WO2021082450A1 - Supercritical purification method for bis(fluorosulfonyl)imide - Google Patents
Supercritical purification method for bis(fluorosulfonyl)imide Download PDFInfo
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- WO2021082450A1 WO2021082450A1 PCT/CN2020/094589 CN2020094589W WO2021082450A1 WO 2021082450 A1 WO2021082450 A1 WO 2021082450A1 CN 2020094589 W CN2020094589 W CN 2020094589W WO 2021082450 A1 WO2021082450 A1 WO 2021082450A1
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- Prior art keywords
- fluorosulfonyl
- bis
- imide
- extraction
- supercritical
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- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000000746 purification Methods 0.000 title claims description 17
- 238000000605 extraction Methods 0.000 claims abstract description 31
- 238000000926 separation method Methods 0.000 claims abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012530 fluid Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000000194 supercritical-fluid extraction Methods 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 150000002466 imines Chemical class 0.000 claims description 15
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 claims description 6
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910021201 NaFSI Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052792 caesium Inorganic materials 0.000 claims 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims 1
- 229910052701 rubidium Inorganic materials 0.000 claims 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 6
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 5
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 5
- 229910010941 LiFSI Inorganic materials 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012025 fluorinating agent Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229940071870 hydroiodic acid Drugs 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229910019730 CsFSI Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- PVMUVDSEICYOMA-UHFFFAOYSA-N n-chlorosulfonylsulfamoyl chloride Chemical compound ClS(=O)(=O)NS(Cl)(=O)=O PVMUVDSEICYOMA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002351 wastewater Substances 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
- C01B21/087—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
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Definitions
- the invention belongs to the technical field of fluorine chemical lithium battery electrolyte, and specifically relates to a supercritical purification method of bis(fluorosulfonyl)imide (HFSI).
- HFSI Bis(fluorosulfonyl)imide
- CAS: 14984-73-7 molecular formula HN(SO 2 F) 2
- HFSI is a strong acid, and its salt has a wide range of applications in catalysis, electrolyte, fluorinating agent, etc.
- its lithium salt LiFSI
- LiPF 6 lithium hexafluorophosphate
- HFSI has become an important product in the study of lithium battery electrolytes.
- it is a very good acid catalyst and has the advantages of environmental friendliness, so it has important economic and social value.
- the bis(fluorosulfonyl)imide studied in the present invention is an important raw material for preparing lithium bis(fluorosulfonyl)imide, because LiFSI used in batteries requires high purity, and only high-purity HFSI can synthesize high-purity LiFSI.
- Patent US4315935, CN102786452, etc. disclose that the synthesis method of HFSI is to first synthesize bis(chlorosulfonyl)imide (HClSI) with chlorosulfonic acid, thionyl chloride and sulfamic acid, and then use fluorinating reagent to fluoride.
- the bis(fluorosulfonyl)imide (HFSI) is obtained.
- the process of synthesizing HFSI by this method is cumbersome.
- the fluorinating agents SbF 3 and BiF 3 used are relatively expensive, and the toxicity is also particularly high.
- the by-product SbCl 3 is easy to sublime, and it is distilled out together with HFSI during vacuum distillation, which makes it difficult to purify HFSI. ; And the use of ZnF 2 will produce a large amount of amine-containing wastewater in the later stage, while the use of HF is more dangerous, and the high toxicity and high corrosiveness make the reaction difficult again.
- the HFSI raw materials obtained by this method are highly toxic and dangerous, consume large amounts, and generate a lot of waste.
- Patents US8337797, US9156692, US5916475, Inorg. Synth. 11,138-43 (1968), etc. disclose the mixed heating reaction of urea and fluorosulfonic acid to prepare HFSI, and the generated HFSI is recovered by vacuum distillation.
- this method will use a polytetrafluoroethylene (PTFE) reactor.
- PTFE polytetrafluoroethylene
- the cost is too high, and the yield is too low, only 40%.
- Fluorosulfonic acid is highly corrosive, expensive, and there are few suppliers.
- the boiling point difference of HFSI is relatively small. It is difficult to separate HFSI from excess or unreacted fluorosulfonic acid by vacuum distillation. After all, the boiling points of the two are not much different, so it is difficult to obtain high-purity HFSI.
- the present invention provides supercritical extraction of the reaction solution of strong inorganic acid and bis(fluorosulfonyl)imide salt by using supercritical fluid CO 2.
- the invention has simple process, easy operation, low production cost, high extraction rate, high purity of the bis(fluorosulfonyl)imine obtained by extraction, high safety factor compared with traditional distillation method, and no pollution to the environment.
- the present invention found a new process after in-depth research: using supercritical fluid CO 2 to extract the reaction liquid of strong inorganic acid and bis(fluorosulfonyl)imide salt.
- the invention has simple process, easy operation, low production cost, high extraction rate, high purity of the bis(fluorosulfonyl)imine obtained by extraction, high safety factor compared with traditional distillation method, and no pollution to the environment.
- the supercritical fluid CO 2 selected in the present invention can process a variety of reaction liquid combinations, mild extraction conditions, simple post-processing, and a wide range of applications.
- the preferred inorganic strong acid is selected from concentrated sulfuric acid, concentrated phosphoric acid, and concentrated nitric acid, and the most preferred is concentrated sulfuric acid.
- Preferred bis(fluorosulfonyl)imide salts include LiFSI, NaFSI, KFSI, RbFSI, CsFSI, Ca(FSI) 2 , Mg(FSI) 2 , NH 4 FSI.
- the preferred molar ratio of bis(fluorosulfonyl)imide salt to strong acid is 1:0.5-1:5.
- the preferred extraction temperature is 25 ⁇ 30°C, and the extraction pressure is 28 ⁇ 35MPa
- the preferred extraction time is 1 to 2 hours.
- the preferred separation pressure is 7-9 MPa, and the separation temperature is 28-32°C.
- the supercritical fluid CO 2 can handle a wide range of reaction liquid types, mild extraction conditions, simple post-processing, and a wide range of applications.
- the reaction liquid selected for the reaction is obtained by the reaction of strong inorganic acid and bis(fluorosulfonyl)imide, which is cheap and low in industrial production cost.
- the reaction uses supercritical fluid CO 2 to extract the product, which can avoid the side reaction of excess acid with the product.
- the reaction uses supercritical fluid CO 2 to extract the product. As long as the temperature and pressure are changed to make CO 2 return to gas, there is no need to heat up distillation and rectification, shorten the purification time, reduce the difficulty of purification, and easily separate and obtain high-purity HFSI.
- the reaction uses supercritical fluid CO 2 to extract the product, without using a large amount of harmful organic solvents, with a high safety factor and no pollution to the environment.
- the present invention provides a high-purity HFSI that can be produced with high efficiency, high quality and low cost, and is suitable for industrial production.
Abstract
A method for supercritical extraction of bis(fluorosulfonyl)imide, comprising: placing a bis(fluorosulfonyl)imide salt and a strong acid into an extraction kettle of a supercritical extraction apparatus, separately heating the extraction kettle and a separator to 20-40°C, introducing supercritical fluid CO2, adjusting the flow to 10-30 kg/h and turning on a high-pressure pump to raise the pressure to 20-40 MPa, and cyclically extracting for 1-4 h; and causing the obtained bis(fluorosulfonyl)imide to flow with the carbon dioxide into the separator, and using a separation pressure of 6-10 MPa and a separation temperature of 25-35°C to obtain a finished product.
Description
本发明属于氟化工锂电池电解质技术领域，具体涉及一种双(氟磺酰)亚胺(HFSI)的超临界提纯方法。The invention belongs to the technical field of fluorine chemical lithium battery electrolyte, and specifically relates to a supercritical purification method of bis(fluorosulfonyl)imide (HFSI).
双(氟磺酰)亚胺(CAS：14984-73-7)，分子式HN(SO
2F)
2，简称HFSI。HFSI是一种强酸，其盐在催化、电解液、氟化剂等方面都有广泛的应用，尤其是其锂盐(LiFSI)的热稳定性很高，200℃以下不分解，化学稳定性也很好，明显优于六氟磷酸锂(LiPF
6)。所以，HFSI成了研究锂电池电解液中间重要的产物，再加上本身是非常好的酸性催化剂，还具有环境友好的优点，因此具有重要的经济和社会价值。
Bis(fluorosulfonyl)imide (CAS: 14984-73-7), molecular formula HN(SO 2 F) 2 , abbreviated as HFSI. HFSI is a strong acid, and its salt has a wide range of applications in catalysis, electrolyte, fluorinating agent, etc. In particular, its lithium salt (LiFSI) has high thermal stability, does not decompose below 200°C, and is chemically stable. Very good, significantly better than lithium hexafluorophosphate (LiPF 6 ). Therefore, HFSI has become an important product in the study of lithium battery electrolytes. In addition, it is a very good acid catalyst and has the advantages of environmental friendliness, so it has important economic and social value.
而本发明所研究的双(氟磺酰)亚胺是制备双(氟磺酰)亚胺锂的重要原料，因为用于电池的LiFSI对纯度要求很高，只有拥有高纯度HFSI才能合成高纯的LiFSI。The bis(fluorosulfonyl)imide studied in the present invention is an important raw material for preparing lithium bis(fluorosulfonyl)imide, because LiFSI used in batteries requires high purity, and only high-purity HFSI can synthesize high-purity LiFSI.
已知文献中双(氟磺酰)亚胺的制备与提取的现有技术如下：The prior art for the preparation and extraction of bis(fluorosulfonyl)imine in the known literature is as follows:
专利US4315935、CN102786452等公开了HFSI的合成方法均是先用氯磺酸、氯化亚砜和氨基磺酸首先合成双(氯磺酰)亚胺(HClSI)，然后再用氟化试剂氟化，得到双(氟磺酰)亚胺(HFSI)。用该方法来合成HFSI工艺繁琐，采用的氟化剂SbF
3、BiF
3等比较贵，毒性也特别大，并且反应副产物SbCl
3易升华，减压蒸馏时与HFSI一起蒸出，难以纯化HFSI；而选用ZnF
2则后期会产生大量的含胺废水，而选用HF则更加危险，高毒高腐蚀性让反应的困难度再次提升。用这类方法得到HFSI原料毒性和危险性较高，消耗量大，也会产生大量的废弃物。
Patent US4315935, CN102786452, etc. disclose that the synthesis method of HFSI is to first synthesize bis(chlorosulfonyl)imide (HClSI) with chlorosulfonic acid, thionyl chloride and sulfamic acid, and then use fluorinating reagent to fluoride. The bis(fluorosulfonyl)imide (HFSI) is obtained. The process of synthesizing HFSI by this method is cumbersome. The fluorinating agents SbF 3 and BiF 3 used are relatively expensive, and the toxicity is also particularly high. The by-product SbCl 3 is easy to sublime, and it is distilled out together with HFSI during vacuum distillation, which makes it difficult to purify HFSI. ; And the use of ZnF 2 will produce a large amount of amine-containing wastewater in the later stage, while the use of HF is more dangerous, and the high toxicity and high corrosiveness make the reaction difficult again. The HFSI raw materials obtained by this method are highly toxic and dangerous, consume large amounts, and generate a lot of waste.
文献(Journal of Fluorine Chemistry 127(2006)193-199)报道了通过使用酸性阳离子交换树脂由双(全氟辛基磺酰)亚胺三乙胺盐制备双(全氟辛基黄酰亚胺)，反应后通过在120-160℃，0.2mmHg条件下升华得到。该方法仅对双(全氟烷基磺酰)亚胺三乙胺盐酸化制备双(全氟烷基磺酰)亚胺有用，所以局限性很大，应用性不够广泛。The literature (Journal of Fluorine Chemistry 127 (2006) 193-199) reported the preparation of bis(perfluorooctyl xanthimide) from bis(perfluorooctylsulfonyl)imide triethylamine salt by using an acidic cation exchange resin. Then it is obtained by sublimation at 120-160°C and 0.2mmHg. This method is only useful for preparing bis(perfluoroalkylsulfonyl)imine by hydrochloric acidification of bis(perfluoroalkylsulfonyl)imine and triethylamine, so it is very limited and not widely applicable.
专利US8337797、US9156692、US5916475及Inorg.Synth.11,138-43(1968)等公开了尿素与氟磺酸混合加热反应制备HFSI，生成的HFSI通过减压蒸馏进行回收。可是本方法会使用聚四氟乙烯(PTFE)材质反应器，造价太高，收率太低只有40％，氟磺酸有强腐蚀性，价格昂贵，并且供应商很少，并且氟磺酸与HFSI的沸点相差较少，用减压蒸馏方式分离HFSI与过量或没反应完的氟磺酸很难，毕竟两者沸点相差不大，因此想得到高纯度的HFSI较困难。Patents US8337797, US9156692, US5916475, Inorg. Synth. 11,138-43 (1968), etc. disclose the mixed heating reaction of urea and fluorosulfonic acid to prepare HFSI, and the generated HFSI is recovered by vacuum distillation. However, this method will use a polytetrafluoroethylene (PTFE) reactor. The cost is too high, and the yield is too low, only 40%. Fluorosulfonic acid is highly corrosive, expensive, and there are few suppliers. The boiling point difference of HFSI is relatively small. It is difficult to separate HFSI from excess or unreacted fluorosulfonic acid by vacuum distillation. After all, the boiling points of the two are not much different, so it is difficult to obtain high-purity HFSI.
中国专利CN105523529A研究报道了在极性非质子溶剂中，双(氟磺酰)亚胺钾与足够量的强酸反应制备双(氟磺酰)亚胺粗品，再经减压蒸馏得到高纯的HFSI。专利中表明所选用的强酸是高氯酸、氢碘酸、氯磺酸、氟磺酸和三氟乙酸。通过实验发现氯磺酸参与反应容易发生副反应，不易得到高纯HFSI。而高氯酸、氢碘酸、氟磺酸和三氟乙酸价格太贵，对设备要求也很高，不利于工业化生产。中国专利CN104961110B研究报道了以双(氟磺酰)亚胺碱金属盐为溶质，配制成溶液后向溶液中鼓入氯化氢气体，从而得到HFSI。该方法难以控制整个反应设备的压力控制，消耗氯化氢气体较多，对设备要求较高，并且后期需要大量的碱液去处理排气，因此会有大量的废液需要处理。中国专利CN107986248A研究报道了先制备双(氟磺酰)亚胺的有机碱盐，再将其与强酸进行置换反应，再通过减压蒸馏得到HFSI。该方法是直接将反应液加热减压蒸馏，而实验结果表明在加热过程中有过量强酸会发生副反应，并且后期很难除去副产物。Chinese patent CN105523529A reported that in a polar aprotic solvent, potassium bis(fluorosulfonyl)imide reacts with a sufficient amount of strong acid to prepare crude bis(fluorosulfonyl)imide, which is then distilled under reduced pressure to obtain high purity HFSI . The patent indicates that the strong acids used are perchloric acid, hydroiodic acid, chlorosulfonic acid, fluorosulfonic acid and trifluoroacetic acid. It is found through experiments that chlorosulfonic acid participates in the reaction and is prone to side reactions, and it is difficult to obtain high-purity HFSI. However, perchloric acid, hydroiodic acid, fluorosulfonic acid and trifluoroacetic acid are too expensive and require high equipment, which is not conducive to industrial production. The Chinese patent CN104961110B research reported that the alkali metal salt of bis(fluorosulfonyl)imide was used as the solute, and then hydrogen chloride gas was blown into the solution to obtain HFSI. This method is difficult to control the pressure control of the entire reaction equipment, consumes more hydrogen chloride gas, requires higher equipment, and requires a large amount of lye to treat the exhaust later, so there will be a large amount of waste liquid to be treated. Chinese patent CN107986248A research reported that the organic base salt of bis(fluorosulfonyl)imide was first prepared, and then replaced with a strong acid, and then HFSI was obtained by distillation under reduced pressure. The method is to directly heat the reaction solution under reduced pressure for distillation, and the experimental results show that excessive strong acid will cause side reactions during the heating process, and it is difficult to remove the by-products in the later stage.
文献(Inorganic Chemistry32(1993)5007-5010；Inorganic Chemistry23(1984)3720-3723) 将5.0g干燥的双(全氟烷基磺酰)亚胺钠溶解在43g浓硫酸(100％)中，置于升华器中，在60℃高真空条件下得到4.2g双(全氟烷基磺酰)亚胺。但是该方法中由于选用100％的浓硫酸使得HFSI难以升华，并且在加热过程中容易发生分解，得到很多副产物，并且在后期难以提纯。Literature (Inorganic Chemistry 32 (1993) 5007-5010; Inorganic Chemistry 23 (1984) 3720-3723) Dissolve 5.0 g of dry sodium bis(perfluoroalkylsulfonyl) imide in 43 g of concentrated sulfuric acid (100%) and place In the sublimator, 4.2 g of bis(perfluoroalkylsulfonyl)imide was obtained under high vacuum at 60°C. However, in this method, the use of 100% concentrated sulfuric acid makes HFSI difficult to sublime, and is prone to decomposition during heating, resulting in many by-products, and it is difficult to purify in the later stage.
本发明针对以上缺点，提供了通过使用超临界流体CO
2对无机强酸和双(氟磺酰)亚胺盐的反应液进行超临界萃取。本发明工艺简单，容易操作，生产成本低，萃取率高，萃取得到的双(氟磺酰)亚胺纯度高，相对于传统的蒸馏方法，安全系数高，不会对环境造成污染。
In view of the above shortcomings, the present invention provides supercritical extraction of the reaction solution of strong inorganic acid and bis(fluorosulfonyl)imide salt by using supercritical fluid CO 2. The invention has simple process, easy operation, low production cost, high extraction rate, high purity of the bis(fluorosulfonyl)imine obtained by extraction, high safety factor compared with traditional distillation method, and no pollution to the environment.
发明内容Summary of the invention
本发明针对已有的技术中缺点，经深入研究后发现了一种新的工艺：使用超临界流体CO
2对无机强酸和双(氟磺酰)亚胺盐的反应液进行萃取。本发明工艺简单，容易操作，生产成本低，萃取率高，萃取得到的双(氟磺酰)亚胺纯度高，相对于传统的蒸馏方法，安全系数高，不会对环境造成污染。
Aiming at the shortcomings of the existing technology, the present invention found a new process after in-depth research: using supercritical fluid CO 2 to extract the reaction liquid of strong inorganic acid and bis(fluorosulfonyl)imide salt. The invention has simple process, easy operation, low production cost, high extraction rate, high purity of the bis(fluorosulfonyl)imine obtained by extraction, high safety factor compared with traditional distillation method, and no pollution to the environment.
一方面本发明选择的超临界流体CO
2可以处理的反应液种类组合多，萃取条件温和，后期处理简单，适应范围广泛。
On the one hand, the supercritical fluid CO 2 selected in the present invention can process a variety of reaction liquid combinations, mild extraction conditions, simple post-processing, and a wide range of applications.
另一方面，我们舍弃传统的繁琐的溶剂萃取方式，这样得到的产品只要改变温度和压力使CO
2变回气体，不用再升温蒸馏和精馏，缩短提纯时间，降低提纯难度，容易分离得到高纯度HFSI。
On the other hand, we abandon the traditional cumbersome solvent extraction method, so that the product obtained only needs to change the temperature and pressure to change the CO 2 back to the gas. There is no need to heat up the distillation and rectification, shorten the purification time, reduce the difficulty of purification, and it is easy to separate and obtain high Purity HFSI.
优选的无机强酸选自浓硫酸、浓磷酸、浓硝酸，最优选的是浓硫酸。The preferred inorganic strong acid is selected from concentrated sulfuric acid, concentrated phosphoric acid, and concentrated nitric acid, and the most preferred is concentrated sulfuric acid.
优选的双(氟磺酰)亚胺盐包括LiFSI、NaFSI、KFSI、RbFSI、CsFSI、Ca(FSI)
2、Mg(FSI)
2、NH
4FSI。
Preferred bis(fluorosulfonyl)imide salts include LiFSI, NaFSI, KFSI, RbFSI, CsFSI, Ca(FSI) 2 , Mg(FSI) 2 , NH 4 FSI.
优选的双(氟磺酰)亚胺盐与强酸的摩尔比为1:0.5-1:5。The preferred molar ratio of bis(fluorosulfonyl)imide salt to strong acid is 1:0.5-1:5.
优选的萃取温度为25～30℃，萃取压力为28～35MPaThe preferred extraction temperature is 25～30℃, and the extraction pressure is 28～35MPa
优选的萃取时间为1～2h。The preferred extraction time is 1 to 2 hours.
优选的分离压力为7～9MPa，分离温度为28～32℃。The preferred separation pressure is 7-9 MPa, and the separation temperature is 28-32°C.
本发明有以下优势：The present invention has the following advantages:
1、超临界流体CO
2可以处理的反应液种类组合多，萃取条件温和，后期处理简单，适应范围广泛。
1. The supercritical fluid CO 2 can handle a wide range of reaction liquid types, mild extraction conditions, simple post-processing, and a wide range of applications.
2、反应选用的反应液是无机强酸与双(氟磺酰)亚胺反应得到，价格便宜，工业化生产成本低廉。2. The reaction liquid selected for the reaction is obtained by the reaction of strong inorganic acid and bis(fluorosulfonyl)imide, which is cheap and low in industrial production cost.
3、反应用超临界流体CO
2萃取产物，可以避免多余的酸与产物发生副反应。
3. The reaction uses supercritical fluid CO 2 to extract the product, which can avoid the side reaction of excess acid with the product.
4、反应用超临界流体CO
2萃取产物，只要改变温度和压力使CO
2变回气体，不用再升温蒸馏和精馏，缩短提纯时间，降低提纯难度，容易分离得到高纯度HFSI。
4. The reaction uses supercritical fluid CO 2 to extract the product. As long as the temperature and pressure are changed to make CO 2 return to gas, there is no need to heat up distillation and rectification, shorten the purification time, reduce the difficulty of purification, and easily separate and obtain high-purity HFSI.
5、反应用超临界流体CO
2萃取产物，不用使用大量有害有机溶剂，安全系数高，不会对环境造成污染。
5. The reaction uses supercritical fluid CO 2 to extract the product, without using a large amount of harmful organic solvents, with a high safety factor and no pollution to the environment.
可见，本发明提供了一种能高效高品质、低成本制得高纯的HFSI，适合工业化生产。It can be seen that the present invention provides a high-purity HFSI that can be produced with high efficiency, high quality and low cost, and is suitable for industrial production.
下面的实施例为用来说明本发明的几个具体的实施方式，但并不将本发明局限于这些具体实施方式。本领域技术人员应该认识到，本发明涵盖了权利要求书范围内所可能包括的所有备选方案、改进方案和等效方案。The following examples are used to illustrate several specific embodiments of the present invention, but the present invention is not limited to these specific embodiments. Those skilled in the art should realize that the present invention covers all alternatives, improvements and equivalents that may be included in the scope of the claims.
实施例1Example 1
双(氟磺酰)亚胺(HFSI)的提纯：Purification of bis(fluorosulfonyl)imide (HFSI):
将双(氟磺酰)亚胺钠与浓硫酸投入超临界萃取装置的萃取釜中，分别将萃取釜和分离器加热到27℃，导入超临界流体CO
2，调节流量为30kg/h，并且打开高压泵升压至40MPa，循环萃取1h；萃取得到的双(氟磺酰)亚胺随二氧化碳流入分离器中，分离压力7MPa，分离温度30℃；CO
2变成气体离开体系，得成品。测试为双(氟磺酰)亚胺HFSI，收率93％，含量≥99.9％。
Put sodium bis(fluorosulfonyl)imide and concentrated sulfuric acid into the extraction kettle of the supercritical extraction device, heat the extraction kettle and separator to 27°C, introduce supercritical fluid CO 2 , adjust the flow rate to 30kg/h, and Turn on the high-pressure pump to increase the pressure to 40MPa, and circulate the extraction for 1 hour; the extracted bis(fluorosulfonyl)imine flows into the separator with carbon dioxide, the separation pressure is 7MPa, and the separation temperature is 30°C; CO 2 becomes a gas and leaves the system to obtain a finished product. The test is bis(fluorosulfonyl)imide HFSI, the yield is 93%, and the content is ≥99.9%.
实施例2Example 2
双(氟磺酰)亚胺(HFSI)的提纯：Purification of bis(fluorosulfonyl)imide (HFSI):
将双(氟磺酰)亚胺钾与浓硝酸投入超临界萃取装置的萃取釜中，分别将萃取釜和分离器加热到25℃，导入超临界流体CO
2，调节流量为20kg/h，并且打开高压泵升压至30MPa，循环萃取2h；萃取得到的双(氟磺酰)亚胺随二氧化碳流入分离器中，分离压力8MPa，分离温度30℃；CO
2变成气体离开体系，得成品。测试为双(氟磺酰)亚胺HFSI，收率95％，含量≥99.9％。
Put potassium bis(fluorosulfonyl)imide and concentrated nitric acid into the extraction kettle of the supercritical extraction device, heat the extraction kettle and separator to 25°C respectively, introduce supercritical fluid CO 2 , adjust the flow rate to 20kg/h, and Turn on the high-pressure pump to increase the pressure to 30MPa, and circulate the extraction for 2h; the extracted bis(fluorosulfonyl)imine flows into the separator with carbon dioxide, the separation pressure is 8MPa, and the separation temperature is 30°C; CO 2 becomes a gas and leaves the system to obtain the finished product. The test is bis(fluorosulfonyl)imide HFSI, the yield is 95%, and the content is ≥99.9%.
实施例3Example 3
双(氟磺酰)亚胺(HFSI)的提纯：Purification of bis(fluorosulfonyl)imide (HFSI):
将双(氟磺酰)亚胺钾与浓硫酸投入超临界萃取装置的萃取釜中，分别将萃取釜和分离器加热到28℃，导入超临界流体CO
2，调节流量为24kg/h，并且打开高压泵升压至35MPa，循环萃取1h；萃取得到的双(氟磺酰)亚胺随二氧化碳流入分离器中，分离压力9MPa，分离温度32℃；CO
2变成气体离开体系，得成品。测试为双(氟磺酰)亚胺HFSI，收率97％，含量≥99.9％。
Put potassium bis(fluorosulfonyl)imide and concentrated sulfuric acid into the extraction kettle of the supercritical extraction device, heat the extraction kettle and separator to 28°C respectively, introduce supercritical fluid CO 2 , adjust the flow rate to 24kg/h, and Turn on the high-pressure pump to increase the pressure to 35MPa, and circulate the extraction for 1h; the extracted bis(fluorosulfonyl)imine flows into the separator with carbon dioxide, the separation pressure is 9MPa, and the separation temperature is 32°C; CO 2 becomes a gas and leaves the system to obtain a finished product. The test is bis(fluorosulfonyl)imide HFSI, the yield is 97%, and the content is ≥99.9%.
实施例4Example 4
双(氟磺酰)亚胺(HFSI)的提纯：Purification of bis(fluorosulfonyl)imide (HFSI):
将双(氟磺酰)亚胺钠与浓磷酸投入超临界萃取装置的萃取釜中，分别将萃取釜和分离器加热到29℃，导入超临界流体CO
2，调节流量为25kg/h，并且打开高压泵升压至40MPa，循环萃取2h；萃取得到的双(氟磺酰)亚胺随二氧化碳流入分离器中，分离压力8MPa，分离温度28℃；CO
2变成气体离开体系，得成品。测试为双(氟磺酰)亚胺HFSI，收率89％，含量≥99.9％。
Put sodium bis(fluorosulfonyl)imide and concentrated phosphoric acid into the extraction kettle of the supercritical extraction device, heat the extraction kettle and separator to 29°C, introduce supercritical fluid CO 2 , adjust the flow rate to 25kg/h, and Turn on the high-pressure pump to increase the pressure to 40MPa, and circulate the extraction for 2h; the extracted bis(fluorosulfonyl)imine flows into the separator with carbon dioxide, the separation pressure is 8MPa, and the separation temperature is 28°C; CO 2 becomes a gas and leaves the system to obtain a finished product. The test is bis(fluorosulfonyl)imide HFSI, the yield is 89%, and the content is ≥99.9%.
Claims (7)
- 超临界提纯双(氟磺酰)亚胺的方法，其特征在于，包括以下步骤：The method for supercritical purification of bis(fluorosulfonyl)imine is characterized in that it comprises the following steps:S001.将双(氟磺酰)亚胺盐与强酸投入超临界萃取装置的萃取釜中；S001. Put the bis(fluorosulfonyl) imide salt and strong acid into the extraction kettle of the supercritical extraction device;S002.分别将萃取釜和分离器加热到20～40℃，导入超临界流体CO 2，调节流量为10～30kg/h，并且打开高压泵升压至20～40MPa，循环萃取1～4h； S002. Heat the extraction kettle and separator to 20-40°C respectively, introduce supercritical fluid CO 2 , adjust the flow rate to 10-30 kg/h, and turn on the high-pressure pump to increase the pressure to 20-40 MPa, and cycle extraction for 1 to 4 hours;S003.萃取得到的双(氟磺酰)亚胺随二氧化碳流入分离器中，分离压力6～10MPa，分离温度25～35℃，得成品；S003. The bis(fluorosulfonyl)imine obtained by extraction flows into the separator with carbon dioxide, the separation pressure is 6-10MPa, and the separation temperature is 25-35°C to obtain the finished product;
- 根据权利要求1所述的双(氟磺酰)亚胺的超临界提纯方法，其特征在于，强酸选自浓硫酸、浓磷酸、浓硝酸。The method for supercritical purification of bis(fluorosulfonyl)imine according to claim 1, wherein the strong acid is selected from concentrated sulfuric acid, concentrated phosphoric acid, and concentrated nitric acid.
- 根据权利要求1所述的双(氟磺酰)亚胺的超临界提纯方法，其特征在于，双(氟磺酰)亚胺盐包括双(氟磺酰)亚胺锂(LiFSI)、双(氟磺酰)亚胺钠(NaFSI)、双(氟磺酰)亚胺钾(KFSI)、双(氟磺酰)亚胺铷(RbFSI)、双(氟磺酰)亚胺铯(CsFSI)、双(氟磺酰)亚胺钙(Ca(FSI) 2)、双(氟磺酰)亚胺镁(Mg(FSI) 2)、双(氟磺酰)亚胺铵(NH 4FSI)。 The method for supercritical purification of bis(fluorosulfonyl)imide according to claim 1, wherein the bis(fluorosulfonyl)imide salt comprises lithium bis(fluorosulfonyl)imide (LiFSI), bis(fluorosulfonyl)imide (LiFSI), Sodium fluorosulfonyl)imide (NaFSI), potassium bis(fluorosulfonyl)imide (KFSI), rubidium bis(fluorosulfonyl)imide (RbFSI), cesium bis(fluorosulfonyl)imide (CsFSI), Calcium bis(fluorosulfonyl)imide (Ca(FSI) 2 ), magnesium bis(fluorosulfonyl)imide (Mg(FSI) 2 ), ammonium bis(fluorosulfonyl)imide (NH 4 FSI).
- 根据权利要求1所述的双(氟磺酰)亚胺的超临界提纯方法，其特征在于双(氟磺酰)亚胺盐与强酸的摩尔比为1:0.5-1:5。The method for supercritical purification of bis(fluorosulfonyl)imide according to claim 1, characterized in that the molar ratio of the bis(fluorosulfonyl)imide to the strong acid is 1:0.5-1:5.
- 根据权利要求1所述的双(氟磺酰)亚胺的超临界提纯方法，其特征在于，所述步骤S002中萃取温度为25～30℃，萃取压力为28～35MPa。The method for supercritical purification of bis(fluorosulfonyl)imine according to claim 1, wherein the extraction temperature in step S002 is 25-30°C, and the extraction pressure is 28-35 MPa.
- 根据权利要求1所述的双(氟磺酰)亚胺的超临界提纯方法，其特征在于，所述步骤S002中萃取时间为1～2h。The method for supercritical purification of bis(fluorosulfonyl)imine according to claim 1, wherein the extraction time in step S002 is 1 to 2 hours.
- 根据权利要求1所述的双(氟磺酰)亚胺的超临界提纯方法，其特征在，所述步骤S003中分离压力为7～9MPa，分离温度为28～32℃。The method for supercritical purification of bis(fluorosulfonyl)imine according to claim 1, wherein the separation pressure in step S003 is 7-9 MPa, and the separation temperature is 28-32°C.
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|---|---|---|---|---|
| CN113666346A (en) * | 2021-08-23 | 2021-11-19 | 泰兴华盛精细化工有限公司 | Short-path distillation efficient purification device and purification method for lithium bis (fluorosulfonyl) imide |
| CN115215306A (en) * | 2022-06-29 | 2022-10-21 | 山东凯盛新材料股份有限公司 | Preparation method and preparation equipment of high-purity bis (chlorosulfonyl) imide |
| WO2023202919A1 (en) * | 2022-04-21 | 2023-10-26 | Specialty Operations France | Process for purifying a lithium salt of bis(fluorosulfonyl)imide |
| WO2023202920A1 (en) | 2022-04-21 | 2023-10-26 | Specialty Operations France | Process for manufacture lithium salt of bis(fluorosulfonyl)imide in solid form |
| WO2023202918A1 (en) | 2022-04-21 | 2023-10-26 | Specialty Operations France | Process for manufacture lithium salt of bis(fluorosulfonyl)imide in solid form |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115676784B (en) * | 2022-12-01 | 2023-10-31 | 森松（江苏）重工有限公司 | Impurity removal and purification system and impurity removal and purification method for difluoro sulfimide |
| CN116002635A (en) * | 2022-12-27 | 2023-04-25 | 浙江研一新能源科技有限公司 | Purification method of lithium bis (fluorosulfonyl) imide |
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| CN109928372A (en) * | 2019-04-12 | 2019-06-25 | 广州理文科技有限公司 | A kind of preparation method of double fluorine sulfimides |
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| CN107986248A (en) * | 2017-11-17 | 2018-05-04 | 南京红太阳生物化学有限责任公司 | A kind of preparation method of double fluorine sulfimides |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113666346A (en) * | 2021-08-23 | 2021-11-19 | 泰兴华盛精细化工有限公司 | Short-path distillation efficient purification device and purification method for lithium bis (fluorosulfonyl) imide |
| WO2023202919A1 (en) * | 2022-04-21 | 2023-10-26 | Specialty Operations France | Process for purifying a lithium salt of bis(fluorosulfonyl)imide |
| WO2023202920A1 (en) | 2022-04-21 | 2023-10-26 | Specialty Operations France | Process for manufacture lithium salt of bis(fluorosulfonyl)imide in solid form |
| WO2023202918A1 (en) | 2022-04-21 | 2023-10-26 | Specialty Operations France | Process for manufacture lithium salt of bis(fluorosulfonyl)imide in solid form |
| CN115215306A (en) * | 2022-06-29 | 2022-10-21 | 山东凯盛新材料股份有限公司 | Preparation method and preparation equipment of high-purity bis (chlorosulfonyl) imide |
| CN115215306B (en) * | 2022-06-29 | 2024-03-08 | 山东凯盛新材料股份有限公司 | Preparation method and preparation equipment of high-purity dichloro sulfonyl imide |
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| CN112739646A (en) | 2021-04-30 |
| CN112739646B (en) | 2023-08-15 |
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