EP3797086A1 - Procede de préparation du sel de lithium du bis(fluorosulfonyl)imide - Google Patents
Procede de préparation du sel de lithium du bis(fluorosulfonyl)imideInfo
- Publication number
- EP3797086A1 EP3797086A1 EP19733854.4A EP19733854A EP3797086A1 EP 3797086 A1 EP3797086 A1 EP 3797086A1 EP 19733854 A EP19733854 A EP 19733854A EP 3797086 A1 EP3797086 A1 EP 3797086A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stream
- solution
- hcl
- flow
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
- B01D47/02—Separating dispersed particles from gases, air or vapours by liquid as separating agent by passing the gas or air or vapour over or through a liquid bath
-
- 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
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/106—Peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/108—Halogens or halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/50—Inorganic acids
- B01D2251/502—Hydrochloric acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/50—Inorganic acids
- B01D2251/506—Sulfuric acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/202—Single element halogens
- B01D2257/2027—Fluorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/80—Water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- the present invention relates to a process for the preparation of lithium salt of imides containing a fluorosulfonyl group.
- 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 LiPF 6
- this salt shows numerous disadvantages such as limited thermal stability, sensitivity to hydrolysis and therefore lower battery safety.
- new salts having the FSO 2 group have been studied and have demonstrated many advantages such as better ionic conductivity and resistance to hydrolysis.
- LiFSI LiN (FSO 2 ) 2
- LiFSI LiN (FSO 2 ) 2
- the present invention relates to a process for the preparation of Ci-S0 2 NHS0 2 CI comprising a step of chlorinating the sulfamic acid with at least one chlorinating agent and at least one sulfur-containing agent, said process leading to a flow F1, preferably a liquid , comprising CI-SO2NHSO2CI and a gas stream F2 comprising HCl and S0 2, said method comprising a step a) treatment of the gas flow F2.
- Stage a) of treatment advantageously makes it possible to avoid the release of HCl and S0 2 , contained in the gas stream F2, into the atmosphere.
- Stage a) of treatment of the gas stream F2 preferably comprises a step of contacting said stream F2 with an aqueous alkaline solution, and / or a step of contacting said stream F2 with a solution of hydrogen peroxide, and / or a step of separating HCl and S0 2 contained in said flow F2, and / or a step of absorption of HCl contained in said gaseous flow F2 in an aqueous solution, and / or a step of absorption of S0 2 contained in said gas stream F2 in a concentrated sulfuric acid solution.
- the gas flow F2 comprises:
- HCl more than 20% by weight of HCl, preferably more than 30% by weight of HCl, and advantageously more than 40% by weight of HCl; and or
- SO 2 more than 30% by weight of SO 2 , preferably more than 40% by weight of SO 2 , and advantageously more than 50% by weight of SO 2 .
- the gas stream F2 may optionally comprise one or more inert gases, such as, for example, nitrogen, helium or argon. It may for example be the inert gas (s) used in the aforementioned chlorination step.
- inert gases such as, for example, nitrogen, helium or argon. It may for example be the inert gas (s) used in the aforementioned chlorination step.
- the stream F1 can optionally comprise the chlorinating agent, such as for example SOCI 2 , for example in a mass content of less than 5% by weight, preferably less than 1% by weight, and advantageously less than 0.5% by weight per relative to the total weight of said stream F1.
- the chlorinating agent such as for example SOCI 2
- the stream F1 can optionally comprise the sulfur-containing agent, such as, for example, H 2 SO 4 , for example in a mass content of less than 5% by weight, preferably less than 1% by weight, and advantageously less than 0.5% by weight. weight relative to the total weight of said stream F1.
- the sulfur-containing agent such as, for example, H 2 SO 4
- the stream F1 may optionally comprise the chlorinating agent and the sulfur-containing agent, such as, for example, SOCI 2 , and H 2 SO 4 for example in a total mass content of less than 5% by weight, preferably less than 1% by weight. and advantageously less than 0.5% by weight relative to the total weight of said stream F1.
- the chlorinating agent and the sulfur-containing agent such as, for example, SOCI 2 , and H 2 SO 4 for example in a total mass content of less than 5% by weight, preferably less than 1% by weight. and advantageously less than 0.5% by weight relative to the total weight of said stream F1.
- the stream F1 can optionally comprise HCl and / or S0 2 , each in a content preferably of less than 5% by weight, preferably less than 1% by weight, and advantageously less than 0.5% by weight relative to the total weight of said F1 flow.
- step a) of treating the F 2 gas flow comprises i) bringing the gas stream F 2 into contact with an aqueous alkaline solution.
- the aqueous alkaline solution may be an aqueous solution of an alkali or alkaline earth metal hydroxide, or an aqueous solution of an alkali or alkaline earth metal carbonate.
- the aqueous alkaline solution is selected from an aqueous solution of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, calcium carbonate, potassium carbonate, and mixtures thereof. .
- the alkaline aqueous solution may be prepared by dissolving at least one alkaline or alkaline earth base in water.
- the contacting i) is performed in a neutralization column, in particular running against the current.
- the neutralization column may include:
- At least one lining such as for example a loose lining and / or a structured lining,
- trays such as for example perforated trays, fixed valve trays, trays movable valves, trays caps, or combinations thereof.
- the pH of the alkaline aqueous solution it is necessary to control the pH of the alkaline aqueous solution, so that it remains basic during the step i) of contacting in the neutralization column.
- the gas stream F2 is introduced at the bottom of the neutralization column, while the aqueous alkaline solution is introduced at the top of said column.
- the step i) of bringing the gas stream F2 into contact, in particular in a neutralization column, with an alkaline aqueous solution makes it possible to form and recover:
- a gaseous stream G1 comprising water and optionally one or more inert gases, preferably recovered at the top of the neutralization column;
- an alkaline flow L1 comprising water, Cl ions and sulphite ions SO 3 2 , preferably recovered at the bottom of the neutralization column, L 1 being preferably liquid.
- the alkaline stream L1 can optionally be directed to a wastewater treatment plant, before eventual release into the environment.
- step a) of treating the gas flow F2 comprises ii) bringing the gas stream F2 into contact with a solution of hydrogen peroxide.
- the SO 2 contained in the gas stream F 2 can then be reacted with hydrogen peroxide to quantitatively form sulfuric acid according to the reaction equation:
- the contacting ii) is carried out in a washing column, in particular operating against the current.
- the hydrogen peroxide solution may be an aqueous solution whose mass content of hydrogen peroxide ranges from 5 to 70% by weight, preferably from 5% to 50% by weight, and advantageously from 5% to 35% by weight. weight.
- the molar ratio of hydrogen peroxide / SO 2 contained in the gas stream F 2 can range from 1 to 25, preferably from 1 to 20, and preferably from 1 to 15.
- the washing column may comprise:
- At least one lining such as for example a loose lining and / or a structured lining,
- trays such as for example perforated trays, fixed valve trays, trays movable valves, trays caps, or combinations thereof.
- the gas flow F2 is introduced at the bottom of the washing column, while the hydrogen peroxide solution is introduced at the top of said column.
- step ii) bringing the gas stream F2 into contact, in particular in a washing column, with a solution of hydrogen peroxide makes it possible to form and recover:
- a gaseous flow G2 comprising water and optionally one or more inert gases, preferably recovered at the top of the washing column;
- an acid stream L2 comprising water, HCl and H 2 SO 4 , preferably recovered at the bottom of the washing column, said stream L 2 being preferably liquid.
- step a) may comprise an additional step ii-1) of treating the L 2 acid stream comprising contacting said L 2 acid stream with an aqueous alkaline solution, or an additional step ii-2) of separating HCl and H 2 S0 contained in the acid stream L2 to form and recover a stream F3 comprising HCl and a stream F'3 comprising H 2 S0.
- the aqueous alkaline solution may be an aqueous solution of an alkali or alkaline earth metal hydroxide, or an aqueous solution of an alkali or alkaline earth metal carbonate.
- the aqueous alkaline solution is selected from an aqueous solution of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, calcium carbonate, potassium carbonate, and mixtures thereof. .
- Step ii-1) can be carried out in a reactor, and preferably in a stirred reactor.
- step ii-1 makes it possible to form and recover:
- a gaseous flow G3 comprising water and optionally one or more inert gases, and
- an alkaline stream L3 comprising water, chloride ions and sulfate ions S0 2 , said stream L3 being preferably liquid.
- the L3 alkaline stream may possibly be directed to a wastewater treatment plant, before eventual release into the environment.
- step a) of treating the gas flow F2 comprises ii) bringing the gas stream F2 into contact with a solution of hydrogen peroxide, followed by a step ii-2) of separation of HCl and H 2 S0 contained in the stream L2 to form and recover a stream F3 comprising HCl and a stream F'3 comprising H 2 S0 4 .
- the separation may be separation by distillation or electrodialysis.
- step ii-2) when step ii-2) is an electrodialysis separation, it makes it possible to form and recover a liquid flow F3 comprising HCl, and a liquid flow F'3 comprising H 2 S0.
- the flow F '3 is preferably a concentrated aqueous solution of H 2 SO 4, preferably comprising a mass content of H 2 SO 4 greater than or equal to 20%, preferably greater than or equal to 50%.
- the F3 flow includes:
- H 2 SO 4 preferably less than 5% by weight.
- the flow F3 may possibly be directed to a wastewater treatment plant, before eventual release into the environment.
- the distillation can be carried out in at least one distillation column.
- the separation step advantageously makes it possible to separate HCl and H 2 SO 4 contained in stream L 2.
- step ii-2) when step ii-2) is a separation by distillation, it makes it possible to form and recover a stream F3 comprising HCl, preferably at the top of the distillation column, and a liquid stream F'3 comprising H 2 S0 4 .
- the stream F3 may be a gas stream or a liquid stream.
- the flow F3 comprises:
- H 2 SO 4 less than 5000 ppm of H 2 SO 4 , preferably less than 1000 ppm of H 2 SO 4 , and advantageously less than 500 ppm of H 2 SO 4 .
- the flow F'3 is preferably a concentrated aqueous solution of H 2 SO 4 , preferably comprising a mass content of H 2 SO 4 greater than or equal to 20%, preferably greater than or equal to 50%.
- the flow F'3 may optionally be subjected to a concentration or dilution step. It can be marketed, and / or recycled in said process.
- the flow F3 When the flow F3 is gaseous, it may be marketed, and / or used as a raw material in another process, and / or subjected to a step of absorption of the hydrochloric acid contained in said flow F3 in an aqueous solution, said the aqueous solution is preferably deionized water, making it possible to form and recover a solution of hydrochloric acid.
- the mass concentration of HCl in the hydrochloric acid solution may be from 5 to 50%, preferably from 15 to 40%, and more particularly from 30 to 35% by weight.
- the hydrochloric acid solution obtained can advantageously be recovered commercially.
- the flow F3 When the flow F3 is liquid, it can be subjected to a concentration or dilution step, for example to obtain a solution of hydrochloric acid at 33% by weight, which can advantageously be recovered commercially.
- step a) of treating the gas flow F2 comprises:
- the gas stream G4 may optionally comprise one or more inert gas (s), such as, for example, nitrogen.
- inert gas such as, for example, nitrogen.
- the above-mentioned compression step iii) may make it possible to compress the gas flow F2 at a pressure greater than 5 bar abs, preferably greater than 7 bar abs, and preferably greater than 10 bar abs, and still more advantageously greater than 15 bar abs. , for example greater than 20 bar abs.
- the above-mentioned separation step iv) can be a distillation or a membrane separation.
- the separation step iv) is a membrane separation, it advantageously leads to a gaseous flow G4 comprising HCl, and to a F4 gas flow comprising S0 2 .
- a membrane separation step typically comprises the use of one or more membranes. When several membranes are used, they can be arranged in series or in a cluster.
- step iv) is a membrane separation carried out with one or more membrane (s).
- the membrane (s) may be inorganic (for example ceramic or glass), organic (for example polymeric) or a mixture of both.
- the membrane separation step is carried out with at least one polymeric membrane, for example based on PVDF, polyamide, polyimide, or mixtures thereof.
- step iv) is a membrane separation, it advantageously leads to a gas stream G4 comprising purified HCl, and to a F4 gas stream (denoted F 4 g ) comprising purified S0 2 .
- step iv) is a distillation carried out in at least one distillation column.
- the distillation column may comprise at least 8 theoretical stages, preferably at least 10 theoretical stages, advantageously at least 12 theoretical stages.
- the molar reflux ratio may be at least 1.5, preferably at least 3, and preferably at least 4.
- the separation by distillation can be carried out:
- a temperature at the bottom of the distillation column ranging from 40 ° C. to 80 ° C., preferably from 40 ° C. to 60 ° C., and preferentially from 50 ° C. to 60 ° C., at a pressure of 10 bar abs; or
- a temperature at the bottom of the distillation column ranging from 40 ° C. to 100 ° C., preferably from 50 ° C. to 90 ° C., and preferentially from 60 ° C. to 80 ° C., at a pressure of 14 bar abs.
- the distillation column may comprise:
- At least one lining such as for example a loose lining and / or a structured lining,
- trays such as for example perforated trays, fixed valve trays, trays movable valves, trays caps, or combinations thereof.
- the separation step iv) is a distillation
- the gaseous flow G4 advantageously comprises purified HCl, preferably recovered at the top of the distillation column
- the liquid F4 stream advantageously comprises purified S0 2 , preferably recovered at the bottom of the distillation column.
- the liquid stream F4 obtained at the end of the separation step iv) by distillation may optionally be subjected to an additional vaporization step to give a gas stream.
- step a) of treating the gas flow F2 comprises: iii) a possible step of compressing said gas flow F2,
- the gas stream G4 obtained at the end of step iv) advantageously comprises less than 100 ppm of SO 2 , preferably less than 80 ppm of SO 2 , and preferably less than 50 ppm of SO 2 .
- ppm are “parts per million” expressed by weight.
- the gas stream G4 obtained at the end of step iv) can advantageously be:
- step a) of treating the gas flow F2 comprises: iii) a possible step of compressing said gas flow F2,
- step v) an additional step of treating the gas flow G4, said step v) comprising:
- o v-2) a step of absorption of the hydrochloric acid contained in said gas stream G4 in an aqueous solution, said aqueous solution preferably being deionized water, for forming and recovering an aqueous solution of hydrochloric acid L5;
- Step v-1) is preferably a step of adsorbing impurities with at least one solid adsorber, such as, for example, activated charcoal or alumina.
- the gas stream G4 obtained at the end of step v-1) can advantageously be marketed, and / or used as a raw material in another process, and / or subjected to the above-mentioned step v-2).
- the purification step v-1) advantageously allows to reduce the content of residual S0 2, for example in a content less than 50 ppm, preferably less than 20 ppm, and preferably less than 10 ppm in the purified gas stream G4 .
- the above-mentioned step v-2) advantageously makes it possible to collect an aqueous solution of hydrochloric acid L5, and a gaseous stream G5 comprising water and optionally one or more inert gas (s).
- the mass concentration of HCl in the aqueous solution of L5 hydrochloric acid may be from 5 to 50%, preferably from 15 to 40%, and more particularly from 30 to 35% by weight.
- the solution L5 can advantageously be commercially valorized.
- the stream F4 advantageously comprises less than 100 ppm of HCl, preferably less than 80 ppm, and preferably less than 50 ppm of HCl.
- the flow F4, liquid or gaseous, obtained at the end of step iv) may advantageously be subjected to an additional step vi) of treatment.
- the treatment step vi) comprises vi-1) bringing said liquid flow F4 into contact with an aqueous alkaline solution.
- the aqueous alkaline solution may be an aqueous solution of an alkali or alkaline earth metal hydroxide, or an aqueous solution of an alkali or alkaline earth metal carbonate.
- the aqueous alkaline solution is selected from an aqueous solution of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, calcium carbonate, potassium carbonate, and mixtures thereof. .
- the contacting vi-1) can be carried out in a reactor, and preferably in a stirred reactor.
- the above-mentioned contacting vi-1) can lead to a gas stream G6 comprising water and optionally one or more inert gases, and to an alkaline stream L6 comprising water, chloride ions and ions. sulfites, said stream L6 being preferably liquid.
- the alkaline stream L6 can optionally be directed to a wastewater treatment plant, before eventual release into the environment.
- the treatment step vi) includes:
- a step vi-4-a) of S0 3 absorption contained in said flow F5 in a concentrated sulfuric acid solution for forming and recovering a gas stream G9 comprising water and optionally one or more inert gas (s), and an L9 oleum;
- step vi-4-b) dilution of L9 oleum in water, to form an aqueous solution L10.
- the alkaline aqueous solution of step vi-2) may be an aqueous solution of an alkali or alkaline earth metal hydroxide, or an aqueous solution of an alkali or alkaline earth metal carbonate.
- the aqueous alkaline solution is selected from an aqueous solution of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, calcium carbonate, potassium carbonate, and mixtures thereof. .
- the contacting vi-2) is performed in a neutralization column, in particular operating against the current.
- the neutralization column may include:
- At least one lining such as for example a loose lining and / or a structured lining,
- trays such as for example perforated trays, fixed valve trays, trays movable valves, trays caps, or combinations thereof.
- the gas stream F4 is introduced at the bottom of the neutralization column, while the aqueous alkaline solution is introduced at the top of said column.
- step vi-2) of bringing the gas stream F4 into contact, in particular in a neutralization column, with an alkaline aqueous solution makes it possible to form and recover:
- a gaseous stream G7 comprising water and optionally one or more inert gases, preferably recovered at the top of the neutralization column;
- an alkaline stream L7 comprising water, Cl ions and sulphite ions, preferably recovered at the bottom of the neutralization column, said stream L8 being preferably liquid.
- the flow L7 can possibly be directed to a wastewater treatment plant, before eventual release into the environment.
- the above-mentioned step vi-3) is carried out in a washing column, in particular operating against the current.
- the washing column may comprise:
- At least one lining such as for example a loose lining and / or a structured lining,
- trays such as for example perforated trays, fixed valve trays, trays movable valves, trays caps, or combinations thereof.
- the gas stream F4 is introduced at the bottom of the washing column, while the hydrogen peroxide solution is introduced at the top of said column.
- the hydrogen peroxide solution may be an aqueous solution whose mass content of hydrogen peroxide ranges from 5% to 70% by weight, preferably from 5% to 50% by weight, and advantageously from 5% to 35% by weight. in weight.
- the molar ratio hydrogen peroxide / SO 2 contained in the gas stream F4 can range from 1 to 25, preferably from 1 to 20, and preferably from 1 to 15.
- the step vi-3) of bringing the gas stream F4 into contact, in particular in a washing column, with a solution of hydrogen peroxide makes it possible to form and recover:
- a gaseous stream G8 comprising water and optionally one or more inert gases, preferably recovered at the top of the washing column;
- a stream L8 comprising water and H 2 SO, preferably recovered at the bottom of the washing column, said stream L8 being preferably liquid.
- the mass concentration of H 2 SO 4 in the aqueous stream L 8 may be greater than or equal to 5%, preferably greater than or equal to 10%, and advantageously greater than or equal to 20%.
- the stream L8 may be optionally subjected to a concentration step.
- Stream L8 may advantageously be marketed, and / or recycled in the above-mentioned chlorination step.
- the above-mentioned step vi-4) is carried out in a reactor.
- the concentrated sulfuric acid solution used in step vi-4-a) is preferably a more than 95% by weight solution of H 2 SO.
- the L9 oleum obtained at the end of step vi-4-a) mentioned above can be directly marketed, and / or subjected to a possible step vi-4-b) of dilution of the L9 oleum in water, to form an aqueous solution L10.
- the solution L10 is advantageously a sulfuric acid solution that can be marketed and / or recycled in the process, for example in the above-mentioned chlorination step and / or in step vi-4-a).
- step a) of treating the gas flow F2 comprises:
- a step of absorption of the hydrochloric acid contained in said gas stream F2 in an aqueous solution said aqueous solution preferably being deionized water, making it possible to form and recover a solution of hydrochloric acid L1 1, and a gas stream G1 1 comprising SO2, water and optionally one or more inert gases;
- the absorption step vii) can be carried out in a column, the gas stream G1 1 being preferably recovered at the top of the column, while the L1 solution 1 preferably being recovered at the bottom of the column.
- the mass concentration of HCl in the hydrochloric acid solution L1 1 can be from 5 to 50%, preferably from 15 to 40%, and more particularly from 30 to 35%.
- the solution L1 1 may optionally comprise S0 2 in a mass content of less than or equal to 100 ppm, preferably less than or equal to 50 ppm, advantageously less than or equal to 20 ppm.
- Stage a) of treatment of the gas stream F2 may comprise a step viii), subsequent to stage vii), comprising the purification of the solution L1 1, preferably by adsorption of residual impurities with at least one solid adsorber, such as, for example, activated charcoal or silica gel. After this complementary adsorption step on silica gel or activated carbon, it is advantageously possible to reach S0 2 contents of less than 1 ppm in the HCl solution.
- the L1 1 solution may advantageously be commercially valuable.
- the above-mentioned step vii) advantageously makes it possible to collect a solution of hydrochloric acid L1 1, and a gaseous stream G1 1 comprising S0 2 , water, and optionally one or more inert gases (s).
- At least 95% by weight, preferably at least 99% by weight, advantageously at least 99.5% by weight, and preferably at least 99.9% by weight of HCl contained in the gas stream F2 are recovered in the liquid flow L1 1.
- At least 95% by weight, preferably at least 99% by weight, advantageously at least 99.5% by weight, and preferably at least 99.9% by weight of S0 2 contained in the gas stream F2 are recovered in the gas stream G1 1.
- Stage a) of treatment of the gas stream F2 may also comprise a step ix) of drying the gas stream G1 1, for example carried out in the presence of calcium sulphate, sodium sulphate, magnesium sulphate, sodium chloride and the like.
- the gaseous stream G1 may be subjected to one of the steps vi-2), vi-3) or vi-4) as defined above.
- step a) of treatment of the gas flow F2 comprises: x) a step of S0 2 absorption contained in said gas stream F2 in a concentrated sulfuric acid solution, making it possible to form and recover a gas stream G12 comprising HCl and optionally one or more inert gas (s), and a stream L12 comprising water, H 2 SO 4 and SO 2, said stream L 12 being preferably liquid.
- the concentrated sulfuric acid solution used in step x) is preferably a solution containing more than 95% by weight of H 2 SO 4 .
- the absorption step x) may be carried out in a column, the gas stream G12 preferably being recovered at the top of the column, while the L12 solution is preferably recovered at the bottom of the column.
- the gas stream G12 comprises more than 50% by weight of HCl, preferably more than 80% by weight of HCl, and advantageously more than 90% by weight of HCl relative to the total weight of said G12 stream.
- the gas stream G12 may advantageously be marketed directly, and / or be subjected to a recovery step to form a commercial solution HCl at 33% (it may for example be a step similar to step vii) above. above).
- a recovery step to form a commercial solution HCl at 33% (it may for example be a step similar to step vii) above. above).
- at least 95% by weight, preferably at least 99% by weight, advantageously at least 99.5% by weight, and preferably at least 99.9% by weight of HCl contained in the gas stream F2 are recovered in the gas stream G12.
- At least 95% by weight, preferably at least 99% by weight, advantageously at least 99.5% by weight, and preferably at least 99.9% by weight of S0 2 contained in the gas stream F2 are recovered in the L12 stream.
- the stream L12 can possibly:
- gaseous stream G13 may advantageously be recycled at any stage of the process comprising S0 2 gas, for example reused in any of the steps vi-2), vi-3) or vi-4) mentioned above;
- the step of contacting the stream L12, in particular in a stirred reactor, with a solution of hydrogen peroxide makes it possible to form and recover:
- a gas stream G14 comprising water and optionally one or more inert gases
- a stream L14 comprising water and H 2 S0 4 , said stream L14 being preferably liquid.
- the mass concentration of H 2 S0 in the aqueous stream L14 may be greater than or equal to 5%, preferably greater than or equal to 10%, and advantageously greater than or equal to 20%.
- the stream L14 may be optionally subjected to a concentration step.
- the stream L14 may advantageously be marketed, and / or recycled in the above-mentioned chlorination step.
- the chlorination step according to the invention can be carried out:
- the sulfur-containing agent may be selected from the group consisting of chlorosulfonic acid (CIS0 3 H), sulfuric acid, oleum, and mixtures thereof.
- 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 (PCI 3 ), phosphoryl trichloride (POCI 3 ), and mixtures thereof.
- the chlorinating agent is thionyl chloride.
- the chlorination step 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 0.9 and 5.
- the molar ratio between the chlorinating agent and the sulfamic acid may be between 2 and 10, preferably between 2 and 5.
- the sulfur-containing agent is chlorosulphonic acid
- the molar ratio between the latter and the sulphamic acid is between 0.9 and 5
- / or the molar ratio between the chlorinating agent and the acid sulfamic 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 0.9 and 5, and or the molar ratio between the chlorinating agent and the sulfamic acid is between 2 and 10.
- the present invention also relates to a process for the preparation of the lithium salt of bis (fluorosulfonyl) imide (LiFSI) comprising the aforementioned process for the preparation of CI-SO2-NH-SO2-Cl.
- LiFSI bis (fluorosulfonyl) imide
- the process for preparing the lithium salt of bis (fluorosulfonyl) imide comprises the following steps:
- the process for preparing bis (fluorosulfonyl) imide lithium salt according to the invention advantageously allows the recovery of certain secondary flows formed during the preparation of said LiFSI, which generates a better economic return of the process.
- a stirred 100-liter steel reactor was charged with sulfamic acid (1 eq, 257.5 moles, 25 kg) and 95% sulfuric acid (1 eq, 257.5 moles). 26.6 kg).
- Thionyl chloride (4 eq, 1030 mol, 122.5 kg) is added gradually to the reactor. The temperature of the reaction medium is gradually increased to 75 ° C. The reaction is carried out at atmospheric pressure.
- the total conversion to sulfamic acid is obtained after 60 hours.
- a condenser is disposed on the vent line of the reactor so as to condense the vaporized thionyl chloride and reflux it into the reaction medium.
- the gases generated by the reaction (HCl and SO 2 ) and not condensed by the condenser are directed to a system for absorbing them (see Examples 2 and 3).
- the gases generated by the reaction of Example 1 are directed to a storage containing 700 kg of a solution of H 2 0 2 5% by weight. This storage is surmounted by a packed column sprayed at the top by the H 2 0 2 solution contained in said storage. A pump is used to withdraw the H 2 0 2 solution from the storage to water the column.
- the gases generated by the reaction (HCl and S0 2 ) are introduced into the H 2 0 2 solution contained in the storage by means of a dip tube. HCI and SO 2 are absorbed into the H 2 O 2 solution and the SO 2 reacts with H 2 O 2 to form H 2 SO 4 .
- the packed column makes it possible to finalize the absorption of the gases generated by the HCl and S0 2 reaction and to completely convert the S0 2 to H 2 SO 4 .
- a solution of 797 kg is obtained comprising 1% by weight of H 2 O 2 , 5% by weight of HCl and 10% by weight of H 2 SO.
- the gases generated by the reaction of Example 1 are directed to an HCl absorption column sprayed with water overhead.
- This column makes it possible to obtain in foot a solution of HCI 33%.
- This column makes it possible to specifically absorb the HCI gas, while the S0 2 gas is not absorbed.
- the S0 2 gas is recovered at the top of the HCl absorption column and is sent to a storage tank containing 300 kg of a 10% by weight solution of H 2 0 2 solution.
- the device for absorbing SO 2 gas in a solution of H 2 0 2 is identical to that described in Example 2.
- the packed column makes it possible to finalize the absorption of SO 2 and to completely convert the S0 2 in H 2 S0 4 .
- 130 kg of a 33% solution of HCl and a solution of 354 kg comprising less than 1% by weight of H 2 O 2 and 23% by weight of H 2 SO are obtained on the one hand. 4 .
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1854313A FR3081457B1 (fr) | 2018-05-23 | 2018-05-23 | Procede de preparation du sel de lithium du bis(fluorosulfonyl)imide |
PCT/FR2019/051148 WO2019224470A1 (fr) | 2018-05-23 | 2019-05-21 | Procede de préparation du sel de lithium du bis(fluorosulfonyl)imide |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3797086A1 true EP3797086A1 (fr) | 2021-03-31 |
Family
ID=63036136
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19733854.4A Pending EP3797086A1 (fr) | 2018-05-23 | 2019-05-21 | Procede de préparation du sel de lithium du bis(fluorosulfonyl)imide |
Country Status (6)
Country | Link |
---|---|
US (1) | US11261087B2 (fr) |
EP (1) | EP3797086A1 (fr) |
JP (1) | JP2021524429A (fr) |
CN (1) | CN112154121A (fr) |
FR (1) | FR3081457B1 (fr) |
WO (1) | WO2019224470A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3081456B1 (fr) | 2018-05-23 | 2020-12-18 | Arkema France | Procede de preparation de sel d'imides contenant un groupement fluorosulfonyle |
CN113336248B (zh) * | 2021-06-09 | 2023-04-07 | 深圳市研一新材料有限责任公司 | 一种氟磺酸锂的制法及氟磺酸锂和应用 |
CN113800486B (zh) * | 2021-09-14 | 2023-06-23 | 山东凯盛新材料股份有限公司 | 双氯磺酰亚胺的生产工艺 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS48101378A (fr) * | 1972-04-05 | 1973-12-20 | ||
US3956385A (en) * | 1973-04-18 | 1976-05-11 | Sumitomo Chemical Company, Limited | Process for producing sulfonylamides |
JPS627419A (ja) * | 1985-01-30 | 1987-01-14 | Kuraray Co Ltd | 酸化イオウ系ガスの分離法 |
JP3976444B2 (ja) * | 1998-06-23 | 2007-09-19 | 株式会社タクマ | 排ガス処理方法および処理装置 |
FR2975694B1 (fr) | 2011-05-24 | 2013-08-02 | Arkema France | Procede de preparation de bis(fluorosulfonyl)imidure de lithium |
CN102764572A (zh) * | 2012-05-15 | 2012-11-07 | 山西三维丰海化工有限公司 | 一种氯化法生产三氯乙酰氯尾气吸收新方法 |
KR101738789B1 (ko) | 2012-08-06 | 2017-05-22 | 닛뽕소다 가부시키가이샤 | 비스(할로술포닐)아민의 제조 방법 |
US8377406B1 (en) * | 2012-08-29 | 2013-02-19 | Boulder Ionics Corporation | Synthesis of bis(fluorosulfonyl)imide |
FR2998297B1 (fr) | 2012-11-22 | 2014-11-14 | Arkema France | Procede de preparation de sel d'imides contenant un groupement fluorosulfonyle |
FR3020060B1 (fr) | 2014-04-18 | 2016-04-01 | Arkema France | Preparation d'imides contenant un groupement fluorosulfonyle |
CN104447329A (zh) * | 2014-10-29 | 2015-03-25 | 山东汇海医药化工有限公司 | 一种2-氯乙酰乙酸乙酯的制备方法 |
CN106006586B (zh) * | 2016-05-27 | 2018-10-19 | 上海康鹏科技有限公司 | 一种双氟磺酰亚胺钾的制备方法 |
FR3081866B1 (fr) * | 2018-06-01 | 2020-05-08 | Arkema France | Procede de preparation de sel d'imides contenant un groupement fluorosulfonyle |
-
2018
- 2018-05-23 FR FR1854313A patent/FR3081457B1/fr active Active
-
2019
- 2019-05-21 CN CN201980034516.9A patent/CN112154121A/zh active Pending
- 2019-05-21 JP JP2020564516A patent/JP2021524429A/ja active Pending
- 2019-05-21 WO PCT/FR2019/051148 patent/WO2019224470A1/fr unknown
- 2019-05-21 US US17/056,781 patent/US11261087B2/en active Active
- 2019-05-21 EP EP19733854.4A patent/EP3797086A1/fr active Pending
Also Published As
Publication number | Publication date |
---|---|
US11261087B2 (en) | 2022-03-01 |
KR20210010470A (ko) | 2021-01-27 |
US20210122634A1 (en) | 2021-04-29 |
FR3081457A1 (fr) | 2019-11-29 |
JP2021524429A (ja) | 2021-09-13 |
FR3081457B1 (fr) | 2020-05-08 |
CN112154121A (zh) | 2020-12-29 |
WO2019224470A1 (fr) | 2019-11-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3797086A1 (fr) | Procede de préparation du sel de lithium du bis(fluorosulfonyl)imide | |
CA2057362C (fr) | Procede pour le traitement de solution aqueuses contenant du sulfure d'hydrogene, du cyanure d'hydrogene et de l'ammoniac | |
KR100654286B1 (ko) | Nf3의 정제 방법 | |
KR100929472B1 (ko) | 염소 가스, 차아염소산 나트륨 수용액 및 액체 염소의 제조방법 | |
CS276380B6 (en) | Process of chlorine industrial isolation | |
US10589223B1 (en) | Method and apparatus for treating a sulfur dioxide containing stream by hydrogen sulfide in aqueous conditions | |
CA2429837C (fr) | Procede d'extraction de mercure a partir d'un gaz | |
RU2008150592A (ru) | Способ получения хлора из хлористого водорода и кислорода | |
FR2924115A1 (fr) | Procede de preparation d'un acide trifluoromethanesulfinique | |
EP0016290B1 (fr) | Procédé continu d'élimination de l'anhydride sulfureux des gaz de combustion, et hydrogène et acide sulfurique ainsi produits | |
AU2002217170A1 (en) | Method for removing mercury from gas | |
JP2006219369A (ja) | 塩素の製造方法 | |
CA2878050A1 (fr) | Procede de preparation d'un compose sulfonimide et de ses sels | |
JP5393702B2 (ja) | グリオキシル酸と塩酸とを含有する水性反応媒体からグリオキシル酸を分離する方法 | |
KR102707720B1 (ko) | 리튬 비스(플루오로설포닐)이미드 염의 제조 방법 | |
JP4535269B2 (ja) | 水素の製造装置及び水素の製造方法 | |
CN111471493B (zh) | 一种净化焦炉煤气脱硫液的方法 | |
WO2020115419A1 (fr) | Procede de preparation de sel d'imides contenant un groupement fluorosulfonyle | |
FR2709481A1 (fr) | Procédé pour l'élimination d'impuretés de l'hydrate d'hydrazine. | |
JP2003001048A (ja) | 湿潤ガスの乾燥方法、硫酸ミストの除去方法およびこれらを用いた塩素の製造方法 | |
FR3002930A1 (fr) | Procede et installation de production de dioxyde de carbone et d'hydrogene | |
US5985226A (en) | Method of recovering chlorine from a gas mixture | |
JP2009196826A (ja) | 塩素の製造方法 | |
EP4301695A1 (fr) | Système et méthode de traitement de gaz résiduaire pour une installation de production d'acide sulfurique | |
US20220219980A1 (en) | Methods for recovering iodine (i2) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20201102 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) |