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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/0053—Details of the reactor
  • B01J19/0066—Stirrers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
• • 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
  • C01B21/0935—Imidodisulfonic acid; Nitrilotrisulfonic acid; Salts thereof
• • 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
  • C01B21/096—Amidosulfonic acid; Salts thereof
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/02—Apparatus characterised by their chemically-resistant properties
  • B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
  • B01J2219/0213—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components of enamel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/02—Apparatus characterised by their chemically-resistant properties
  • B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
  • B01J2219/0236—Metal based
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/02—Apparatus characterised by their chemically-resistant properties
  • B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
  • B01J2219/0245—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components of synthetic organic material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/02—Apparatus characterised by their chemically-resistant properties
  • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
  • B01J2219/0259—Enamel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/02—Apparatus characterised by their chemically-resistant properties
  • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
  • B01J2219/0277—Metal based
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/02—Apparatus characterised by their chemically-resistant properties
  • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
  • B01J2219/0277—Metal based
  • B01J2219/0286—Steel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/02—Apparatus characterised by their chemically-resistant properties
  • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
  • B01J2219/0277—Metal based
  • B01J2219/029—Non-ferrous metals
• • 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
  • H01M10/0567—Liquid materials characterised by the additives
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• Li-ion batteries require the development of higher power batteries. This involves increasing the nominal voltage of the Li-ion batteries. To reach the targeted voltages, electrolytes of high purity are necessary.
• Anions of sulfonylimide type by their very low basicity, are increasingly used in the field of energy storage in the form of inorganic salts in batteries, or organic salts in supercapacitors or in the field of liquids ionic.
• LiPF 6 the most currently used salt is LiPF 6 .
• This salt shows many disadvantages such as limited thermal stability, sensitivity to hydrolysis and therefore lower battery safety.
• new salts having the fluorosulfonyl group FSO2 have been studied and have demonstrated many advantages such as better ionic conductivity and resistance to hydrolysis.
• LiFSI has shown very interesting properties that make it a good candidate to replace LiPF 6 .
• the present invention relates to a process for preparing a lithium salt of bis (fluorosulfonyl) imide F- (SO 2 ) -NLi- (SO 2 ) -F comprising a step (a) comprising a step of chlorinating the acid Sulfamic H0- (S0 2 ) -NH 2 to obtain the bis (chlorosulfonyl) imide Cl- (S0 2 ) -NH- (S0 2 ) -CI, said step (a) being carried out in a reactor made of a material M3 corrosion-resistant, or in a reactor containing a base layer made of a material M1 coated with a surface layer made of a material M2 resistant to corrosion.
• lithium salt of bis (fluorosulfonyl) imide lithium
• lithium bis (sulfonyl) imide lithium
• LiFSI lithium
• LiN (FSC> 2) 2 lithium
• Bis (sulfonyl) imide lithium or “lithium bis (fluorosulfonyl) imide” or "F- (SC> 2) -NU- (SO 2 ) -F".
• the surface layer of the reactor of step (a) is the layer likely to be in contact with the reaction medium of step (a) of chlorination (for example starting reagents, products generated, etc.), the reaction medium may comprise any type of phase: liquid, and / or gas, and / or solid.
• the surface layer of the reactor of step (a) is at least in contact with at least one of the starting reagents, such as, for example, sulfamic acid.
• the surface layer has a thickness of between 0.01 and 20 mm, said thickness of said inner surface layer being less than that of said base layer.
• said inner surface layer has a thickness of between 0.05 and 15 mm, preferably between 0.1 and 10 mm, advantageously between 0.1 and 5 mm.
• the material M1 comprises:
• At least 60% by weight of iron preferably at least 70% by weight, advantageously at least 75% by weight, still more preferably at least 80% by weight, more preferably at least 85% by weight, in particular at less than 90% by weight, more particularly at least 95% by weight, and even more preferably at least 97% by weight of iron relative to the total weight of the material M1; and you)
• less than 2% by weight of carbon advantageously less than 1, 5% by weight, preferably less than 1% by weight, more preferably less than 0.75% by weight, in particular less than 0.5% by weight, more particularly less than 0.2% by weight, preferably less than 0.1% by weight of carbon relative to the total weight of the material M1; and or
• molybdenum less than 3% by weight of molybdenum, advantageously less than 2% by weight, preferably less than 1, 5% by weight, preferably less than 1, 25% by weight, more preferably less than 1% by weight of molybdenum relative to the total weight of the material M1; and or
• chromium less than 20% by weight of chromium, preferably less than 5% by weight of chromium, advantageously less than 4% by weight, preferably less than 3% by weight, more preferably less than 2% by weight, in particular less than 1% by weight % by weight of chromium relative to the total weight of the material M1; and or
• nickel less than 15% by weight of nickel, preferably less than 5% by weight, advantageously less than 4% by weight, preferably less than 3% by weight, more preferably less than 2% by weight, in particular less than 1% by weight, weight of nickel relative to the total weight of the material M1; and or
• manganese less than 2.5% by weight of manganese, advantageously less than 2% by weight, preferably less than 1.5% by weight, more preferably less than 1% by weight of manganese relative to the total weight of material M1.
• the material M1 comprises:
• less than 2% by weight of carbon advantageously less than 1, 5% by weight, preferably less than 1% by weight, preferably less than 0.75% by weight, more preferably less than 0.5% by weight, more particularly less than 0.2% by weight, and even more preferably between 0.01% and 0.2% by weight of carbon relative to the total weight of the material M1; and or
• molybdenum less than 3% by weight of molybdenum, advantageously less than 2% by weight, preferably less than 1, 5% by weight, preferably less than 1, 25% by weight, more preferably less than 1% by weight, still more advantageously between 0.1% and 1% by weight of molybdenum relative to the total weight of the material M1, and / or
• chromium less than 5% by weight of chromium, preferably less than 4% by weight, advantageously less than 3% by weight, preferably less than 2% by weight, in particular between 0.5% and 2% by weight of chromium relative to the total weight of the material M1; and or
• manganese less than 2.5% by weight of manganese, advantageously less than 2% by weight, preferably less than 1.5% by weight, more preferably less than 1% by weight, in particular between 0.1% and 1% by weight, weight of manganese relative to the total weight of the material M1.
• the material M1 comprises at least 60% by weight of iron, preferably at least 70% by weight of iron, advantageously at least 75% by weight, still more advantageously at least 80% by weight, more preferably at least 85% by weight. % by weight, in particular at least 90% by weight, more particularly at least 95% by weight, and even more preferably at least 97% by weight of iron relative to the total weight of the material M1; and less than 2% by weight of carbon, advantageously less than 1.5% by weight, preferably less than 1% by weight, preferably less than 0.75% by weight, more preferably less than 0.5% by weight, more particularly less than 0.2% by weight, and even more preferably between 0.01% and 0.2% by weight of carbon relative to the total weight of the material M1; and less than 3% by weight of molybdenum, preferably less than 2% by weight, preferably less than 1, 5% by weight, preferably less than 1, 25% by weight, more preferably less than 1% by weight, still more advantageously between 0.1% and 1% by weight of molyb
• the material M1 comprises:
• silicon less than 2% by weight of silicon, advantageously less than 1.5% by weight, preferably less than 1.25% by weight, more preferably less than 1% by weight of silicon relative to the total weight of the material M1.
• the material M1 comprises at least 60% by weight of iron, more particularly at least 70% by weight of iron relative to the total weight of the material M1; and less than 2% by weight of carbon, advantageously less than 1, 5% by weight, preferably less than 1% by weight, more preferably less than 0.75% by weight, in particular less than 0.5% by weight more particularly less than 0.2% by weight, still more preferably less than 0.1% by weight relative to the total weight of the material M1; and from 10% to 20% by weight of chromium, preferably from 15% to 20% by weight, in particular from 16% to 18.5% by weight of chromium relative to the total weight of the material M1; and less than 15% by weight of nickel, preferably between 10% and 14% by weight of nickel relative to the total weight of the material M1; and less than 3% by weight of molybdenum, advantageously between 2% and 3.0% by weight of molybdenum relative to the total weight of the material M1; and less 2.5% by weight of manganese, advantageously 2% by weight of manganes
• the material M2 is chosen from nickel-based alloys comprising at least 45% by weight of nickel, more preferably at least 50% by weight of nickel, in particular at least 55% by weight of nickel, more particularly at least 60% by weight of nickel, preferably at least 65% by weight of nickel, more preferably at least 70% by weight of nickel relative to the total weight of the material M2.
• the material M2 may be chosen from nickel-based alloys comprising from 45% to 95% by weight of nickel, preferably from 50% to 90% by weight of nickel relative to the total weight of the material M2.
• the M2 material may also comprise chromium in a content of less than 35% by weight relative to the total weight of the material M2, advantageously less than 30% by weight, preferably less than 20% by weight, more preferably less than 15% by weight, in particular less than 10% by weight, more particularly less than 5% by weight relative to the total weight of the material M2.
• the M2 material may also comprise molybdenum in a content of less than 35% by weight relative to the total weight of the material M2, advantageously less than 30% by weight, preferably less than 20% by weight, more preferably less than 15% by weight, in particular less than 10% by weight, more particularly less than 5% by weight relative to the total weight of the material M2.
• the material M2 (nickel-based alloys) comprises at least 40% by weight of nickel relative to the total weight of the material M2, preferably at least 45% by weight, more preferably at least 50% by weight, at least 55% by weight, more particularly at least 60% by weight, preferably at least 65% by weight, more preferably at least 70% by weight of nickel relative to the total weight of material M2; and less than 35% by weight of chromium, advantageously less than 30% by weight, preferably less than 20% by weight, more preferably less than 15% by weight, in particular less than 10% by weight, more particularly less than 5% by weight.
• % by weight of chromium relative to the total weight of the material M2 % by weight of chromium relative to the total weight of the material M2; and less than 35% by weight of molybdenum, preferably less than 30% by weight, preferably less than 25% by weight, more preferably less than 20% by weight, in particular less than 15% by weight, more preferably less than 10% by weight. % by weight of molybdenum, based on the total weight of the material M2.
• the M2 material may also comprise cobalt in a content of less than 10% by weight relative to the total weight of the material M2, advantageously less than 8% by weight, preferably less than 6% by weight, more preferably less than 4% by weight, in particular less than 3% by weight, more particularly less than 2% by weight relative to the total weight of the material M2.
• the M2 material may also comprise tungsten in a content of less than 5% by weight relative to the total weight of the material M2, advantageously less than 4% by weight, preferably less than 3% by weight, more preferably less than 2% by weight, in particular less than 1% by weight relative to the total weight of the material M2.
• the M2 material may also comprise iron in a content of less than 25% by weight relative to the total weight of the material M2, advantageously less than 20% by weight, preferably less than 15% by weight, more preferably less than 10% by weight, in particular less than 7% by weight, more particularly less than 5% by weight relative to the total weight of the material M2.
• the M2 material may also comprise manganese in a content of less than 5% by weight relative to the total weight of the alloy, advantageously less than 4% by weight, preferably less than 3% by weight. , more preferably less than 2% by weight, in particular less than 1% by weight, more particularly less than 0.5% by weight relative to the total weight of the material M2.
• the M2 material may also comprise copper in a content of less than 50% by weight, advantageously less than 45% by weight, preferably less than 40% by weight, more preferably less than 35% by weight. , in particular less than 30% by weight, more particularly less than 25% by weight of copper relative to the total weight of the material M2.
• % by weight of chromium relative to the total weight of the material M2 and less than 25% by weight of iron, preferably less than 20% by weight, preferably less than 15% by weight, more preferably less than 10% by weight, in particular less than 7% by weight, more particularly less than 5% by weight.
• % by weight of iron relative to the total weight of the material M2 and optionally less than 35% by weight of molybdenum, advantageously less than 30% by weight, preferably less than 20% by weight, more preferably less than 15% by weight, in particular less than 10% by weight, more particularly less than 5% by weight of molybdenum relative to the total weight of the material M2.
• the material M2 may comprise less than 4% by weight of titanium relative to the total weight of the material M2, advantageously less than 3% by weight, preferably less than 2% by weight, more preferably less than 1% by weight, especially less than 0.5% by weight, more particularly less than 0.05% by weight of titanium relative to the total weight of the material M2, in a preferred way the material M2 is devoid of titanium.
• the material M2 may comprise less than 6% by weight of niobium relative to the total weight of the material M2, advantageously less than 4% by weight, preferably less than 2% by weight, more preferably less than 1% by weight, in particular less than 0.5% by weight, more particularly less than 0.05% by weight of niobium relative to the total weight of the material M2, preferably the material M2 is free of niobium.
• the reactor used in step (a) of the method according to the invention comprises a base layer made of a material M1 coated with a surface layer made of a material M2 resistant to corrosion said material M1 comprising:
• At least 60% by weight of iron preferably at least 70% by weight of iron, advantageously at least 75% by weight, still more advantageously at least 80% by weight, more preferably at least 85% by weight, in particular at least 90% by weight, more particularly at least 95% by weight, and even more preferably at least 97% by weight of iron relative to the total weight of the material M1; and less than 2% by weight of carbon, advantageously less than 1.5% by weight, preferably less than 1% by weight, preferably less than 0.75% by weight, more preferably less than 0.5% by weight, more particularly less than 0.2% by weight, and even more preferably between 0.01% and 0.2% by weight of carbon relative to the total weight of the material M1; and less than 3% by weight of molybdenum, advantageously less than 2% by weight, preferably less than 1, 5% by weight, preferably less than 1, 25% by weight, more preferably less than 1% by weight, even more advantageously between 0.1% and 1% by weight of molybdenum relative to the total weight of the material M1, and
• the material M2 being chosen from alloys based on nickel, in particular chosen from alloys comprising at least 40% by weight of nickel, advantageously at least 45% by weight, more preferably at least 50% by weight, in particular at least less than 55% by weight, more particularly at least 60% by weight, preferably at least 65% by weight, even more preferably at least 70% by weight of nickel relative to the total weight of material M2; and / or chromium in a content of less than 35% by weight relative to the total weight of the material M2, advantageously less than 30% by weight, preferably less than 20% by weight, more preferably less than 15% by weight, in particular less than 10% by weight, more particularly less than 5% by weight relative to the total weight of the material M2; and / or molybdenum in a content of less than 35% by weight relative to the total weight of the material M2, advantageously less than 30% by weight, preferably less than 25% by weight, more preferably less than 20% by weight, in particular less than 15% by weight, more particularly less than 10% by weight relative to the total weight of
• At least 60% by weight of iron preferably at least 70% by weight of iron, advantageously at least 75% by weight, still more advantageously at least 80% by weight, more preferably at least 85% by weight, in particular at least 90% by weight, more particularly at least 95% by weight, and even more preferably at least 97% by weight of iron relative to the total weight of the material M1; and less than 2% by weight of carbon, advantageously less than 1.5% by weight, preferably less than 1% by weight, preferably less than 0.75% by weight, more preferably less than 0.5% by weight, more particularly less than 0.2% by weight, and even more preferably between 0.01% and 0.2% by weight of carbon relative to the total weight of the material M1; and less than 3% by weight of molybdenum, advantageously less than 2% by weight, preferably less than 1, 5% by weight, preferably less than 1, 25% by weight, more preferably less than 1% by weight, even more advantageously between 0.1% and 1% by weight of molybdenum relative to the total weight of the material M1, and
• the material M2 being chosen from fluorinated polymers, and in particular thermoplastic fluorinated polymers, such as for example PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PFA (copolymers of C 2 F 4 and ether perfluorinated vinyl), FEP (copolymers of tetrafluoroethylene and perfluoropropene, such as, for example, copolymer of C 2 F 4 and C 3 F 6 ), ETFE (copolymer of tetrafluoroethylene and ethylene, and FKM (copolymer of hexafluoropropylene and difluoroethylene).
• PVDF polyvinylidene fluoride
• PTFE polytetrafluoroethylene
• PFA copolymers of C 2 F 4 and ether perfluorinated vinyl
• FEP copolymers of tetrafluoroethylene and perfluoropropene, such as, for example, cop
• the corrosion rate of the material M2 is less than 100 mGh / year, preferably less than 90 mGh / year, advantageously less than 80 mGh / year, preferably less than 70 mGh / year, more advantageously less than 60 mGh / year, and in particular less than 50 mh ⁇ / year. This rate is measured according to the method of coupons ASTM D 2 328-65 T.
• the reactor of step (a) can be made of a M3 material resistant to corrosion.
• the reactor is made of a solid material M3 resistant to corrosion.
• the material M3 is pure nickel.
• the term "the material M3 is pure nickel", a material M3 comprising at least 99% by weight of nickel, preferably at least 99.1%, preferably at least 99.2% , advantageously at least 99.3%, still more preferably at least 99.4%, for example at least 99.5%, and in particular at least 99.6%, relative to the total weight of said material M3.
• the material M3 is pure nickel, it may also further comprise:
• the material M3 comprises between 0.1% and 1% by weight of iron, in particular between 0.3% and 0.8% by weight of iron, more particularly between 0.3% and 0.5% by weight of iron relative to total weight of material M3; and or
• N 2 O 2 comprising at least 99% by weight of nickel, at most 0.02% by weight of carbon, and at most 0.40% by weight of iron, at most 0.35% by weight. % by weight of manganese, at most 0.35% by weight of silicon, and at most 0.25% of copper; or the Ni200 comprising at least 99% by weight of nickel, at most 0.15% by weight of carbon, at most 0.40% by weight of iron, at most 0.35% by weight of manganese, at most 0, 35% by weight of silicon, and at most 0.25% of copper.
• the corrosion rate of the material M3 is less than 100 mGh / year, preferably less than 90 mGh / year, advantageously less than 80 mGh / year, preferably less than 70 mGh / year, even more advantageously less than 60 mGh / year, and in particular less than 50 mhg / year. This rate is measured according to the method of coupons ASTM D 2 328-65 T.
• the reactor is supplied with starting reagents via feed lines.
• the reactor may also comprise effluent or outlet lines for evacuating the reaction medium from the reactor.
• the feed or outlet lines of the reactor are made of specific material capable of also resisting corrosion, for example made of the aforementioned material M3.
• the supply lines may be tubular.
• the supply or output lines may be made of a material comprising a base layer made of a material M1 mentioned above coated with a surface layer, may be in contact with the reaction medium, made of a material M2 mentioned above.
• the reactor of step (a) is a stirred reactor equipped with stirring mobile (s).
• turbines for example straight-blade turbines called Rushton or turbines with curved blades or turbines with curved blades
• helical ribbons for example propellers (for example blade propellers). profiled), anchors, and their combinations.
• the mobile (s) agitation (s) can (wind) be fixed (s) on a central stirring shaft, and can (wind) be of the same or different nature.
• the stirring shaft may be driven by a motor, advantageously located outside the reactor.
• the design and size of the agitating mobiles can be chosen by those skilled in the art depending on the type of mixture to be produced (mixture of liquids, liquid and solid mixture, mixture of liquid and gas, mixture of liquid, gas and solid) and desired mixing performance.
• the stirring mobile is selected from the stirring motives best adapted to ensure good homogeneity of the reaction medium.
• the stirring unit is advantageously chosen from stirring motives best adapted to ensure good homogeneity of the reaction medium, and good suspension of the solid in the liquid phase.
• the mobile stirring device (s) is (are) made of a material resistant to corrosion, such as for example made of material M3 as defined above, or may comprise a base layer made of a previously mentioned M1 material coated with a layer surface, likely to be in contact with the reaction medium, made of a material M2 mentioned above resistant to corrosion.
• the reactor of step (a) can be heated by means of a double jacket surrounding the reactor in which a heating fluid, for example steam or hot water, can circulate.
• a heating fluid for example steam or hot water
• step (a) is carried out in a reactor having an overall thermal conductivity greater than or equal to 10 W / m / ° C, preferably greater than or equal to 15 W / m / ° C.
• the overall thermal conductivity is that of the material M3.
• the chlorination step (a) is carried out starting from the sulphamic acid, with at least one sulfur-containing acid and at least one chlorinating agent.
• reaction time of between 1 hour and 7 days, preferably between 1 hour and 5 days and advantageously between 1 hour and 3 days; and or
• the sulfur-containing agent may be selected from the group consisting of chlorosulfonic acid (CISO 3 H), sulfuric acid, oleum, and mixtures thereof.
• the sulfur agent is sulfuric acid.
• the chlorinating agent may be selected from the group consisting of thionyl chloride (SOCI 2 ), oxalyl chloride (COCI) 2 , phosphorus pentachloride (PCI 5 ), phosphonyl trichloride (PC), phosphoryl trichloride (POCI 3 ), and mixtures thereof.
• the chlorinating agent is thionyl chloride.
• the chlorination step (a) can be carried out in the presence of a catalyst, such as, for example, chosen from a tertiary amine (such as methylamine, triethylamine, or diethylmethylamine); pyridine; and 2,6-lutidine.
• a catalyst such as, for example, chosen from a tertiary amine (such as methylamine, triethylamine, or diethylmethylamine); pyridine; and 2,6-lutidine.
• the molar ratio between the sulfuric acid and the sulfamic acid may be between 0.7 and 5, preferably between 1 and 5.
• the molar ratio between the chlorinating agent and the acid may be between 3 and 10, preferably between 2 and 5.
• the sulfur-containing agent is chlorosulphonic acid
• the molar ratio between this and the sulphamic acid is between 1 and 5
• / or the molar ratio between the chlorinating agent and the sulphamic acid is between 2 and 5.
• the sulfur-containing agent is sulfuric acid (or oleum)
• the molar ratio of sulfuric acid (or oleum) to sulphamic acid is between 0.7 and 5.
• the sulfur-containing agent is sulfuric acid (or oleum)
• the molar ratio of sulfuric acid (or oleum) to sulphamic acid is between 1 and 5
• / or molar ratio between the chlorinating agent and the sulfamic acid is between 3 and 10.
• sulfur and chlorinating agents are in particular corrosive.
• sulfur and chlorinating agents are in particular corrosive.
• certain products formed such as for example bis (chlorosulfonyl) imide CI- (SC> 2) - NH- (SO 2 ) -CI and HCl.
• reaction medium starting reagents, and / or products formed
• the process according to the invention may further comprise a step (b), subsequent to step (a), comprising the reaction of bis (chlorosulfonyl) imide CI- (S0 2 ) -NH- (SC> 2 ) -CI with a fluorinating agent, to form bis (fluorosulfonyl) imide F- (SO 2 ) -NH- (SC 2 ) -F.
• the fluorinating agent may be selected from the group consisting of HF (preferably anhydrous HF), KF, ASF 3 , BIF 3 , ZnF 2 , SnF 2 , PbF 2 , CuF 2 , and mixtures thereof, the fluorinating agent preferably being HF, and even more preferably anhydrous HF.
• anhydrous HF means THF containing less than 500 ppm water, preferably less than 300 ppm water, preferably less than 200 ppm water.
• Step (b) of the process is preferably carried out in at least one SOI organic solvent.
• the organic solvent SOI preferably has a donor number of between 1 and 70 and advantageously of between 5 and 65.
• the donor index of a solvent represents the value -DH, DH being the enthalpy of the interaction between the solvent and antimony pentachloride (according to the method described in Journal of Solution Chemistry, Vol.13, No. 9, 1984).
• organic solvent SOI there may be mentioned in particular esters, nitriles, dinitriles, ethers, diethers, amines, phosphines, and mixtures thereof.
• the organic solvent SOI is selected from the group consisting of methyl acetate, ethyl acetate, butyl acetate, acetonitrile, propionitrile, isobutyronitrile, glutaronitrile , dioxane, tetrahydrofuran, triethylamine, tripropylamine, diethylisopropylamine, pyridine, trimethylphosphine, triethylphosphine, diethylisopropylphosphine, and mixtures thereof.
• the organic solvent SOI is dioxane.
• Step (b) may be carried out at a temperature between 0 ° C. and the boiling temperature of the SOI organic solvent (or of the SOI organic solvent mixture).
• step (b) is carried out at a temperature of between 5 ° C. and the boiling temperature of the organic solvent SOI (or of the mixture of organic solvents SOI), preferably between 25 ° C. and the boiling point.
• SOI organic solvent (or SOI organic solvent mixture) is carried out at a temperature between 0 ° C. and the boiling temperature of the SOI organic solvent (or of the SOI organic solvent mixture).
• Step (b), preferably with anhydrous hydrofluoric acid, may be carried out at a pressure P, preferably between 0 and 16 bar abs.
• This step (b) is preferably carried out by dissolving the bis (chlorosulfonyl) imide CI- (SO 2 ) -NH- (SC 2 ) -CI in the organic solvent SOI, or the mixture of organic solvents SOI, beforehand in the reaction step with the fluorinating agent, preferably with anhydrous HF.
• the weight ratio between the bis (chlorosulfonyl) imide CI- (SO 2 ) -NH- (SC 2 ) -CI and the organic solvent SOI, or the mixture of organic solvents SOI, is preferably between 0.001 and 10, and advantageously between 0.005 and 5.
• the anhydrous IHF is introduced into the reaction medium in liquid form or in gaseous form, preferably in gaseous form.
• the molar ratio x between the fluorinating agent, preferably anhydrous HF, and the bis (chlorosulfonyl) imide CI- (SO 2 ) -NH- (SC 2 ) -CI involved is preferably between 2 and 10, and advantageously between 2 and 5.
• reaction step with the fluorinating agent preferably anhydrous THF
• step (b) is carried out in an open medium, in particular with the release of HCl in gas form.
• step (b) is carried out in a reactor made of a corrosion-resistant material M4, or in a reactor containing a base layer made of a material M5 coated with a layer of surface made of M6 material resistant to corrosion.
• the surface layer of the reactor of step (b) is the layer likely to be in contact with the reaction medium of the fluorination step (b) (for example starting reagents, products generated, etc.), the reaction medium may comprise any type of phase: liquid, and / or gas, and / or solid.
• the surface layer of the reactor of step (b) is at least in contact with at least one of the starting reagents, for example bis (chlorosulfonyl) imide.
• the starting reagents for example bis (chlorosulfonyl) imide.
• the base layer and the surface layer can be arranged against one another by plating.
• plating is for example the case when the material M6 is a nickel-based alloy, as defined below.
• the plating is performed by weld plating, explosion-etched plating, hot-rolling plating, or cold-rolling plating, preferably by blast plating.
• the surface layer has a thickness of between 0.01 and 20 mm, said thickness of said inner surface layer being less than that of said base layer.
• said inner surface layer has a thickness of between 0.05 and 15 mm, preferably between 0.1 and 10 mm, advantageously between 0.1 and 5 mm.
• the reactor is made of a solid material M4 resistant to corrosion.
• the material M4 may be chosen from the material M3 as defined above, or a material M4 comprising:
• the material M4 comprises at least 60% by weight of iron, more particularly at least 70% by weight of iron relative to the total weight of the material M4; and less than 2% by weight of carbon, advantageously less than 1, 5% by weight, preferably less than 1% by weight, more preferably less than 0.75% by weight, in particular less than 0.5% by weight more preferably less than 0.2% by weight, still more preferably less than 0.1% by weight based on the total weight of the material M4; and from 10% to 20% by weight of chromium, preferably from 15% to 20% by weight, in particular from 16% to 18.5% by weight of chromium relative to the total weight of the material M4; and less than 15% by weight of nickel, preferably between 10% and 14% by weight of nickel relative to the total weight of the material M4; and less than 3% by weight of molybdenum, advantageously between 2% and 3% by weight of molybdenum relative to the total weight of the material M4; and less than 2.5% by weight of manganese, advantageously 2% by weight
• the material M5 is the material M1 as defined above. More preferably, the material M5 comprises at least 60% by weight of iron, preferably at least 70% by weight of iron, advantageously at least 75% by weight, still more advantageously at least 80% by weight, more preferably at least 85% by weight.
• % by weight in particular at least 90% by weight, more particularly at least 95% by weight, and even more preferably at least 97% by weight of iron relative to the total weight of the M5 material; and less than 2% by weight of carbon, advantageously less than 1.5% by weight, preferably less than 1% by weight, preferably less than 0.75% by weight, more preferably less than 0.5% by weight, more particularly less than 0.2% by weight, and even more preferably between 0.01% and 0.2% by weight of carbon relative to the total weight of the material M5; and less than 3% by weight of molybdenum, advantageously less than 2% by weight, preferably less than 1, 5% by weight, preferably less than 1, 25% by weight, more preferably less than 1% by weight, even more advantageously between 0.1% and 1% by weight of molybdenum relative to the total weight of the M5 material, and / or less than 5% by weight of chromium, preferably less than 4% by weight, advantageously less from 3% by weight, preferably less than 2% by weight, in
• the material M6 may be chosen from the group consisting of enamel, polymers (in particular fluorinated polymers), and nickel-based alloys (the nickel-based alloys being in particular those defined above for the material M2).
• the material M6 is chosen from polymers, in particular polyolefins (such as, for example, polyethylene), and fluorinated polymers, such as, for example, PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PFAs (copolymers of C 2 F 4 and perfluorinated vinyl ether), FEP (copolymers of tetrafluoroethylene and perfluoropropene, such as for example copolymer of C2F4 and C 3 F 6 ), ETFE (copolymer of tetrafluoroethylene and of ethylene, and FKM (copolymer hexafluoropropylene and difluoroethylene), more preferably the material M6 is selected from PTFE and PFA.
• polyolefins such as, for example, polyethylene
• fluorinated polymers such as, for example, PVDF (polyvinylidene fluoride), PTFE (polytetra
• the reactor used in step (b) of the process according to the invention comprises a base layer made of a material M5 coated with a surface layer made of a M6-resistant material. corrosion, said M5 material comprising:
• At least 60% by weight of iron preferably at least 70% by weight of iron, advantageously at least 75% by weight, still more advantageously at least 80% by weight, more preferably at least 85% by weight, in particular at least 90% by weight, more particularly at least 95% by weight, and even more preferably at least 97% by weight of iron relative to the total weight of the material M5; and less than 2% by weight of carbon, advantageously less than 1.5% by weight, preferably less than 1% by weight, preferably less than 0.75% by weight, more preferably less than 0.5% by weight, more particularly less than 0.2% by weight, and even more preferably between 0.01% and 0.2% by weight of carbon relative to the total weight of the material M5; and less than 3% by weight of molybdenum, advantageously less than 2% by weight, preferably less than 1, 5% by weight, preferably less than 1, 25% by weight, more preferably less than 1% by weight, even more advantageously between 0.1% and 1% by weight of molybdenum relative to the total weight of the M5 material, and
• the material M6 being chosen from fluorinated polymers, and in particular thermoplastic fluorinated polymers, such as, for example, PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PFAs (copolymers of C2F4 and of vinyl ether) perfluorinated), FEP (copolymers of tetrafluoroethylene and perfluoropropene, such as, for example, copolymer of C 2 F 4 and C 3 F 6 ), ETFE (copolymer of tetrafluoroethylene and ethylene, and FKM (copolymer of hexafluoropropylene and difluoroethylene), more preferably the M6 material being selected from PTFE and PFA.
• PVDF polyvinylidene fluoride
• PTFE polytetrafluoroethylene
• PFAs copolymers of C2F4 and of vinyl ether perfluorinated
• FEP copolymers of
• the reactor used in step (b) of the process according to the invention is made of a material M4 resistant to corrosion, said material M4 comprising at least 60% by weight of iron, more particularly at least 70% by weight of iron relative to the total weight of the material M4; and less than 2% by weight of carbon, advantageously less than 1, 5% by weight, preferably less than 1% by weight, more preferably less than 0.75% by weight, in particular less than 0.5% by weight more preferably less than 0.2% by weight, still more preferably less than 0.1% by weight based on the total weight of the material M4; and from 10% to 20% by weight of chromium, preferably from 15% to 20% by weight, in particular from 16% to 18.5% by weight of chromium relative to the total weight of the material M4; and less than 15% by weight of nickel, preferably between 10% and 14% by weight of nickel relative to the total weight of the material M4; and less than 3% by weight of molybdenum, advantageously between 2% and 3% by weight of molybdenum, advantageously between
• the corrosion rate of the material M6 is less than 100 mGh / year, preferably less than 90 mGh / year, advantageously less than 80 mGh / year, preferably less than 70 mGh / year, more advantageously less than 60 mGh / year, and in particular less than 50 mh ⁇ / year. This rate is measured according to the method of coupons ASTM D 2 328-65 T.
• the reactor is supplied with starting reagents via feed lines.
• the reactor may also comprise effluent or outlet lines for evacuating the reaction medium from the reactor.
• the feed or outlet lines of the reactor are made of specific material capable of also resisting corrosion, for example made of the aforementioned material M4.
• the supply lines may be tubular.
• the supply or output lines may be made of a material comprising a base layer made of a material M5 mentioned above coated with a surface layer, likely to be in contact with the reaction medium, made of a M6 material resistant to corrosion.
• the reactor of step (b) is a stirred reactor equipped with stirring mobile (s).
• turbines for example straight-blade turbines called Rushton or turbines with curved blades or turbines with curved blades
• helical ribbons for example propellers (for example blade propellers). profiled), anchors, and their combinations.
• the design and size of the mobile (s) stirring may be chosen by the skilled person depending on the type of mixture to achieve (mixing liquids, liquid and solid mixture, mixing liquid and gas, mixture of liquid, gas and solid) and desired mixing performance.
• the stirring mobile is selected from the stirring motives best adapted to ensure good homogeneity of the reaction medium.
• the mobile stirring device (s) is (are) made of a material resistant to corrosion such as for example made of material M4 as defined above, or may comprise a layer base material made of a aforementioned M5 material coated with a surface layer, capable of being in contact with the reaction medium, made of a material M6 mentioned above resistant to corrosion.
• a material resistant to corrosion such as for example made of material M4 as defined above, or may comprise a layer base material made of a aforementioned M5 material coated with a surface layer, capable of being in contact with the reaction medium, made of a material M6 mentioned above resistant to corrosion.
• the reactor of step (b) can be heated by means of a double jacket surrounding the reactor in which a heating fluid, for example steam or hot water, can circulate.
• a heating fluid for example steam or hot water
• the overall thermal conductivity is that of the material M4.
• the fluorination reaction typically leads to the formation of HCl, the majority of which can be degassed from the reaction medium (just like the excess HF if the fluorinating agent is HF), for example by stripping a gas. neutral (such as nitrogen, helium or argon).
• the anhydrous HF and HCl mentioned above are in particular corrosive.
• the use of the reactor as defined above advantageously makes it possible to resist the corrosivity of the reaction medium (starting reagents, and / or products formed) under the reaction conditions, and thus to avoid contamination of the medium by metal ions. from the reactor materials.
• the process according to the invention may further comprise a step (c), subsequent to step (b), comprising the preparation of an alkaline or alkaline earth salt of bis (fluorosulfonyl) imide by neutralization of bis (fluorosulfonyl) imide.
• Step (c) of the process according to the invention may be carried out by bringing bis (fluorosulfonyl) imide into contact with an aqueous solution of a base chosen from alkali metal or alkaline-earth metal carbonate of formula MCC> 3, nH 2 O or the alkali metal or alkaline earth metal hydroxides MoH, nH 2 O, with M representing a monovalent cation of alkali or alkaline earth metal and n being able to vary from 0 to 10.
• MOH represents LiOH, NaOH, KOH RbOH, and CsOH.
• MCO3 is Na2CC3, K2CO3, Rb2CC3, CS2CO3, L12CO3, MCO3 preferably representing Na2CO3, K2CO3, Rb2CC3, or CS2CO3.
• M does not represent Li + .
• the base used is not a base comprising lithium.
• the base used comprises potassium.
• Step (c) advantageously allows the preparation of a compound of formula (I) below:
• Step (c) may be carried out for example by adding an aqueous solution of the chosen base.
• the molar ratio base / bis (fluorosulfonyl) imide F- (SO 2 ) -NH- (SC 2 ) -F can be for example from 1 to 5 when the base is a hydroxide, or from 0.5 to 5 (or from 2 to 10), when the base is a carbonate.
• the temperature of the reaction of step (c) may for example be between -10 ° C and 40 ° C.
• the solution obtained at the end of step (c) comprising the alkali or alkaline earth salt of bis (fluorosulfonyl) imide, preferably of formula (I), can then be filtered, resulting in a filtrate F and a cake G.
• the desired salt may be present in the filtrate F and / or in the cake G.
• the fluorides of alkali or alkaline earth metals are especially present in the cake G but can also be found in the filtrate F.
• the filtrate F can be subjected to at least one extraction step with a SO 2 organic solvent which is typically poorly soluble in water, in order to extract the desired salt, preferably of formula (I) mentioned above, in an organic phase.
• the extraction step typically leads to the separation of an aqueous phase and an organic phase.
• the above-mentioned organic solvent SO 2 is in particular chosen from the following families: esters, nitriles, ethers, chlorinated solvents, aromatic solvents, and mixtures thereof.
• the organic solvent SO 2 is chosen from dichloromethane, ethyl acetate, butyl acetate, tetrahydrofuran, acetonitrile, diethyl ether, and mixtures thereof.
• the organic solvent S0 2 is butyl acetate.
• the mass quantity of organic solvent used can vary between 1/6 and 1 times the weight of the filtrate F.
• the number of extractions can be between 2 and 10.
• the organic phase, resulting from the extraction (s) has a desired mass content of salt, preferably of formula (I), ranging from 5% to 50% by weight.
• the separated organic phase (obtained after the extraction) can then be concentrated to reach a desired salt concentration, preferably of formula (I), of between 5 and 55%, preferably between 10% and 50% in bulk, said concentration can be achieved by any means of evaporation known to those skilled in the art.
• a desired salt concentration preferably of formula (I)
• said concentration can be achieved by any means of evaporation known to those skilled in the art.
• the aforementioned cake G can be washed with an organic solvent SO 3 selected from the following families: esters, nitriles, ethers, chlorinated solvents, aromatic solvents, and mixtures thereof.
• the organic solvent SO 3 is chosen from dichloromethane, ethyl acetate, butyl acetate, tetrahydrofuran, acetonitrile, diethyl ether, and mixtures thereof.
• the organic solvent SO 3 is butyl acetate.
• the mass quantity of organic solvent S03 used may vary between 1 and 10 times the weight of the cake.
• the total amount of organic solvent SO 3 intended for the washing can be used at one time or in several times, in particular in order to optimize the dissolution of the desired salt, preferably of formula (I) mentioned above.
• the organic phase, resulting from the washing (s) of the cake G has a desired mass content of salt, preferably of formula (I), ranging from 5% to 50% by weight.
• the separated organic phase resulting from the washing (s) of the cake G can then be concentrated to reach a desired concentration of salt, preferably of formula (I), of between 5 and 55%, preferably between 10% and 50%. % by mass, said concentration can be achieved by any means of evaporation known to those skilled in the art.
• the organic phases resulting from (s) the extraction (s) of the filtrate F and (the) washing (s) of the cake G can be collected together, before the possible concentration step.
• step (c) is carried out in a reactor made of a corrosion-resistant material M7, or in a reactor containing a base layer made of a material M8 coated with a layer of surface made of M9 material resistant to corrosion.
• the surface layer of the reactor of step (c) is the layer likely to be in contact with the reaction medium of the neutralization step (c) (for example starting reagents, products generated, etc.), the reaction medium may comprise any type of phase: liquid, and / or gas, and / or solid.
• the surface layer of the reactor of step (c) is at least in contact with at least one of the starting reagents, for example bis (fluorosulfonyl) imide.
• the base layer and the surface layer can be arranged against one another by plating. This is for example the case when the material M9 is a nickel-based alloy, as defined below.
• the plating is performed by weld plating, explosion-etched plating, hot-rolling plating, or cold-rolling plating, preferably by blast plating.
• the surface layer has a thickness of between 0.01 and 20 mm, said thickness of said inner surface layer being less than that of said base layer.
• said inner surface layer has a thickness of between 0.05 and 15 mm, preferably between 0.1 and 10 mm, advantageously between 0.1 and 5 mm.
• the material M7 is the material M4 as defined above. More preferably, the material M7 comprises at least 60% by weight of iron, more particularly at least 70% by weight of iron relative to the total weight of the material M7; and less than 2% by weight of carbon, advantageously less than 1, 5% by weight, preferably less than 1% by weight, more preferably less than 0.75% by weight, in particular less than 0.5% by weight more preferably less than 0.2% by weight, still more preferably less than 0.1% by weight based on the total weight of the material M7; and from 10% to 20% by weight of chromium, preferably from 15% to 20% by weight, in particular from 16% to 18.5% by weight of chromium relative to the total weight of the material M7; and less than 15% by weight of nickel, preferably between 10% and 14% by weight of nickel relative to the total weight of the M7 material; and less than 3% by weight of molybdenum, advantageously between 2% and 3% by weight of molybdenum relative to the total weight of the material M7; and
• the material M8 is the material M1 as defined above. More preferably, the material M8 comprises at least 60% by weight of iron, preferably at least 70% by weight of iron, advantageously at least 75% by weight, still more advantageously at least 80% by weight, more preferably at least 85% by weight.
• % by weight in particular at least 90% by weight, more particularly at least 95% by weight, and even more preferably at least 97% by weight of iron relative to the total weight of the material M8; and less than 2% by weight of carbon, advantageously less than 1.5% by weight, preferably less than 1% by weight, preferably less than 0.75% by weight, more preferably less than 0.5% by weight, more particularly less than 0.2% by weight, and even more preferably between 0.01% and 0.2% by weight of carbon relative to the weight total material M8; and less than 3% by weight of molybdenum, advantageously less than 2% by weight, preferably less than 1, 5% by weight, preferably less than 1, 25% by weight, more preferably less than 1% by weight, even more advantageously between 0.1% and 1% by weight of molybdenum relative to the total weight of the material M8, and / or less than 5% by weight of chromium, preferably less than 4% by weight, advantageously less than 3% by weight, preferably less than 2% by weight, in particular between 0.
• the material M9 is the material M6 as defined above. More preferably, the material M9 is chosen from polymers, in particular polyolefins (such as, for example, polyethylene), and fluorinated polymers, such as, for example, PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PFAs (copolymers of C 2 F 4 and perfluorinated vinyl ether), FEP (copolymers of tetrafluoroethylene and perfluoropropene, such as for example copolymer of C2F4 and C 3 F 6 ), ETFE (copolymer of tetrafluoroethylene and of ethylene, and FKM (copolymer of hexafluoropropylene and difluoroethylene), more preferably the material M9 is selected from PTFE and PFA.
• polyolefins such as, for example, polyethylene
• fluorinated polymers such as, for example, PVDF (poly
• the reactor used in step (c) of the process according to the invention comprises a base layer made of an M8 material coated with a surface layer made of a M9-resistant material. corrosion, said M8 material comprising:
• At least 60% by weight of iron preferably at least 70% by weight of iron, advantageously at least 75% by weight, still more advantageously at least 80% by weight, more preferably at least 85% by weight, in particular at least 90% by weight, more particularly at least 95% by weight, and even more preferably at least 97% by weight of iron relative to the total weight of the material M8; and less than 2% by weight of carbon, advantageously less than 1.5% by weight, preferably less than 1% by weight, preferably less than 0.75% by weight, more preferably less than 0.5% by weight, more particularly less than 0.2% by weight, and even more preferably between 0.01% and 0.2% by weight of carbon relative to the total weight of the material M8; and less than 3% by weight of molybdenum, advantageously less than 2% by weight, preferably less than 1, 5% by weight, preferably less than 1, 25% by weight, more preferably less than 1% by weight, even more advantageously between 0.1% and 1% by weight of molybdenum relative to the total weight of the material M8, and
• the reactor used in step (c) of the process according to the invention is made of a material M7 resistant to corrosion, said material M7 comprising at least 60% by weight of iron, more particularly at least 70% by weight of iron relative to the total weight of the material M7; and less than 2% by weight of carbon, advantageously less than 1, 5% by weight, preferably less than 1% by weight, more preferably less than 0.75% by weight, in particular less than 0.5% by weight more preferably less than 0.2% by weight, still more preferably less than 0.1% by weight based on the total weight of the material M7; and from 10% to 20% by weight of chromium, preferably from 15% to 20% by weight, in particular from 16% to 18.5% by weight of chromium relative to the total weight of the material M7; and less than 15% by weight of nickel, preferably between 10% and 14% by weight of nickel relative to the total weight of the M7 material; and less than 3% by weight of molybdenum, advantageously between 2% and 3% by weight of molybdenum, advantageously between
• the reactor of step (c) is supplied with starting reagents by feed lines.
• the reactor may also comprise effluent or outlet lines for evacuating the reaction medium from the reactor.
• the feed or outlet lines of the reactor are made of specific material capable of also resisting corrosion, for example made of the aforementioned material M7.
• the supply lines may be tubular.
• the supply or output lines may be made of a material comprising a base layer made of a material M8 mentioned above coated with a surface layer, likely to be in contact with the reaction medium, made of a material M9 mentioned above.
• the reactor of step (c) is a stirred reactor equipped with stirring mobile (s).
• turbines for example straight-blade turbines called Rushton or turbines with curved blades or turbines with curved blades
• helical ribbons for example propellers (for example blade propellers). profiled), anchors, and their combinations.
• the mobile (s) agitation (s) can (wind) be fixed (s) on a central stirring shaft, and can (wind) be of the same or different nature.
• the stirring shaft may be driven by a motor, advantageously located outside the reactor.
• the design and size of the agitating mobiles can be chosen by those skilled in the art depending on the type of mixture to be produced (mixture of liquids, liquid and solid mixture, mixture of liquid and gas, mixture of liquid, gas and solid) and desired mixing performance.
• the stirring mobile is selected from the stirring motives best adapted to ensure good homogeneity of the reaction medium.
• the stirring unit is advantageously chosen from stirring motives best adapted to ensure good homogeneity of the reaction medium, and its stirring speed is advantageously adapted to obtain good mixing of the medium in case of increase in viscosity.
• the mobile stirring device (s) is (are) made of a material resistant to corrosion, such as for example made of material M7 as defined above, or may comprise a base layer made of a previously mentioned M8 material coated with a surface layer, capable of being in contact with the reaction medium, made of a corrosion-resistant material M9 mentioned above.
• the reactor of step (c) may comprise cooling means.
• the reactor of step (c) can be cooled by means of a double jacket surrounding the reactor in which can circulate a cooling fluid, for example water.
• step (c) is carried out in a reactor having an overall thermal conductivity greater than or equal to 10 W / m / ° C, preferably greater than or equal to 15 W / m / ° C.
• the overall thermal conductivity l d, 9 of the reactor composed of M8 and M9 is calculated according to the following formula: 18.9- (3 ⁇ 4 + eg) / ((be / Ce) + (eg / Xg))
• a thickness es representing the thickness of the material M8, eg representing the thickness of the material M9, lb representing the thermal conductivity of the material M8 and Xg representing the thermal conductivity of the material M9.
• the overall thermal conductivity is that of the material M7.
• the neutralization reaction in particular involves compounds which may be corrosive such as bis (fluorosulfonyl) imide F- (S0 2 ) -NH- (SC> 2 ) -F and optionally residual HF.
• compounds which may be corrosive such as bis (fluorosulfonyl) imide F- (S0 2 ) -NH- (SC> 2 ) -F and optionally residual HF.
• reaction medium starting reagents, and / or products formed
• the process according to the invention may further comprise a possible cation exchange step (d), subsequent to step (c), comprising the reaction between the alkaline earth salt of bis (fluorosulfonyl) imide and a salt of lithium to obtain the lithium salt of bis (fluorosulfonyl) imide.
• a possible cation exchange step (d) comprising the reaction between the alkaline earth salt of bis (fluorosulfonyl) imide and a salt of lithium to obtain the lithium salt of bis (fluorosulfonyl) imide.
• the process according to the invention comprises this step (d) when the salt obtained in step (c) is not the lithium salt of bis (fluorosulfonyl) imide.
• Step (d) is in particular a cation exchange reaction for converting a compound of formula (I) mentioned above F- (S0 2 ) -NM- (SC> 2 ) -F (I), M being such as previously described, to a lithium salt of bis (fluorosulfonyl) imide.
• the lithium salt is selected from LiF, LiCI, Ü 2 CO 3, LiOH, UNO 3 L1BF 4, and mixtures thereof.
• the lithium salt may be dissolved in a polar organic solvent selected from the following families: alcohols, nitriles and carbonates.
• a polar organic solvent selected from the following families: alcohols, nitriles and carbonates.
• alcohols such as methanol, ethanol, acetonitrile, dimethylcarbonate and ethylmethylcarbonate.
• the molar ratio of the compound of formula (I) relative to the lithium salt may vary: it may be at least 1 and less than 5.
• the molar ratio of compound of formula (I) / lithium salt is between 1, 2 and 2.
• the reaction medium may be stirred for 1 to 24 hours, and / or at a temperature of, for example, 0 ° C to 50 ° C.
• the reaction medium can be filtered and then optionally concentrated.
• the concentration step may optionally be carried out by a thin-film evaporator, an atomizer, a rotary evaporator, or any other apparatus for the evaporation of solvent.
• the filtration can be carried out using a filter or wringer.
• the filter or wringer is preferably made of a material M 'comprising:
• less than 2% by weight of carbon advantageously less than 1.5% by weight, preferably less than 1% by weight, more preferably less than 0.75% by weight, in particular less than 0.5% by weight; more particularly less than 0.2% by weight, still more preferably less than 0.1% by weight relative to the total weight of the material M '; and
• the filter or wringer preferably comprises a base layer made of a material M1 coated with a surface layer made of a corrosion-resistant material M2, said material M1 comprising:
• At least 60% by weight of iron preferably at least 70% by weight of iron, advantageously at least 75% by weight, still more advantageously at least 80% by weight, more preferably at least 85% by weight, in particular at least 90% by weight, more particularly at least 95% by weight, and even more preferably at least 97% by weight of iron relative to the total weight of the material M1; and less than 2% by weight of carbon, advantageously less than 1.5% by weight, preferably less than 1% by weight, preferably less than 0.75% by weight, more preferably less than 0.5% by weight, more particularly less than 0.2% by weight, and even more preferably between 0.01% and 0.2% by weight of carbon relative to the total weight of the material M1; and less than 3% by weight of molybdenum, advantageously less than 2% by weight, preferably less than 1, 5% by weight, preferably less than 1, 25% by weight, more preferably less than 1% by weight, even more advantageously between 0.1% and 1% by weight of molybdenum relative to the total weight of the material M1, and
• the material M2 being chosen from alloys based on nickel, in particular chosen from alloys comprising at least 40% by weight of nickel, advantageously at least 45% by weight, more preferably at least 50% by weight, in particular at least less than 55% by weight, more particularly at least 60% by weight, preferably at least 65% by weight, even more preferably at least 70% by weight of nickel relative to the total weight of material M2; and / or chromium in a content of less than 35% by weight relative to the total weight of the material M2, advantageously less than 30% by weight, preferably less than 20% by weight, more preferably less than 15% by weight, in in particular less than 10% by weight, more particularly less than 5% by weight relative to the total weight of the material M2; and / or molybdenum in a content of less than 35% by weight relative to the weight total material M2, preferably less than 30% by weight, preferably less than 25% by weight, more preferably less than 20% by weight, in particular less than 15% by weight, more particularly less than 10% by weight relative to the total weight of the
• Reactor Step (d) may be carried out in a silicon carbide or fluoropolymer-based reactor or in a steel reactor comprising an inner surface, said inner surface capable of being in contact with the salt of bis (fluorosulfonyl) imide lithium being coated with a polymeric coating or silicon carbide coating.
• the aforementioned fluoropolymer is advantageously chosen from PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PFA (copolymers of C 2 F 4 and perfluorinated vinyl ether), and ETFE (copolymer of tetrafluoroethylene and of ethylene).
• the fluorinated polymer is advantageously chosen from PVDF, PFA and ETFE.
• the polymeric coating may be a coating comprising at least one of the following polymers: polyolefins such as for example polyethylene, or fluorinated polymers such as, for example, PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PFA ( copolymers of C 2 F 4 and perfluorinated vinyl ether), FEP (copolymers of tetrafluoroethylene and perfluoropropene, such as, for example, copolymer of C 2 F 4 and C 3 F 6 ), ETFE (copolymer of tetrafluoroethylene and ethylene, and FKM (copolymer of hexafluoropropylene and difluoroethylene)
• the polymeric coating comprises at least one fluorinated polymer, and in particular PFA, PTFE or PVDF.
• the reactor of step (d) is a stirred reactor provided with mobile (s) stirring.
• turbines for example straight-blade turbines called Rushton or turbines with curved blades or turbines with curved blades
• helical ribbons for example propellers (for example blade propellers). profiled), anchors, and their combinations.
• the mobile stirring device (s) can (wind) be fixed (s) on a central stirring shaft, and may be identical or different in nature.
• the stirring shaft may be driven by a motor, advantageously located outside the reactor.
• the design and size of the agitating mobiles can be chosen by those skilled in the art depending on the type of mixture to be produced (mixture of liquids, liquid and solid mixture, mixture of liquid and gas, mixture of liquid, gas and solid) and desired mixing performance.
• the stirring mobile is selected from the stirring motives best adapted to ensure good homogeneity of the reaction medium.
• the mobile stirring member (s) is (are) made of a steel material, preferably carbon steel, comprising an outer surface, said outer surface likely to be in contact with the bis (fluorosulfonyl) imide lithium salt being covered by a polymeric coating preferably as defined above, or by a coating of silicon carbide.
• the process according to the invention may further comprise a possible step (e) of purification of the lithium salt of bis (fluorosulfonyl) imide.
• the step (e) of purification of the lithium salt of bis (fluorosulfonyl) imide can be carried out by any known conventional method. This may be for example an extraction method, a washing method with solvents, a reprecipitation method, a recrystallization method, or their combination.
• the lithium salt of bis (fluorosulfonyl) imide may be in the form of a solid, or a composition comprising from 1% to 99.9% by weight of lithium salt of bis (fluorosulfonyl) imide.
• step (e) is a crystallization step of
• the LiFSI is crystallized in the cold, in particular at a temperature of less than or equal to 25 ° C.
• the crystallization of LiFSI is carried out in an organic solvent (“crystallization solvent”) chosen from chlorinated solvents, such as, for example, dichloromethane, from alkanes such as, for example, pentane, hexane, cyclohexane and heptane, and from aromatic solvents, such as, for example, toluene, in particular at a temperature of less than or equal to 25 ° C.
• the crystallized LiFSI at the end of step (e) is recovered by filtration.
• step (e) comprises the following steps: i ') possible dissolution of LiFSI in an organic solvent OS1; i) liquid-liquid extraction of the bis (fluorosulfonyl) imide lithium salt with deionized water, and recovery of an aqueous solution of said bis (fluorosulfonyl) imide lithium salt;
• steps i), ii), iii), or iv) is performed in: an equipment based on silicon carbide or based on a fluoropolymer; or
• a steel equipment preferably made of carbon steel, comprising an inner surface, said inner surface capable of being in contact with the bis (fluorosulfonyl) imide lithium salt being covered by a polymeric coating or by a coating of carbide of silicon.
• the equipment may be a reactor, an evaporator, a mixer-settler, a liquid-liquid extraction column, a settling tank, an exchanger.
• the silicon carbide equipment is preferably a solid silicon carbide equipment.
• the equipment based on a fluoropolymer is preferably a solid fluoropolymer equipment.
• the fluorinated polymer is advantageously chosen from PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PFA (copolymers of C 2 F 4 and perfluorinated vinyl ether), and ETFE (copolymer of tetrafluoroethylene and ethylene). ).
• the fluoropolymer of the equipment is advantageously chosen from PVDF, PFA and ETFE.
• the polymeric coating may be a coating comprising at least one of the following polymers: polyolefins such as for example polyethylene, or fluorinated polymers such as, for example, PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PFA ( copolymers of C 2 F 4 and perfluorinated vinyl ether), FEP (copolymers of tetrafluoroethylene and perfluoropropene, such as, for example, copolymer of C 2 F 4 and C 3 F 6 ), ETFE (copolymer of tetrafluoroethylene and ethylene, and FKM (copolymer of hexafluoropropylene and difluoroethylene).
• polyolefins such as for example polyethylene
• fluorinated polymers such as, for example, PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PFA ( copolymers of C
• the polymeric coating comprises at least one fluorinated polymer, and in particular PFA, PTFE or PVDF.
• step i) is carried out in equipment as defined above, said equipment preferably being an extraction column or a mixer-settler; and / or step ii) is carried out in equipment as defined above, said equipment preferably being an evaporator or an exchanger; and or
• step iii) is carried out in equipment as defined above, said equipment preferably being an extraction column or a mixer-settler; and or step iv) is carried out in equipment as defined above, said equipment preferably being an evaporator or an exchanger.
• Step (e) may not include the aforementioned step i ') if the LiFSI obtained in step (d) already comprises an organic solvent.
• Step i) can be carried out in equipment selected from an extraction column, a mixer-settler, and mixtures thereof.
• the liquid-liquid extraction step i) is carried out in: an extraction column or a mixer-settler, based on silicon carbide or based on a fluoropolymer, preferably such as previously defined; or an extraction column or a mixer-settler, preferably steel made of carbon steel, said extraction column or said mixer-settler comprising an inner surface, said inner surface likely to be in contact with the lithium salt of bis (fluorosulfonyl) imide being covered by a polymeric coating preferably as defined above or by a coating of silicon carbide.
• the liquid-liquid extraction step i) is carried out in:
• An extraction column or a mixer-settler based on a fluorinated polymer such as for example PVDF (polyvinylidene fluoride), or PFA (copolymers of C 2 F 4 and perfluorinated vinyl ether); or
• an extraction column or a mixer / settler made of steel, preferably carbon steel, said extraction column or said mixer-settling tank comprising an inner surface, said inner surface likely to be in contact with the lithium salt of bis (fluorosulfonyl) imide being covered by a polymeric coating preferably as defined above.
• Feeding the settler chamber from the mixer chamber can be by overflow, by the bottom of the mixing chamber, or by a perforated wall between the mixer chamber and the settler chamber.
• the extraction column may include: at least one lining such as for example loose packing and / or structured packing. These may include Rashig rings, Pali rings, Saddle rings, Berl saddles, Intalox saddles, or marbles;
• trays such as, for example, perforated trays, fixed valve trays, movable tray trays, cap trays, or combinations thereof;
• atomization devices from one phase to another, such as for example nozzles,
• the polymeric material may comprise at least one polymer chosen from polyolefins such as, for example, polyethylene, and fluorinated polymers such as for example PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PFA (copolymers of C 2 F 4 and perfluorinated vinyl ether), FEP ( copolymers of tetrafluoroethylene and perfluoropropene, such as for example a copolymer of C 2 F 4 and C 3 F 6 ), ETFE (copolymer of tetrafluoroethylene and of ethylene, and FKM (copolymer of hexafluoropropylene and difluoroethylene).
• polyolefins such as, for example, polyethylene
• fluorinated polymers such as for example PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PFA (copolymers of C 2 F 4 and perflu
• the extraction column may also comprise quiches integral with the side walls of said column.
• the bicanages advantageously make it possible to limit the phenomenon of axial remixing.
• packing a solid structure adapted to increase the contact area between the two liquids contacted.
• the height and / or diameter of the extraction column typically depends on the nature of the liquids to be separated.
• the extraction column may be static or agitated.
• the extraction column is stirred, preferably mechanically. It comprises, for example, one or more agitating mobiles fixed on an axial rotary shaft.
• agitating mobiles fixed on an axial rotary shaft.
• turbines for example straight-blade turbines known as Rushton turbines or turbines with curved blades or turbines with curved blades
• propellers for example profiled blade propellers
• discs and mixtures thereof.
• the agitation advantageously allows the formation of fine droplets to disperse a liquid phase in the other, and thus increase the interfacial exchange area.
• the stirring speed is chosen so as to maximize the interfacial exchange area.
• the mobile stirring member (s) is (are) made of a steel material, preferably carbon steel, comprising an outer surface, said outer surface likely to be in contact with the bis (fluorosulfonyl) imide lithium salt being covered by a polymeric coating preferably as defined above, or by a coating of silicon carbide.
• step i) can be repeated at least once, preferably repeated from 1 to 10 times, preferably from 1 to 4 times.
• step i) is repeated, it may be carried out in several mixer-settlers in series.
• Step i) can be carried out continuously or discontinuously, preferably continuously.
• step i) comprises the addition of deionized water to the LiFSI solution in the above-mentioned organic solvent OS1, for example obtained during previous synthesis steps, to allow the dissolution of said salt, and extracting said salt in water (aqueous phase).
• a quantity of deionized water corresponding to at least half of the mass of the initial solution may be added in a first extraction, then an amount greater than or equal to about 1/3 of the mass of the initial solution during the second extraction, then an amount greater than or equal to about 1/4 of the mass of the initial solution during the third extraction.
• step i In case of multiple extractions (repetition of step i)), the extracted aqueous phases are combined together to form a single aqueous solution.
• Step i) advantageously makes it possible to obtain an aqueous phase and an organic phase, which are separated.
• Step ii) is thus advantageously carried out on the aqueous solution extracted in step a) (single aqueous phase or combined aqueous phases in case of repetition of step i)).
• an aqueous solution of LiFSI is advantageously obtained.
• the mass content of LiFSI in the aqueous solution is between 5% and 35%, preferably between 10% and 25%, relative to the total mass of the solution.
• Step (e) may comprise a concentration step ii) between step i) and step iii), preferably to obtain an aqueous LiFSI solution comprising a LiFSI mass content of between 20% and 80%, in particular between 25% and 80%, preferably between 25% and 70%, and advantageously between 30% and 65% relative to the total mass of the solution.
• the concentration step may be carried out under reduced pressure, for example at a pressure of less than 50 mbar abs (preferably less than 30 mbar abs), and / or at a temperature of between 25 ° C and 60 ° C, preferably between 25 ° C and 50 ° C, preferably between 25 ° C and 40 ° C.
• Step ii) can be performed in at least one equipment selected from an evaporator or exchanger.
• the concentration step ii) is carried out in:
• an exchanger or evaporator made of steel, preferably of carbon steel, said exchanger or evaporator comprising an inner surface, said inner surface likely to be in contact with the bis (fluorosulfonyl) imide lithium salt being covered by a polymeric coating, preferably as defined above or by a coating of silicon carbide.
• step ii) is carried out in:
• an exchanger or evaporator made of steel, preferably of carbon steel, said exchanger or evaporator comprising an inner surface, said inner surface likely to be in contact with the lithium salt of bis (fluorosulfonyl) imide being covered by a coating of carbide of silicon.
• the purification step (e) according to the invention comprises step ii). After concentration ii) of the aqueous solution obtained at the end of step a), a concentrated aqueous LiFSI solution is obtained.
• Step iii) can be carried out on the aqueous solution obtained at the end of step i) or of the concentration step ii) or of any other intermediate step.
• Step iii) can be carried out in equipment selected from an extraction column, a mixer-settler, and mixtures thereof.
• the liquid-liquid extraction step iii) is carried out in: an extraction column or a mixer-settler, based on silicon carbide or based on a fluoropolymer, preferably such as previously defined; or an extraction column or a mixer-settler, preferably steel made of carbon steel, said extraction column or said mixer-settler comprising an inner surface, said inner surface likely to be in contact with the lithium salt of bis (fluorosulfonyl) imide being covered by a polymeric coating preferably as defined above or by a coating of silicon carbide.
• step iii) of liquid-liquid extraction is carried out in:
• a fluorinated polymer such as for example PVDF (polyvinylidene fluoride), or PFA (copolymers of C 2 F 4 and perfluorinated vinyl ether)
• an extraction column or a mixer / settler made of steel, preferably carbon steel, said extraction column or said mixer-settling tank comprising an inner surface, said inner surface likely to be in contact with the lithium salt of bis (fluorosulfonyl) imide being covered
• the mobile stirring member (s) is (are) made of a steel material, preferably carbon steel, comprising an outer surface, said outer surface likely to be in contact with the bis (fluorosulfonyl) imide lithium salt being covered with a polymeric coating preferably as defined above, or with a coating of silicon carbide.
• Step iii) advantageously makes it possible to recover an organic phase, saturated with water, containing LiFSI (it is a solution of LiFSI in the at least one organic solvent OS2, said solution being saturated with water).
• the OS2 extraction solvent of LiFSI salt dissolved in deionized water is advantageously:
• the organic solvent OS2 is selected from the group consisting of esters, nitriles, ethers, chlorinated solvents, aromatic solvents, and mixtures thereof.
• the solvent OS2 is chosen from ethers, esters, and mixtures thereof.
• the solvent OS2 is chosen from methyl-t-butyl ether, cyclopentylmethyl ether and acetate. ethyl, propyl acetate, butyl acetate, and mixtures thereof, said organic solvent OS2 being advantageously butyl acetate.
• step iii) can be repeated at least once, preferably repeated from 1 to 10 times, preferably from 1 to 4 times.
• step iii) can be carried out in several mixer-settlers in series.
• the extracted organic phases are combined together to form a single organic solution.
• step iii) comprises adding the at least one organic solvent OS2 to the aqueous LiFSI solution, to allow the dissolution of said salt, and the extraction of said salt in the organic phase.
• the mass quantity of organic solvent (s) OS2 used can vary between 1/6 and 1 times the mass of the aqueous phase.
• the mass ratio of organic solvent (s) S 2 / water, during an extraction of step b) varies from 1/6 to 1/1, the number of extractions varying in particular from 2 to 10.
• the mass content of LiFSI in solution in the organic phase obtained at the end of step iii) is between 5% and 35%, preferably between 10% and 25% by weight relative to the total mass of the solution.
• Stage iv-1) advantageously makes it possible to obtain a LiFSI solution in the at least one organic solvent OS2 comprising a LiFSI content by mass of between 20% and 60%, and preferably between 30% and 50% by weight relative to to the total mass of the solution.
• the pre-concentration step iv-1) can be carried out:
• under reduced pressure for example at a pressure of less than 50 mbar abs, in particular at a pressure of less than 30 mbar abs.
• the pre-concentration step iv-1) is carried out in: an exchanger or an evaporator, based on silicon carbide or based on a fluoropolymer preferably as defined above; or an exchanger or an evaporator, made of steel, preferably carbon steel, said exchanger or evaporator comprising an inner surface, said inner surface capable of being in contact with the bis (fluorosulfonyl) imide lithium salt being covered by a polymeric coating of preferably as defined above or by a coating of silicon carbide.
• step iv-1) is carried out in:
• an exchanger or evaporator made of steel, preferably of carbon steel, said exchanger or evaporator comprising an inner surface, said inner surface likely to be in contact with the lithium salt of bis (fluorosulfonyl) imide being covered by a coating of carbide of silicon.
• Step iv-2) can be carried out in equipment chosen from an evaporator, such as for example a thin-film evaporator (and preferably a short-path thin-film evaporator), or an exchanger.
• an evaporator such as for example a thin-film evaporator (and preferably a short-path thin-film evaporator), or an exchanger.
• an exchanger or evaporator made of steel, preferably of carbon steel, said exchanger or evaporator comprising an inner surface, said inner surface likely to be in contact with the bis (fluorosulfonyl) imide lithium salt being covered by a polymeric coating, preferably as defined above or by a coating of silicon carbide.
• the above-mentioned step (e) comprises a step iv-2) of concentrating the bis (fluorosulfonyl) imide lithium salt by evaporation of said at least one organic solvent OS2, in a short-film thin film evaporator. route, preferably under the following conditions:
• step iv-2) concentration is conducted at a pressure between 10 -2 mbar and 5 mbar abs abs, preferably between 5.10 and 2 mbar abs 2 mbar abs, preferably between 5.10 and 1 mbar 2 abs, even more preferably between 0.1 and 1 mbar abs, and in particular between 0.1 and 0.6 mbar abs.
• step iv-2) is carried out at a temperature between 30 ° C and 95 ° C, preferably between 40 ° C and 90 ° C, preferably between 40 ° C and 85 ° C, and in particular between 50 ° C and 80 ° C.
• step iv-2) is carried out with a residence time of less than or equal to 10 minutes, preferably less than or equal to 5 minutes, and preferably less than or equal to 3 minutes.
• the term “residence time” means the time that elapses between the entry of the lithium salt solution of bis (fluorosulfonyl) imide (in particular obtained at the result of step b) above) in the evaporator and the outlet of the first drop of the solution.
• the temperature of the condenser of the short-path thin-film evaporator is between -55 ° C. and 10 ° C., preferably between -50 ° C. and 5 ° C., more preferably between -50 ° C. and -5 ° C. 45 ° C and -10 ° C, and preferably between -40 ° C and -15 ° C.
• Short-path thin-film evaporators are also known under the name “Wiped film short path” (WFSP). They are typically so called because the vapors generated during evaporation make a “short trip" (short distance) before being condensed to the condenser.
• WFSP Wiped film short path
• evaporators marketed by the companies Buss SMS Ganzler ex Luwa AG, UIC Gmbh or VTA Process.
• short-path thin-film evaporators may include a solvent vapor condenser positioned within the apparatus itself (particularly in the center of the apparatus), unlike other types of film evaporators. thin (which are not short path) in which the condenser is located outside the device.
• the formation of a thin film of product to be distilled on the internal hot wall of the evaporator can typically be provided by continuously spreading on the evaporation surface by mechanical means. specified below.
• the evaporator may in particular be provided at its center, an axial rotor on which are mounted the mechanical means that allow the formation of the film on the wall.
• They may be rotors equipped with fixed blades: three-blade or four-blade lobed rotors in flexible or rigid materials, distributed over the entire height of the rotor or rotors equipped with moving blades, pallets, scrapers, guided rubbers.
• the rotor may be constituted by a succession of articulated pallets on pivot mounted on a shaft or axis via radial supports.
• Other rotors may be equipped with mobile rollers mounted on secondary axes and said rollers are pressed on the wall by centrifugation.
• the LiFSI salt solution is introduced into the short-path thin film evaporator with a flow rate of between 700 g / h and 1200 g / h, preferably between 900 g / h and 110 g / h for a evaporation surface of 0.04m 2 .
• the LiFSI can be obtained in solid form, and in particular in crystallized form, or in the form of a concentrated solution, the concentrated solution comprising less than 35% by weight of residual solvent, preferably less than 30% by weight.
• step (e) comprises a step (v) of crystallization of the lithium salt of bis (fluorosulfonyl) imide obtained at the end of step iv) mentioned above.
• the LiFSI is cold-crystallized, in particular at a temperature of less than or equal to 25 ° C.
• the crystallization step v) of LiFSI is carried out in an organic solvent S3 ("crystallization solvent") chosen from chlorinated solvents, such as, for example, dichloromethane, from alkanes such as, for example, pentane, hexane, cyclohexane, or heptane, and from aromatic solvents, such as, for example, toluene, in particular at a temperature of less than or equal to 25 ° C.
• the crystallized LiFSI at the end of step v) is recovered by filtration.
• metal ions is intended in particular to mean ions derived from transition metals (such as, for example, Cr, Mn, Fe, Ni, Cu), ions derived from poor metals (such as for example Al, Zn and Pb), ions derived from alkali metals (such as for example Na), ions derived from alkaline earth metals (such as for example Mg and Ca), and ions derived from silicon.
• the process according to the invention advantageously leads to a LiFSI having a reduced content of ions derived from the following metals: Cr, Mn, Fe, Ni, Cu, Al, Zn, Mo, Co, Pb, Na, Si, Mg, It.
• the process according to the invention advantageously leads to a composition comprising at least 99.9% by weight of LiFSI, preferably at least 99.95% by weight, preferably at least 99.99% by weight of LiFSI, and said LiFSI optionally comprising at least one of the following impurities in the indicated contents: 0 ⁇ H 2 0 ⁇ 100 ppm, 0 ⁇ Cl ⁇ 100 ppm, 0 ⁇ S0 4 2 to 100 ppm, 0 ⁇ F ⁇ 200 ppm, ⁇ FSO3L1 ⁇ 20 ppm, 0 ⁇ FSC>2NH2> 20 ppm, 0 ⁇ K ⁇ 100 ppm, 0 ⁇ Na ⁇ 10 ppm, 0 ⁇ Si ⁇ 40 ppm, 0 ⁇ Mg ⁇ 10 ppm, 0 ⁇ Fe ⁇ 10 ppm ⁇ 0 ⁇ 10ppm, 0 ⁇ Pb ⁇ 10ppm, 0 ⁇ Cu ⁇ 10ppm
• between x and y" or “ranging from x to y” means an interval in which the terminals x and y are included.
• the temperature "between 30 and 100 ° C” includes in particular the values 30 ° C and 100 ° C.
• the coupon A consists of a steel material coated with an enamel layer.
• the coupon B (comparative) consists of a 316L stainless steel material.
• the corrosion rate of coupons A and B was determined after 76 hours, by microscopic observation. The data are shown in the table below:
• the coupon A has a significant stability over time, even under severe operating conditions.
• the coupon B has a very high degree of corrosion, and therefore generates a very high risk of contamination with metal ions.

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