution opening device 13 at a flow speed of 240g/min to prepare a liquid 30% LiFSI/EMC crude product;
(6) And (3) the liquid 30% LiFSI/EMC crude product obtained in the step (5) enters a stirring device 27 in an overflow mode to be stirred for 1h, and then is filtered by a first filtering device 14, subjected to heat exchange by a heat exchange device 15 with the temperature of minus 45 ℃ and filtered by a second filtering device 16, and the obtained liquid 30% LiFSI/EMC product is stored in a difluoro sulfonimide salt storage device 17.
Preparation example 3
The present preparation example provides a method for continuously producing a liquid bis-fluorosulfonyl imide salt, using the continuous production apparatus system provided in example 1, wherein the apparatus in the continuous production apparatus system is replaced with high-purity nitrogen for 1h to form an inert atmosphere, the method comprising the steps of:
(1) After the HFSI is preheated to 60 ℃ by the first preheating device 6, the first back pressure valve 20 and the first mass flowmeter 21 are regulated and controlled to be pumped into the first micro-channel flow reaction device 7 at a flow rate of 100 g/min;
the purity of the HFSI is more than 99.9 percent, the mass content of free chlorine is less than 1ppm, the mass content of sulfate radical is less than 30ppm, and the mass content of fluorosulfonate radical is less than 500ppm;
(2) Drying 3.5kg of lithium caproate by a drying device 1 at 120 ℃ for 8 hours until the water content reaches 120ppm, conveying the dried lithium caproate to a premixing device 2 through a metal salt solution conveying pump 3 by a vibration hopper under the drying device 1, simultaneously introducing 15.5kg of a caproic acid solvent into the premixing device 2, and stirring and mixing in the premixing device 2 for 2 hours at normal temperature to obtain 19.0kg of lithium caproate solution; then the first stop valve 24 is opened, the obtained lithium caproate solution is preheated to 60 ℃ by the second preheating device 4, and the second back pressure valve 22 and the second mass flowmeter 23 are regulated and controlled to be pumped into the first micro-channel flow reaction device 7 at the flow rate of 280 g/min;
wherein the molar ratio of the HFSI in step (1) to the lithium caproate in step (2) is 1.31:1;
(3) Setting the temperature of the first micro-channel flow reaction device 7 to be 60 ℃, setting the temperature of the second micro-channel flow reaction device 8 to be 90 ℃, setting the temperature of the third micro-channel flow reaction device 9 to be 120 ℃, regulating the pressure in front of the third back pressure valve 25 to be 0.25MpaG, and preparing a LiFSI crude product through salification reaction;
(4) After gas-liquid separation is carried out on the LiFSI crude product obtained in the step (3) in a flash evaporation separation device 10 with the temperature of 120 ℃, the liquid-phase LiFSI crude product enters a vertical wiped film evaporator 11, is subjected to first deacidification treatment for 30min at the temperature of 150 ℃ and the pressure of 5-7 kPaA, then enters a horizontal wiped film evaporator 12, and is subjected to second deacidification treatment for 220min at the temperature of 150 ℃ and the pressure of 500 PaA;
(5) The molten LiFSI crude product after the second deacidification treatment in the step (4) enters a dilution opening device 13 with the temperature of 5 ℃ at a constant speed through a flow limiting orifice plate at a speed of 103g/min, an external circulating pump 26 of the dilution opening device 13 is opened, and simultaneously DMC solvent with the temperature of 5 ℃ flows into the dilution opening device 13 at a flow speed of 240g/min to prepare liquid 30% LiSSI/DMC crude product;
(6) And (3) the liquid 30% LiFSI/DMC crude product obtained in the step (5) enters a stirring device 27 in an overflow mode to be stirred for 1h, and then is filtered by a first filtering device 14, subjected to heat exchange by a heat exchange device 15 with the temperature of minus 15 ℃ and filtered by a second filtering device 16, and the obtained liquid 30% LiFSI/DMC product is stored in a difluoro sulfonimide salt storage device 17.
Preparation example 4
The present preparation example provides a method for continuously producing a liquid bis-fluorosulfonyl imide salt, using the continuous production apparatus system provided in example 1, wherein the apparatus in the continuous production apparatus system is replaced with high-purity nitrogen for 1h to form an inert atmosphere, the method comprising the steps of:
(1) After the HFSI is preheated to 100 ℃ by the first preheating device 6, the first back pressure valve 20 and the first mass flowmeter 21 are regulated and controlled to pump into the first micro-channel flow reaction device 7 at a flow rate of 100 g/min;
the purity of the HFSI is more than 99.9 percent, the mass content of free chlorine is less than 1ppm, the mass content of sulfate radical is less than 30ppm, and the mass content of fluorosulfonate radical is less than 500ppm;
(2) 2320g of NaF is dried for 8 hours to 55ppm of moisture in a drying device 1 at the temperature of 140 ℃, then 1160g of dried NaF is conveyed to a premixing device 2 through a metal salt solution conveying pump 3 by a vibrating hopper under the drying device 1, 5800g of anhydrous hydrofluoric acid solvent is simultaneously introduced into the premixing device 2, and stirred and mixed in the premixing device 2 for 4 hours at normal temperature, so as to obtain 6960g of NaHF 2 A solution; thereafter, the first shut-off valve 24 is opened to obtain NaHF 2 After the solution is preheated to 100 ℃ by the second preheating device 4, the second back pressure valve 22 and the second mass flowmeter 23 are regulated and controlled to pump into the first micro-channel flow reaction device 7 at the flow rate of 116 g/min;
wherein the molar ratio of the HFSI in the step (1) to the NaF in the step (2) is 1.20:1;
(3) Setting the temperature of the first micro-channel flow reaction device 7 as 100 ℃, setting the temperature of the second micro-channel flow reaction device 8 as 110 ℃, setting the temperature of the third micro-channel flow reaction device 9 as 120 ℃, regulating the pressure in front of the valve to 1.15MpaG by regulating the third back pressure valve 25, and preparing a NaFSI crude product through salification reaction;
(4) After gas-liquid separation is carried out on the NaFSI crude product obtained in the step (3) in a flash evaporation separation device 10 with the temperature of 120 ℃, the liquid-phase NaFSI crude product enters a vertical wiped film evaporator 11, is subjected to first deacidification treatment for 30min at the temperature of 120 ℃ and the pressure of 10-12 kPaA, then enters a horizontal wiped film evaporator 12, and is subjected to second deacidification treatment for 160min at the temperature of 120 ℃ and the pressure of 1 kPaA;
(5) Enabling the molten NaFSI crude product after the second deacidification treatment in the step (4) to enter a dilution opening device 13 with the temperature of-15 ℃ at a constant speed through a flow limiting orifice plate at a speed of 93.5g/min, opening an external circulating pump 26 of the dilution opening device 13, and simultaneously enabling an EMC solvent with the temperature of-15 ℃ to flow into the dilution opening device 13 at a flow speed of 218g/min to prepare a liquid 30% NaFSI/EMC crude product;
(6) And (3) the liquid 30% NaFSI/EMC crude product obtained in the step (5) enters a stirring device 27 in an overflow mode to be stirred for 1h, and then is filtered by a first filtering device 14, subjected to heat exchange by a heat exchange device 15 with the temperature of minus 30 ℃ and filtered by a second filtering device 16, and the obtained liquid 30% NaFSI/EMC product is stored in a difluoro sulfonimide salt storage device 17.
Preparation example 5
The present preparation example provides a method for continuously producing a liquid bis-fluorosulfonyl imide salt, using the continuous production apparatus system provided in example 1, wherein the apparatus in the continuous production apparatus system is replaced with high-purity nitrogen for 1h to form an inert atmosphere, the method comprising the steps of:
(1) After the HFSI is preheated to 75 ℃ by the first preheating device 6, the first backpressure valve 20 and the first mass flowmeter 21 are regulated and controlled to pump into the first micro-channel flow reaction device 7 at a flow rate of 100 g/min;
the purity of the HFSI is more than 99.9 percent, the mass content of free chlorine is less than 1ppm, the mass content of sulfate radical is less than 30ppm, and the mass content of fluorosulfonate radical is less than 500ppm;
(2) Drying 4532g of potassium acetate at 120 ℃ for 8 hours in a drying device 1 until the water content reaches 30ppm, conveying 2266g of dried potassium acetate to a premixing device 2 through a metal salt solution conveying pump 3 by a vibrating hopper under the drying device 1, introducing 7550g of glacial acetic acid solvent into the premixing device 2, and stirring and mixing for 4 hours in the premixing device 2 at normal temperature to obtain 9819g of potassium acetate solution; then, opening a first stop valve 24, preheating the obtained potassium acetate solution to 75 ℃ through a second preheating device 4, and regulating and controlling a second back pressure valve 22 and a second mass flowmeter 23 to pump the potassium acetate solution into a first micro-channel flow reaction device 7 at a flow rate of 163-164 g/min;
wherein the molar ratio of the HFSI in the step (1) to the potassium acetate in the step (2) is 1.43:1;
(3) Setting the temperature of the first micro-channel flow reaction device 7 to be 75 ℃, setting the temperature of the second micro-channel flow reaction device 8 to be 95 ℃, setting the temperature of the third micro-channel flow reaction device 9 to be 115 ℃, regulating and controlling the third back pressure valve 25 to adjust the pressure before the valve to be 0.5-0.6 MpaG, and preparing a KFSI crude product through salification reaction;
(4) After gas-liquid separation is carried out on the KFSI crude product obtained in the step (3) in a flash evaporation separation device 10 with the temperature of 115 ℃, the liquid-phase KFSI crude product enters a vertical wiped film evaporator 11, is subjected to first deacidification treatment for 30min at the temperature of 120 ℃ and the pressure of 12-15 kPaA, then enters a horizontal wiped film evaporator 12, and is subjected to second deacidification treatment for 160min at the temperature of 120 ℃ and the pressure of 1 kPaA;
(5) The molten KFSI crude product after the second deacidification treatment in the step (4) enters a dilution opening device 13 with the temperature of 5 ℃ at a constant speed through a flow limiting orifice plate at a speed of 120g/min, an external circulating pump 26 of the dilution opening device 13 is opened, and simultaneously DMC solvent with the temperature of 5 ℃ flows into the dilution opening device 13 at a flow speed of 282g/min to prepare liquid 30% KFSI/DMC crude product;
(6) And (3) the liquid 30% KFSI/DMC crude product obtained in the step (5) enters a stirring device 27 in an overflow mode to be stirred for 1h, and then is filtered by a first filtering device 14, subjected to heat exchange by a heat exchange device 15 with the temperature of minus 15 ℃ and filtered by a second filtering device 16, and the obtained liquid 30% KFSI/DMC product is stored in a difluoro sulfonimide salt storage device 17.
Preparation example 6
The present preparation example provides a method for continuously producing a liquid bis-fluorosulfonyl imide salt, using the continuous production apparatus system provided in example 1, wherein the apparatus in the continuous production apparatus system is replaced with high-purity nitrogen for 1h to form an inert atmosphere, the method comprising the steps of:
(1) After the HFSI is preheated to 75 ℃ by the first preheating device 6, the first backpressure valve 20 and the first mass flowmeter 21 are regulated and controlled to pump into the first micro-channel flow reaction device 7 at a flow rate of 100 g/min;
the purity of the HFSI is more than 99.9 percent, the mass content of free chlorine is less than 1ppm, the mass content of sulfate radical is less than 30ppm, and the mass content of fluorosulfonate radical is less than 500ppm;
(2) Drying 7.5kg of sodium trifluoroacetate in a drying device 1 at 150 ℃ for 8 hours until the moisture reaches 35ppm, then conveying 3.75kg of dried sodium trifluoroacetate to a premixing device 2 through a metal salt solution conveying pump 3 by a vibrating hopper under the drying device 1, simultaneously introducing 12.5kg of a trifluoroacetic acid solvent into the premixing device 2, and stirring and mixing in the premixing device 2 at normal temperature for 3 hours to obtain 16.25kg of sodium trifluoroacetate solution; then, the first stop valve 24 is opened, the obtained sodium trifluoroacetate solution is preheated to 75 ℃ by the second preheating device 4, and the second back pressure valve 22 and the second mass flowmeter 23 are regulated and controlled to pump into the first micro-channel flow reaction device 7 at a flow rate of 270 g/min;
wherein the molar ratio of the HFSI in step (1) to the sodium trifluoroacetate in step (2) is 1.21:1;
(3) Setting the temperature of the first micro-channel flow reaction device 7 at 75 ℃, setting the temperature of the second micro-channel flow reaction device 8 at 85 ℃, setting the temperature of the third micro-channel flow reaction device 9 at 95 ℃, regulating the pressure in front of the valve to 0.6-0.8 MpaG by regulating the third back pressure valve 25, and preparing a NaFSI crude product through salification reaction;
(4) After gas-liquid separation is carried out on the NaFSI crude product obtained in the step (3) in a flash evaporation separation device 10 with the temperature of 95 ℃, the liquid-phase NaFSI crude product enters a vertical wiped film evaporator 11, is subjected to first deacidification treatment for 30min at the temperature of 120 ℃ and the pressure of 10-12 kPaA, then enters a horizontal wiped film evaporator 12, and is subjected to second deacidification treatment for 160min at the temperature of 140 ℃ and the pressure of 1 kPaA;
(5) Enabling the molten NaFSI crude product after the second deacidification treatment in the step (4) to enter a dilution opening device 13 with the temperature of minus 15 ℃ at a constant speed through a flow limiting orifice plate at a speed of 112g/min, opening an external circulating pump 26 of the dilution opening device 13, and simultaneously enabling a DEC solvent with the temperature of minus 15 ℃ to flow into the dilution opening device 13 at a flow speed of 260g/min to prepare a liquid 30% NaFSI/DEC crude product;
(6) And (3) the liquid 30% NaFSI/DEC crude product obtained in the step (5) enters a stirring device 27 in an overflow mode to be stirred for 1h, and then is filtered by a first filtering device 14, subjected to heat exchange by a heat exchange device 15 with the temperature of minus 40 ℃ and filtered by a second filtering device 16, and the obtained liquid 30% NaFSI/DEC product is stored in a difluoro sulfonimide salt storage device 17.
Preparation example 7
The preparation example provides a method for continuously producing liquid difluoro sulfonyl imide salt, the continuous production device system provided in the embodiment 2 is adopted, except that in the step (4), after the vapor-liquid separation is carried out by the flash separation device 10, the obtained vapor phase HF is recycled into the premixing device 2, the flow rate of the HF in a recycling pipeline is 68-70 g/min, and meanwhile, the dried LiF is supplemented according to the feeding rate of 17g/min and enters the premixing device 2 for continuous mixing; the HFSI obtained after deacidification treatment by the vertical wiped film evaporator 11 and the horizontal wiped film evaporator 12 is reused in the bis-fluorosulfonyl imide recovery unit 18, and the other conditions are the same as those in preparation example 1.
Preparation example 8
This preparation example provides a method for continuously producing a liquid bis-fluorosulfonyl imide salt, and the conditions are the same as those of preparation example 1 except that the continuous production apparatus system provided in example 3 is used.
Preparation example 9
The present preparation example provides a method for continuously producing a liquid bis-fluorosulfonyl imide salt, and the conditions are the same as those of preparation example 1 except that the pre-valve pressure is adjusted to 0.1mpa by controlling the third back-pressure valve 25 in step (3).
Preparation example 10
The present preparation example provides a method for continuously producing a liquid bis-fluorosulfonyl imide salt, and the conditions are the same as those of preparation example 1 except that the pre-valve pressure is adjusted to 1.5mpa by controlling the third back-pressure valve 25 in step (3).
Comparative preparation example 1
This comparative preparation example provides a method for continuously producing a liquid bis-fluorosulfonyl imide salt, and the conditions are the same as those of preparation example 1 except that the continuous production apparatus system provided in comparative example 1 is employed.
The liquid bis-fluorosulfonyl imide salt products prepared in the preparation examples and the comparative preparation examples are subjected to performance characterization and yield calculation, and the results are shown in table 1;
the testing method comprises the following steps:
moisture content: testing using karl fischer coulomb method;
Hazen color number: testing was performed using a U.S. hash LICO690 colorimeter;
acid value: titration with 0.0192mol/L aqueous sodium hydroxide;
free chlorine, sulfate and fluorosulfonate content: the test was performed using ion chromatography, column model sameirfeir AS22 anion analysis column 4 x 250mm; the inhibition liquid is a sulfuric acid solution with the concentration of 150 mmol/L; the preparation step of the eluent: 1) Buffer (mother liquor) is prepared firstly: 4.5428g NaHCO 3 ，8.4813g Na 2 CO 3 Adding 200mL of distilled water for dissolution, carrying out ultrasonic dissolution assistance and suction filtration; 2) And (3) configuring a mobile phase: taking 20mL of mother solution, 1380g of distilled water and 600mL of acetonitrile, and stirring and mixing uniformly for later use.
TABLE 1
As can be seen from table 1:
(1) By adopting the continuous production device system and the production method provided by the invention, the prepared liquid difluoro sulfonimide salt has high yield, the prepared MFSI product has high purity, the water content is less than or equal to 15ppm, the acid value is less than or equal to 35ppm, the Hazen color number is less than 30, the mass content of free chlorine is less than 1ppm, the mass content of sulfate radical is less than 20ppm, the mass content of fluoro sulfonate radical is less than 400ppm, and the product meets the application standard in electrolyte;
(2) As can be seen from comparison of the comprehensive preparation examples 1 and 8, when the horizontal wiped film evaporator 12 is not arranged, the acid solvent in the MFSI crude product cannot be thoroughly removed, so that the acid value and Hazen color number of the product are increased and exceed the standard Hazen color number;
(3) As can be seen from comparison of the comprehensive preparation examples 1 and 9-10, when the pressure drop of the microchannel flow reaction device is low, the reaction solvent is lost too quickly, metal salt can be precipitated and settled in the microchannel, and the reaction channel is easy to be blocked, so that the conversion rate of the product is low, the HFSI residue is large, and the acid value is high; when the pressure drop of the micro-channel flow reaction device is higher, polymerization side reaction is easy to occur, so that the color number of the product is increased, and corresponding sulfate radical and fluorosulfonate radical ions are higher;
(4) As is clear from the comparison between the synthesis of preparation example 1 and comparative preparation example 1, when the reaction apparatus was the first microchannel flow reaction apparatus 7 alone, the reaction was insufficient, resulting in a significant decrease in the product yield.
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. A continuous production device system of liquid bis-fluorosulfonyl imide salt, which is characterized by comprising a feeding system, a continuous flow reaction system and a purification system which are connected in sequence;
the feeding system comprises a bisfluorosulfonyl imide feeding unit and a metal salt feeding unit which are connected in parallel;
the continuous flow reaction system comprises at least three microchannel flow reaction devices; the micro-channel flow reaction devices are arranged in series;
The difluoro sulfimide feeding unit and the metal salt feeding unit are respectively and independently connected with the micro-channel flow reaction device;
the purification system comprises a flash separation device, at least one thin film evaporation device, a dilution device, a first filtering device and a heat exchange device which are connected in sequence;
the microchannel flow reactor is connected to the flash separation device.
2. The continuous production apparatus system of claim 1, wherein the bis-fluorosulfonyl imide feed unit comprises a bis-fluorosulfonyl imide storage unit and a first preheating unit connected in sequence;
a bisfluorosulfonyl imide delivery pump is arranged between the bisfluorosulfonyl imide storage device and the first preheating device;
the first preheating device is connected with the micro-channel flow reaction device, and a first back pressure valve and a first mass flowmeter are sequentially arranged on a connected pipeline;
the metal salt feeding unit comprises a metal salt storage device, a drying device, a premixing device and a second preheating device which are sequentially connected;
a metal salt solution delivery pump is arranged between the premixing device and the second preheating device;
the second preheating device is connected with the micro-channel flow reaction device, and a second back pressure valve, a second mass flowmeter and a first stop valve are sequentially arranged on a connected pipeline;
The premixing device is connected with the flash separation device, and a third mass flowmeter is arranged on a connected pipeline.
3. The continuous production apparatus system of claim 1, wherein the material of the microchannel flow reactor comprises silicon carbide;
the diameter of the channel of the micro-channel flow reaction device is 0.1-5 mm;
the channel structure of the micro-channel flow reaction device comprises any one or a combination of at least two of a heart type, a zigzag type, a thorn type, a baffle type or a Y type;
the liquid holding volume of the micro-channel flow reaction device is 7-70 mL;
a third back pressure valve is arranged between the micro-channel flow reaction device and the flash separation device.
4. The continuous production apparatus system of claim 1, wherein the thin film evaporation apparatus comprises a vertical wiped film evaporator or a horizontal wiped film evaporator;
the purification system comprises a flash separation device, a vertical type wiped film evaporator, a horizontal type wiped film evaporator, a dilution device, a first filtering device and a heat exchange device which are connected in sequence;
the thin-film opening device comprises a falling film thin-film opening tower;
the dilution device is externally provided with a circulating pump;
a stirring device is arranged between the thinning device and the first filtering device;
The filter element material of the first filter device comprises any one or a combination of at least two of ceramic, polytetrafluoroethylene, expanded polytetrafluoroethylene, polyethylene, polyvinylidene fluoride and silicon carbide;
the pore size of the first filter means comprises any one or a combination of at least two of 0.45 μm, 1 μm or 5 μm;
the heat exchange device further comprises a second filtering device and a difluoro sulfonimide salt storage device which are sequentially connected;
the filter element material of the second filter device comprises any one or a combination of at least two of ceramic, polytetrafluoroethylene, expanded polytetrafluoroethylene, polyethylene, polyvinylidene fluoride and silicon carbide;
the pore size of the second filter means comprises any one or a combination of at least two of 0.22 μm, 0.45 μm or 1 μm.
5. The continuous flow production apparatus system of claim 1, wherein the continuous flow reaction system further comprises a bis-fluorosulfonyl imide recovery unit;
the inlet of the difluoro sulfimide recovery device is connected with the thin film evaporation device;
the outlet of the difluoro sulfonimide recovery device is connected with the first preheating device, and a difluoro sulfonimide recovery pump is arranged on a connected pipeline.
6. A process for the continuous production of liquid bis-fluorosulfonyl imide salts, characterized in that it is carried out with a continuous production apparatus system according to any one of claims 1-5, said process comprising the steps of:
(1) Delivering the difluoro sulfonimide into a continuous flow reaction system through a difluoro sulfonimide feeding unit, simultaneously delivering metal salt and acid solvent into the continuous flow reaction system through a metal salt feeding unit, and preparing a difluoro sulfonimide salt crude product through a salifying reaction;
(2) And (3) carrying out gas-liquid separation on the crude product of the difluoro sulfonimide salt obtained in the step (1) through a flash evaporation separation device to obtain a gas-phase acid solvent and a liquid-phase difluoro sulfonimide salt crude product, then carrying out deacidification treatment on the liquid-phase difluoro sulfonimide salt crude product through at least one thin film evaporation device, and then sequentially diluting through a dilution device, filtering through a first filtering device and exchanging heat through a heat exchange device to obtain the high-purity liquid difluoro sulfonimide salt.
7. The method of claim 6, wherein the metal salt of step (1) has the formula M + n X n- N is more than or equal to 1;
wherein the M + n X n- Wherein M comprises an alkali metal; the M is + n X n- Wherein X comprises any one of F, cl, br, sulfuric acid group, phosphoric acid group, formic acid group, acetic acid group, propionic acid group, butyric acid group, valeric acid group, caproic acid group or adipic acid group;
The alkali metal comprises any one of Li, na, K, rb or Cs;
the acid solvent in the step (1) comprises any one or a combination of at least two of anhydrous hydrofluoric acid, concentrated sulfuric acid, fuming sulfuric acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, adipic acid, trifluoroacetic acid, benzoic acid, phenylacetic acid, methylbenzenesulfonic acid, oxalic acid or citric acid;
the mass ratio of the metal salt to the acid solvent in the step (1) is 55:45-10:90;
the purity of the bisfluorosulfonyl imide in the step (1) is more than 99.9%;
in the bisfluorosulfonyl imide obtained in the step (1), the mass content of free chlorine is less than 1ppm, the mass content of sulfate radical is less than 30ppm, and the mass content of fluorosulfonate radical is less than 500ppm;
the molar ratio of the bisfluorosulfonyl imide to the metal salt in the step (1) is (0.80-1.50): 1;
the continuous flow reaction system in the step (1) comprises a first micro-channel flow reaction device, a second micro-channel flow reaction device and a third micro-channel flow reaction device which are sequentially connected in series;
the temperature of the first micro-channel flow reaction device is 60-110 ℃;
the temperature of the second micro-channel flow reaction device is 85-135 ℃;
the temperature of the third micro-channel flow reaction device is 95-150 ℃;
The pressures of the first micro-channel flow reaction device, the second micro-channel flow reaction device and the third micro-channel flow reaction device are all 0.25-1.2 MpaG;
the total residence time of the materials in the continuous flow reaction system is 5-20 min.
8. The method of claim 6, wherein delivering feedstock to the continuous flow reaction system in step (1) comprises:
(a) Preheating the bisfluorosulfonyl imide by a first preheating device and then conveying the bisfluorosulfonyl imide to a continuous flow reaction system;
(b) Drying the metal salt by a drying device, conveying the metal salt to a premixing device, conveying an acid solvent to the premixing device for mixing, preheating the obtained metal salt mixed solution by a second preheating device, and conveying the preheated metal salt mixed solution to a continuous flow reaction system;
wherein, the step (a) and the step (b) are not in sequence;
the temperature of the first preheating device in the step (a) is 60-110 ℃;
the moisture content of the dried metal salt in the step (b) is less than or equal to 120ppm;
and (b) the temperature of the second preheating device is 60-110 ℃.
9. The method of claim 6, wherein the flash separation device in step (2) has a temperature of 95-150 ℃;
the at least one thin film evaporation device in the step (2) comprises a vertical type film scraping evaporator and a horizontal type film scraping evaporator which are sequentially connected in series;
The temperature of the vertical film scraping evaporator is 120-150 ℃;
the pressure of the vertical wiped film evaporator is 5-15 kPaA;
the retention time of the material in the vertical film scraping evaporator is 25-35 min;
the temperature of the horizontal wiped film evaporator is 120-150 ℃;
the pressure of the horizontal wiped film evaporator is 500-1000 PaA;
the retention time of the material in the horizontal wiped film evaporator is 60-300 min;
the carbonate compound flows through the dilution opening device in the step (2);
the carbonate compound comprises any one or a combination of at least two of methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate and ethylene carbonate;
the temperature of the thinning device in the step (2) is-15-5 ℃;
the retention time of the material in the thinning device in the step (2) is 30-180 min;
the material is diluted by the dilution device in the step (2) and then comprises the following components: stirring and dissolving for 0.5-2h by a stirring device;
the temperature of the heat exchange device in the step (2) is-15 ℃ to-45 ℃;
the material further comprises the following components after heat exchange by the heat exchange device in the step (2): filtered by a second filter device.
10. The method according to claim 6, wherein the impurity metal ion mass content in the liquid bis-fluorosulfonyl imide salt is < 1ppm;
The moisture of the liquid difluoro sulfimide salt is less than or equal to 15ppm;
the acid value of the liquid difluoro sulfonyl imide salt is less than or equal to 35ppm;
the Hazen color number of the liquid bis-fluorosulfonyl imide salt is less than 30;
in the liquid bis (fluorosulfonyl) imide salt, the mass content of free chlorine is less than 1ppm, the mass content of sulfate radical is less than 20ppm, and the mass content of fluorosulfonate radical is less than 400ppm.
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