Ammonia sulfonyl fluoride compositions and methods for preparing ammonia sulfonyl fluoride compositions

Abstract

This invention provides a method for producing an aminosulfonyl fluoride composition, the method comprising: providing a solution comprising fluorosulfonic acid, urea, and a solvent; reacting the solution at a reaction temperature of 80°C to about 170°C to produce a mixture comprising aminosulfonyl fluoride, bis(fluorosulfonyl)imide, ammonium fluorosulfate, and the solvent; separating the ammonium fluorosulfate from the mixture; and separating the mixture into an aminosulfonyl fluoride composition and a recycled composition, the aminosulfonyl fluoride composition comprising a higher concentration of aminosulfonyl fluoride and bis(fluorosulfonyl)imide than the recycled composition. The molar ratio of the fluorosulfonic acid to the urea in the solution is about 1.80:1 to about 2.00:1.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Patent Application No. 17 / 582,562, filed January 24, 2022, and U.S. Provisional Application No. 63 / 143,102, filed January 29, 2021, both of which are incorporated herein by reference in their entirety. Technical Field

[0003] This disclosure relates to aminosulfonyl fluoride compositions and methods for producing aminosulfonyl fluoride compositions. Background Technology

[0004] Ammoniasulfonyl fluoride (H2NSO2F) is a strong acid that can be used in a variety of applications, including as a raw material for the production of lithium sulfamyl fluoride, which is used in lithium-ion batteries.

[0005] HFSI (fluorosulfonyl)imide is a key raw material for producing lithium bis(fluorosulfonyl)imide (LiFSI) used in lithium-ion batteries. HFSI can be prepared by several methods.

[0006] US Patent 8,337,797 to Honda et al. discloses that HFSI can be prepared by the reaction of urea with fluorosulfonic acid as shown in Equation 1:

[0007] Equation 1: 5HSO3F + 2CO(NH2)2 → HN(SO2F)2 + 2CO2 + 3NH4SO3F.

[0008] Honda discloses a two-step batch process for producing HFSI from urea and fluorosulfonic acid. In the first step, urea is dissolved in fluorosulfonic acid at a temperature low enough to prevent a reaction between urea and fluorosulfonic acid in Equation 1. In the second step, a urea / fluorosulfonic acid solution is slowly added to a separate reaction vessel containing a reaction medium that is sufficiently heated to allow the reaction of Equation 1 to proceed. The controlled addition allows control over the heat generated by the exothermic reaction of Equation 1. US8,337,797 discloses that the heated reaction medium can be either fluorosulfonic acid or HFSI, but a mixture of fluorosulfonic acid and HFSI is preferred, wherein HFSI is used to further control the reaction, especially at the beginning, when the urea / fluorosulfonic acid solution is first added to the heated reaction medium. However, the batch process disclosed in US8,337,797 is insufficient for the efficient commercial-scale production of HFSI.

[0009] International Publication WO2011 / 111780, also granted to Honda et al., discloses a recovery method for continuously removing reaction liquids from a reaction vessel, such as by continuously discharging reaction liquids (containing ammonium salt byproducts) in a slurry state through an overflow outlet. The disclosed method is carried out in a production batch, wherein the product HFSI is added back to the reaction vessel before being used in the next production batch of the reaction.

[0010] Therefore, there is a need to develop efficient methods for the large-scale production of commercial quantities of aminosulfonyl fluoride and more efficient methods for the large-scale production of commercial quantities of HFSI. Summary of the Invention

[0011] This disclosure provides an aminosulfonyl fluoride composition, a method for producing the aminosulfonyl fluoride composition, and a method for producing HFSI from the aminosulfonyl fluoride composition.

[0012] In one embodiment, the present invention provides a method for producing an aminosulfonyl fluoride composition. The method includes providing a solution comprising fluorosulfonic acid, urea, and a solvent, wherein the molar ratio of fluorosulfonic acid to urea is from about 1.80:1 to about 2.00:1; reacting the solution at a reaction temperature of about 80°C to about 170°C to produce a mixture comprising aminosulfonyl fluoride, bis(fluorosulfonyl)imide, ammonium fluorosulfate, and a solvent; separating the ammonium fluorosulfate from the mixture; and separating the mixture into an aminosulfonyl fluoride composition and a recycled composition, the aminosulfonyl fluoride composition comprising a higher concentration of aminosulfonyl fluoride and bis(fluorosulfonyl)imide than the recycled composition.

[0013] In another embodiment, the present invention provides a composition comprising aminosulfonyl fluoride and bis(fluorosulfonyl)imide, wherein the concentration of aminosulfonyl fluoride is about 1 mol% to about 10 mol% of the combination of aminosulfonyl fluoride and bis(fluorosulfonyl)imide.

[0014] In another embodiment, the present invention provides a composition comprising aminosulfonyl fluoride and bis(fluorosulfonyl)imide, wherein the concentration of aminosulfonyl fluoride is from about 50% by weight to about 99.9% by weight of the composition.

[0015] The above and other features of this disclosure, and the ways in which they are implemented, will become more apparent and better understood by referring to the following description of the embodiments in conjunction with the accompanying drawings. Attached Figure Description

[0016] Figure 1 This is a process flow diagram according to some embodiments of the present disclosure, which illustrates an integrated method for the continuous production of aminosulfonyl fluoride compositions.

[0017] Figure 2This is a process flow diagram according to some embodiments of the present disclosure, which illustrates an integrated method for the continuous production of bis(fluorosulfonyl)imide from an aminosulfonyl fluoride composition.

[0018] Figure 3 This is a graph showing the change in concentration of sulfonyl fluoride as a function of the ratio of fluorosulfonic acid to urea. Detailed Implementation

[0019] This disclosure provides an integrated method for scalable production of commercial quantities of aminosulfonyl fluoride compositions from the reaction of fluorosulfonic acid and urea. Surprisingly, limiting the ratio of fluorosulfonic acid to urea has been found to significantly improve process yield.

[0020] This disclosure also provides an integrated method for scalable production of commercial quantities of bis(fluorosulfonyl)imide from an aminosulfonyl fluoride composition. In some embodiments, the method includes recycling unreacted fluorosulfonic acid in an efficient and continuous manner. Alternatively or additionally, in some embodiments, the method includes directing the recycled unreacted fluorosulfonic acid to a storage tank.

[0021] As disclosed herein, aminosulfonyl fluoride is produced from a solution comprising urea, fluorosulfonic acid, and a solvent. Surprisingly, it has been found that at a molar ratio of fluorosulfonic acid to urea of ​​2.0:1, bis(fluorosulfonyl)imide can be used to produce aminosulfonyl fluoride at a concentration exceeding 3 mol% of the combination of aminosulfonyl fluoride and bis(fluorosulfonyl)imide. At a molar ratio of fluorosulfonic acid to urea of ​​1.9:1, bis(fluorosulfonyl)imide can be used to produce aminosulfonyl fluoride at a concentration exceeding 7 mol% of the combination of aminosulfonyl fluoride and bis(fluorosulfonyl)imide. Conversely, at a molar ratio of fluorosulfonic acid to urea of ​​2.5:1, a concentration of aminosulfonyl fluoride less than 0.5 mol% is produced, and at a molar ratio of fluorosulfonic acid to urea of ​​3.0:1 or greater, the concentration of aminosulfonyl fluoride is less than 0.1 mol% (see Examples below).

[0022] However, the solubility limit of urea in fluorosulfonic acid is approximately 1 mole of urea for every 2.5 moles of fluorosulfonic acid, or a molar ratio of fluorosulfonic acid to urea of ​​approximately 2.5:1. Therefore, a compatible solvent is needed to maintain the urea in the solution at the desired molar ratio of fluorosulfonic acid to urea of ​​2.0:1 or lower. Compatible solvents may include, for example, bis(fluorosulfonyl)imide, sulfolane, and dimethylformamide.

[0023] For example, in a solution of urea, flusulfonic acid, and a solvent, the molar ratio of flusulfonic acid to urea can be as low as about 1.80:1, about 1.82:1, about 1.84:1, about 1.86:1, about 1.88:1, or about 1.90:1, or as high as about 1.92:1, about 1.94:1, about 1.96:1, about 1.98:1, or about 2.00:1, or any range defined between any two of the foregoing values, such as about 1.80:1. The molar ratios are approximately 1 to 2.00:1, 1.82:1 to 1.98:1, 1.84:1 to 1.96:1, 1.86:1 to 1.94:1, 1.88:1 to 1.92:1, 1.80:1 to 1.98:1, 1.80:1 to 1.96:1, 1.80:1 to 1.94:1, 1.80 to 1.88, or 1.92:1 to 1.98:1. Preferably, the molar ratio of fluorosulfonic acid to urea in the solution is approximately 1.80:1 to 1.98:1. More preferably, the molar ratio of fluorosulfonic acid to urea in the solution is approximately 1.82:1 to 1.96:1. Most preferably, the molar ratio of fluorosulfonic acid to urea in the solution is approximately 1.84:1 to 1.94:1.

[0024] In some embodiments, a solution of urea and fluorosulfonic acid can be formed by mixing urea and a solvent together until the urea dissolves, and then adding the urea / solvent solution to the fluorosulfonic acid. Urea and fluorosulfonic acid are believed to react according to Equation 2:

[0025] Equation 2: 2HSO3F + CO(NH2)2 → H2NSO2F + CO2 + NH4SO3F.

[0026] In the reaction of Equation 2, urea (CO(NH2)2) and fluorosulfonic acid (HSO3F) react to form aminosulfonyl fluoride (H2NSO2F), and byproducts carbon dioxide (CO2) and ammonium fluorosulfate (NH4SO3F).

[0027] For example, the reaction temperature of Equation 2 can be as low as about 80°C, about 90°C, about 100°C, about 110°C, or about 120°C, or as high as about 130°C, about 140°C, about 150°C, about 160°C, or about 170°C, or any range defined between any two of the foregoing values, such as about 80°C to about 170°C, about 90°C to about 160°C, about 100°C to about 150°C, about 110°C to about 140°C, about 120°C to about 130°C, about 130°C to about 150°C, or about 110°C to about 120°C. Preferably, the reaction temperature is about 110°C to about 140°C. More preferably, the reaction temperature is about 120°C to about 140°C. Most preferably, the reaction temperature is about 120°C to about 130°C.

[0028] The amount of urea available is greater than or equal to the stoichiometric amount calculated according to Equation 2 to limit the availability of fluorosulfonic acid for the side reactions described below. In some embodiments, unreacted urea precipitates out together with ammonium fluorosulfate. In some embodiments, if the conditions are acidic and the temperature is above about 130°C, the unreacted urea decomposes to produce ammonia and carbon dioxide. Ammonia can react with fluorosulfonic acid to produce ammonium fluorosulfate.

[0029] Two side reactions may also occur that consume the required ammoniasulfonyl fluoride. In one of the reactions that consumes the ammoniasulfonyl fluoride, according to Equation 3, the ammoniasulfonyl fluoride reacts with available fluorosulfonic acid to form bis(fluorosulfonyl)imide and byproducts carbon dioxide, ammonium fluorosulfate, and water:

[0030] The equation is: 3HSO3F + H2NSO2F → HN(SO2F)2 + H2O.

[0031] Evidence for the reaction schemes of Equations 2 and 3 was found by monitoring the levels of sulfamyl fluoride with alternating additions of urea and fluorosulfonic acid. It was found that adding urea increased the concentration of sulfamyl fluoride, and adding fluorosulfonic acid decreased its concentration. Without being bound by any theory, it is believed that by limiting the available fluorosulfonic acid (by limiting the ratio of fluorosulfonic acid to urea), more fluorosulfonic acid is consumed in the reaction of Equation 2, leaving less fluorosulfonic acid to be consumed in the reaction of Equation 3, thus reducing the amount of sulfamyl fluoride consumed in the formation of bis(fluorosulfonyl)imide. In this way, the concentration of sulfamyl fluoride in the resulting composition can be increased to a level suitable for further commercial use, such as the production of additional bis(fluorosulfonyl)imide, or suitable for separation from bis(fluorosulfonyl)imide to produce sulfamyl fluoride compositions.

[0032] In another reaction that consumes ammonia sulfonyl fluoride, according to Equation 4, ammonia sulfonyl fluoride reacts with the water produced in Equation 3 to form additional ammonium fluorosulfate:

[0033] The equation is: 4H₂O + H₂NSO₂F → NH₄SO₃F.

[0034] As described above, limiting the water available for the reaction in Equation 4 can be achieved by limiting the reaction in Equation 3. Alternatively, the water available for the reaction in Equation 4 can be limited by removing water from the mixture. For example, in some embodiments, a stream of dry inert gas (such as nitrogen or carbon dioxide) can be bubbled through the mixture to remove water from it.

[0035] The mixture produced by the reaction in Equation 2 includes aminosulfonyl fluoride, ammonium fluorosulfate, and a solvent. This mixture may also include bis(fluorosulfonyl)imide, because the reaction in Equation 3 is not completely inhibited and some of the aminosulfonyl fluoride produced by the reaction in Equation 2 can react with some of the fluorosulfonic acid that has not yet been consumed by the reaction in Equation 2. If the solvent is insufficient to dissolve the produced ammonium fluorosulfate, the mixture may be in the form of a slurry. Alternatively, the mixture may be in the form of a solution.

[0036] In some embodiments, the solvent-to-urea and fluorosulfonic acid weight ratio is high enough to completely dissolve the reaction byproducts in the mixture, including ammonium fluorosulfate, to prevent the need for slurry treatment. However, increasing the amount of solvent reduces process efficiency, requiring a larger system and increased energy to separate the sulfamethoxymethyl ether composition from the solvent. Therefore, in some embodiments, it is desirable to use a lower solvent-to-urea and fluorosulfonic acid weight ratio to form a slurry containing undissolved ammonium fluorosulfate.

[0037] The carbon dioxide gas produced can be vented or captured for other uses. The water produced can be separated and neutralized because it contains residual acid.

[0038] Ammonium fluorosulfate can be separated from a mixture. For example, it can be separated by evaporation, spray drying, filtration, or any combination thereof.

[0039] After separating ammonium fluorosulfate from the mixture, the mixture is separated into an aminosulfonyl fluoride composition and a recycled composition. The aminosulfonyl fluoride composition contains a higher concentration of aminosulfonyl fluoride than the recycled composition. In some embodiments, the recycled composition is recycled back to the reaction. Alternatively or otherwise, in some embodiments, the recycled composition may be directed to a storage tank for later use. For example, separation can be achieved by distillation.

[0040] For example, it has been found that the concentration of aminosulfonyl fluoride in the aminosulfonyl fluoride composition can be as low as about 1 mol%, about 2 mol%, about 3 mol%, about 4 mol%, or about 5 mol%, or as high as about 6 mol%, about 7 mol%, about 8 mol%, about 9 mol%, or about 10 mol%, or any range defined between any two of the foregoing values, such as about 1 mol% to about 10 mol%, about 2 mol% to about 9 mol%, about 3 mol% to about 8 mol%, about 4 mol% to about 7 mol%, about 5 mol% to about 6 mol%, about 5 mol% to about 8 mol%, about 2 mol% to about 5 mol%, or about 6 mol% to about 10 mol%. Preferably, the concentration of aminosulfonyl fluoride in the aminosulfonyl fluoride composition is about 2 mol% to about 9 mol%. More preferably, the concentration of aminosulfonyl fluoride in the aminosulfonyl fluoride composition is about 3 mol% to about 8 mol%. Most preferably, the concentration of aminosulfonyl fluoride in the aminosulfonyl fluoride composition is about 4 mol% to about 8 mol. The concentration of aminosulfonyl fluoride in the aminosulfonyl fluoride composition is the mol% of the combination of aminosulfonyl fluoride and bis(fluorosulfonyl)imide.

[0041] In some embodiments, ammonia sulfonyl fluoride can be separated from the ammonia sulfonyl fluoride composition to form a concentrated ammonia sulfonyl fluoride composition. For example, separation can be achieved by distillation. The concentrated ammonia sulfonyl fluoride composition can be used, for example, to produce electrolytes for lithium-ion batteries.

[0042] For example, the concentration of aminosulfonyl fluoride in the concentrated aminosulfonyl fluoride composition may be as low as about 50 wt%, about 60 wt%, about 70 wt%, about 80 wt%, or about 90 wt%, or as high as about 95 wt%, about 97 wt%, about 98 wt%, about 99 wt%, about 99.5 wt%, or about 99.9 wt%, or any range defined between any two of the foregoing values, such as about 50 wt% to about 99.9 wt%, about 60 wt% to about 99.5 wt%, about 70 wt% to about 99 wt%, about 80 wt% to about 98 wt%, about 90 wt% to about 97 wt%, about 50 wt% to about 70 wt%, about 98 wt% to about 99.9 wt%, or about 99.5 wt% to about 99.9 wt%. Preferably, the concentration of aminosulfonyl fluoride in the aminosulfonyl fluoride composition is about 90 wt% to about 99.9 wt%. More preferably, the concentration of aminosulfonyl fluoride in the aminosulfonyl fluoride composition is from 95 wt% to about 99.9 wt%. Most preferably, the concentration of aminosulfonyl fluoride in the aminosulfonyl fluoride composition is from 99.5 wt% to about 99.9 wt%. The concentration of aminosulfonyl fluoride in the concentrated aminosulfonyl fluoride composition is wt%.

[0043] Ammoniasulfonyl fluoride compositions and / or concentrated ammoniasulfonyl fluoride compositions can be used to produce bis(fluorosulfonyl)imide (HFSI) by employing the reaction of Equation 3 as the main reaction. The ammoniasulfonyl fluoride compositions and / or concentrated ammoniasulfonyl fluoride compositions can be mixed with additional fluorosulfonic acid in a reactor to react and form a crude HFSI product composition and a volatile composition. The volatile composition can be removed by operating the reactor under vacuum (vacuum reactor) and / or by passing a carrier gas such as nitrogen or argon through the reactor. The volatile composition contains unreacted fluorosulfonic acid and water. The crude HFSI product composition contains bis(fluorosulfonyl)imide, ammonium fluorosulfate, unreacted fluorosulfonic acid, and unreacted ammoniasulfonyl fluoride.

[0044] For example, the reaction temperature for reacting the aminosulfonyl fluoride in the aminosulfonyl fluoride composition with fluorosulfonic acid can be as low as about 80°C, about 90°C, about 100°C, about 110°C, or about 120°C, or as high as about 130°C, about 140°C, about 150°C, about 160°C, or about 170°C, or any range defined between any two of the foregoing values, such as about 80°C to about 170°C, about 90°C to about 160°C, about 100°C to about 150°C, about 110°C to about 140°C, about 120°C to about 130°C, about 130°C to about 150°C, or about 110°C to about 120°C. Preferably, the reaction temperature is about 110°C to about 140°C. More preferably, the reaction temperature is about 120°C to about 140°C. Most preferably, the reaction temperature is about 120°C to about 130°C.

[0045] The reaction pressure used to react the ammonia sulfonyl fluoride in the ammonia sulfonyl fluoride composition with fluorosulfonic acid is less than 1 bar absolute pressure, in order to extract the volatile composition including water. As shown in Equation 4 above, since water can react with some of the ammonia sulfonyl fluoride to produce ammonium fluorosulfate instead of bis(fluorosulfonyl)imide, dehydration can increase the yield of bis(fluorosulfonyl)imide. Dehydration reduces this consumption of ammonia sulfonyl fluoride, thereby increasing the yield of bis(fluorosulfonyl)imide from ammonia sulfonyl fluoride.

[0046] Therefore, by dividing the production of bis(fluorosulfonyl)imide into two steps—a first step of preparing an aminosulfonyl fluoride composition and / or a concentrated aminosulfonyl fluoride composition and a second step of reacting the aminosulfonyl fluoride in the aminosulfonyl fluoride composition with fluorosulfonic acid and removing water—the amount of ammonium fluorosulfate produced can be reduced overall, thereby improving the overall yield and efficiency of the method.

[0047] The crude HFSI product composition contains bis(fluorosulfonyl)imide, ammonium fluorosulfate, some unreacted fluorosulfonic acid, and some unreacted aminosulfonyl fluoride. When the reaction is substantially complete, only a small amount of aminosulfonyl fluoride remains in the crude HFSI product composition due to the stoichiometric excess of fluorosulfonic acid.

[0048] The concentration of aminosulfonyl fluoride in the crude HFSI product composition may be less than about 0.5 mol%, less than about 0.4 mol%, less than about 0.3 mol%, less than about 0.2 mol%, or less than about 0.1 mol%, or within any range defined between any two of the foregoing values.

[0049] Ammonium fluorosulfate is separated from the crude HFSI product composition to form the HFSI product composition. For example, ammonium fluorosulfate can be separated by evaporation, spray drying, filtration, or any combination thereof.

[0050] After separating ammonium fluorosulfate from the crude HFSI product composition, the resulting HFSI product composition is further separated into a concentrated HFSI product composition and a topstream composition. The concentrated HFSI product composition contains a higher concentration of bis(fluorosulfonyl)imide than the topstream composition. The topstream composition contains water and unreacted fluorosulfonic acid. Separation can be achieved, for example, by distillation.

[0051] In some embodiments, the topstream is separated into an aqueous composition and an FSA-rich composition. The FSA-rich composition contains a higher concentration of fluorosulfonic acid than the aqueous composition. In some embodiments, the FSA-rich composition is recycled back to the reactor. Alternatively or otherwise, in some embodiments, the FSA-rich composition may be directed to a storage tank for later use. For example, separation can be achieved by distillation.

[0052] In some embodiments, the volatile composition is separated into a condensate stream and a non-condensate stream. The condensate stream contains most of the unreacted fluorosulfonic acid from the volatile composition. The condensate stream can be recycled back to the reactor. The non-condensate stream contains water and the remaining unreacted fluorosulfonic acid from the volatile composition. The non-condensate stream can be separated into an aqueous composition and an FSA-rich composition. The FSA-rich composition contains a higher concentration of fluorosulfonic acid than the aqueous composition. In some embodiments, the FSA-rich composition is recycled back to the reactor. Alternatively or additionally, in some embodiments, the FSA-rich composition can be directed to a storage tank for later use. For example, separation can be achieved by distillation.

[0053] In some embodiments, the separation of the non-condensed stream into an aqueous composition and an FSA-rich composition can be carried out in the same separation system as the separation of the topstream into an aqueous composition and an FSA-rich composition. In other embodiments, these separation steps are carried out in their own separation systems.

[0054] In some embodiments, the above method is a continuous process. In other embodiments, the above method is semi-batch. Semi-batch means that although a significant portion of the process is continuous, the entire process is not continuous. For example, in some semi-batch embodiments, an aminosulfonyl fluoride composition can be produced continuously and stored for a period of time, and then at a later time, the stored aminosulfonyl fluoride composition can be used to produce bis(fluorosulfonyl)imide continuously.

[0055] Figure 1 This is a process flow diagram according to some embodiments of the present disclosure, which illustrates an integrated method for the continuous production of aminosulfonyl fluoride compositions. Figure 1 A system 10 is shown, comprising a container 12 configured to be connected to a urea inlet 14 and a solvent inlet 16. The solvent in the solvent inlet 16 is in liquid form and can be continuously pumped into the container 12. Alternatively, the solvent in the solvent inlet 16 can be added in batches. The urea in the urea inlet 14 is in solid form and can be continuously supplied to the container 12 via, for example, a solids delivery system (not shown). Alternatively, the urea in the urea inlet 14 can be added to the container 12 in batches.

[0056] The container 12 is equipped with a mixing device 18, such as a stirrer, and optional heating and cooling mechanisms (not shown), such as heat transfer coils. In the container 12, urea from the urea input stream 14 and solvent from the solvent input stream 16 are mixed by the mixing device 18.

[0057] Reactor 20 is fluidly connected to container 12 to receive a urea solution 22 containing urea and a solvent from container 12. Reactor 20 includes a first fluorosulfonic acid input 24 to supply fluorosulfonic acid to reactor 20. The fluorosulfonic acid and urea solution form a solution containing fluorosulfonic acid, urea, and a solvent within the reactor. The molar ratio of fluorosulfonic acid to urea is as described above. Reactor 20 may also include an inert gas input 25 to provide dry inert gas bubbled through the solution. Reactor 20 is heated to the temperature described above, and the reactants react according to Equation 2 to produce a mixture 26 containing aminosulfonyl fluoride, bis(fluorosulfonyl)imide, ammonium fluorosulfate, and a solvent. Carbon dioxide produced in the reaction can be discharged from reactor 20 through reactor vent 28. Dry inert gas is bubbled through the solution to absorb water produced by the side reaction of Equation 3 above. The inert gas containing the absorbed water can also be discharged from reactor through reactor vent 28. Reactor 20 is configured to maintain the reaction temperature, for example, by means of fluid flowing through a heat exchanger or jacketed reactor (not shown) or by means of an electrically heated coil (not shown).

[0058] A first separator 30 is fluidly connected to reactor 20 to receive a mixture 26 comprising sulfonyl fluoride, bis(fluorosulfonyl)imide, ammonium fluorosulfate, unreacted fluorosulfonic acid, and a solvent. The first separator 30 is configured to separate ammonium fluorosulfate from mixture 26 to produce mixture 32. Ammonium fluorosulfate is removed by purging 34. For example, the first separator 30 may be an evaporator, spray dryer, filter, centrifuge, or any combination thereof.

[0059] The second separator 36 is fluidly connected to the first separator 30 to receive a mixture 32 comprising sulfonyl fluoride, bis(fluorosulfonyl)imide, unreacted fluorosulfonic acid, and a solvent. The second separator 36 is configured to produce a sulfonyl fluoride composition 38 and a recycled composition 40. For example, the second separator 36 may be a distillation column. The concentration of sulfonyl fluoride in the sulfonyl fluoride composition 38 is greater than the concentration of sulfonyl fluoride in the recycled composition 40. The concentration of sulfonyl fluoride in the sulfonyl fluoride composition 38 is as described above.

[0060] Reactor 20 is fluidly connected to a second separator 36 to receive the recirculated composition 40. Alternatively or otherwise, the second separator 36 is fluidly connected to a recirculation tank (not shown). The recirculated composition 40 can be directed to reactor 20 for continuous operation or to the recirculation tank for semi-batch operation.

[0061] In some embodiments, the ammonia sulfonyl fluoride composition 38 may be directed to a product storage tank (not shown) for subsequent processing. In other embodiments, the ammonia sulfonyl fluoride composition 38 may be directed to a distillation column (not shown) to produce a concentrated ammonia sulfonyl fluoride composition, as described above. The concentrated ammonia sulfonyl fluoride composition can be used as a precursor for a salt used in lithium-ion battery electrolytes.

[0062] In some implementation schemes, such as Figure 2 As shown, bis(fluorosulfonyl)imide can be produced using aminosulfonyl fluoride composition 38 (or concentrated aminosulfonyl fluoride composition). Figure 2 This is a process flow diagram according to some embodiments of the present disclosure, which illustrates an integrated method for the continuous production of bis(fluorosulfonyl)imide from an aminosulfonyl fluoride composition and / or a concentrated aminosulfonyl fluoride composition. Figure 2 A system 42 is shown comprising a reactor 44 configured to be connected to a supply source of ammonia sulfonyl fluoride composition 38 and an additional supply source of fluorosulfonic acid 46. The ammonia sulfonyl fluoride composition 38 and the additional fluorosulfonic acid 46 form a mixture within the reactor 44. The reactor 44 is heated to the reaction temperature as described above. The reactants react according to Equation 3 to produce crude HFSI product composition 48 and volatile composition 50.

[0063] Reactor 44 is configured to maintain the reaction temperature, for example, by means of fluid flowing through a heat exchanger or reactor jacket (not shown) or by means of an electrically heated coil (not shown). In some embodiments, the reactor is a vacuum reactor that uses a vacuum to remove the volatile composition 50 from reactor 44. In some embodiments, a carrier gas, such as nitrogen or argon, is supplied to the reactor to remove the volatile composition 50 from reactor 44.

[0064] Crude HFSI product composition 48 comprises bis(fluorosulfonyl)imide, ammonium fluorosulfate, unreacted fluorosulfonic acid, and unreacted aminosulfonyl fluoride. The concentration of unreacted aminosulfonyl fluoride in crude HFSI product composition 48 is as described above. Volatile composition 50 comprises water and unreacted fluorosulfonic acid.

[0065] Condenser 52 is fluidly connected to reactor 44 to separate volatile composition 50 into uncondensed stream 54 and condensed stream 56. Condensed stream 56 contains the majority of the unreacted fluorosulfonic acid from volatile composition 50. Condensed stream 56 is fluidly connected to reactor 44 to return the unreacted fluorosulfonic acid to reactor 44. Uncondensed stream 54 contains water and the remaining unreacted fluorosulfonic acid.

[0066] A third separator 58 is fluidly connected to reactor 44 to receive crude HFSI product composition 48. The third separator 58 is configured to separate ammonium fluorosulfate from the crude HFSI product composition 48 to produce HFSI product composition 60. Ammonium fluorosulfate is removed by purging 62. For example, the third separator 58 may be an evaporator, spray dryer, filter, centrifuge, or any combination thereof.

[0067] A fourth separator 64 is fluidly connected to a third separator 56 to receive an HFSI product composition 60 comprising bis(fluorosulfonyl)imide, unreacted fluorosulfonic acid, and unreacted aminosulfonyl fluoride. The fourth separator 64 is also fluidly connected to a condenser 52 to receive a non-condensed stream 54 comprising water and some unreacted fluorosulfonic acid. The fourth separator 64 is configured to separate the HFSI product composition 60 into a concentrated HFSI product composition 66 and a top stream 68. For example, the fourth separator 64 may be a distillation column. The concentrated product composition 66 contains bis(fluorosulfonyl)imide at the concentration described above. The concentrated product composition 66 may be directed to a product storage tank (not shown) for further processing, purification, or use as an electrolyte in lithium-ion batteries. The top stream 68 contains water and unreacted fluorosulfonic acid.

[0068] A fifth separator 70 is fluidly connected to a fourth separator 64 to receive a top stream 68 containing water and unreacted fluorosulfonic acid from an HFSI product composition 60 and an uncondensed stream 54. The fifth separator 70 is configured to separate the top stream 68 into an aqueous composition 72 and an FSA-rich composition 74. For example, the fifth separator 70 may be a distillation column. The aqueous composition 72 may contain water produced as shown in Equation 3 and acids produced in other side reactions. The aqueous composition 72 may be sent to an alkaline scrubber (not shown) for treatment. The FSA-rich composition 74 may contain unreacted fluorosulfonic acid.

[0069] Alternatively or otherwise, in some embodiments, condenser 52 is directly fluidly connected to fifth separator 70 to receive uncondensed stream 54 containing water and some unreacted fluorosulfonic acid. Fifth separator 70 is configured to separate uncondensed stream 54 together with top stream 68 into aqueous composition 72 and FSA-rich composition 74.

[0070] Reactor 44 is fluidly connected to a fifth separator 70 to receive an FSA-rich composition 74. Alternatively or otherwise, the fifth separator 64 is fluidly connected to a recirculation tank (not shown). The FSA-rich composition 74 can be directed to reactor 44 for continuous operation or to the recirculation tank for semi-batch operation.

[0071] As used herein, the phrase “any range between any two of the preceding values” literally means any range that can be selected from any two values ​​listed before such a phrase, regardless of whether those values ​​are in the lower or higher part of the list. For example, a pair of values ​​can be selected from two lower values, two higher values, or a lower value and a higher value. As used herein, the singular forms “a,” “a,” and “the” include the plural unless the context explicitly indicates otherwise.

[0072] Regarding imprecise terminology, the terms "about" and "approximately" are used interchangeably to refer to a measurement that includes the stated measurement and any measurement reasonably close to it. A measurement reasonably close to the stated measurement deviates from it by a considerably small amount, as understood and readily determined by one of ordinary skill in the art. Such deviations may be attributable to measurement error or to minor adjustments made to optimize performance. Where the value of such a considerably small difference would not be readily determined by one of ordinary skill in the art, the terms "about" and "approximately" may be understood to mean ±10% of the stated value.

[0073] It should be understood that the above description is merely illustrative of this disclosure. Various alternatives and modifications can be devised by those skilled in the art without departing from this disclosure. Therefore, this disclosure is intended to cover all such alternatives, modifications, and variations that fall within the scope of the appended claims.

[0074] Example

[0075] The effect of the ratio of fluorosulfonic acid to urea on the production of ammoniasulfonyl fluoride

[0076] In this embodiment, the effect of the fluorosulfonic acid to urea ratio on the yield of ammonia sulfonyl fluoride in the ammonia sulfonyl fluoride composition was demonstrated. Eight experiments were conducted, each with a different fluorosulfonic acid to urea ratio. For each experiment, a mixture of fluorosulfonic acid and urea was added to a reactor containing residual fluorosulfonic acid, preheated to 80°C to 140°C. The addition typically took about 1 to 2 hours. Once the addition was complete, the reaction mixture was maintained at 80°C to 140°C for another 2 to 3 hours to ensure the reaction was complete. The contents of the reactor were then heated to about 160°C and distilled under reduced pressure of 0 to 10 Torr to separate the generated HFSI and unreacted fluorosulfonic acid from the generated ammonium fluorosulfate. The recovered distillate was analyzed by 19F NMR to determine the molar percentages of HFSI, fluorosulfonic acid, and ammonia sulfonyl fluoride. The results are shown in Figure 3 middle.

[0077] Figure 3 This is a graph showing the variation of the concentration of sulfamethoxyfluoride in each experiment with the molar ratio of fluorosulfonic acid to urea (FSA:urea). Figure 3 As shown, at FSA:urea ratios of 3:1 or greater, the concentration of sulfamyl fluoride is less than 0.1 mol%. Even at FSA:urea ratios as low as 2.5:1, the concentration of sulfamyl fluoride remains below 0.5 mol%. The concentration only significantly increases to approximately 3.5 mol% when the FSA:urea ratio reaches 2.0:1. Below 2.0:1, the concentration of sulfamyl fluoride increases significantly, resulting in a concentration of 7.2 mol% at an FSA:urea ratio of 1.9:1. This surprising result demonstrates that this method can produce a considerable yield of sulfamyl fluoride at FSA:urea ratios equal to or below 2.0:1.

[0078] aspect

[0079] Aspect 1 is a method for producing an aminosulfonyl fluoride composition, the method comprising providing a solution comprising fluorosulfonic acid, urea, and a solvent, wherein the molar ratio of fluorosulfonic acid to urea is from about 1.80:1 to about 2.00:1; reacting the solution at a reaction temperature of about 80°C to about 170°C to produce a mixture comprising aminosulfonyl fluoride, bis(fluorosulfonyl)imide, ammonium fluorosulfate, and the solvent; separating the ammonium fluorosulfate from the mixture; and separating the mixture into the aminosulfonyl fluoride composition and a recycled composition, the aminosulfonyl fluoride composition comprising a higher concentration of aminosulfonyl fluoride and bis(fluorosulfonyl)imide than the recycled composition.

[0080] Aspect 2 is the method according to aspect 1, further comprising recycling the recycled composition back to the reaction step.

[0081] Aspect 3 is the method according to aspect 1 or aspect 2, wherein the method is a continuous method.

[0082] Aspect 4 is the method according to aspect 1 or aspect 2, wherein the method is a semi-intermittent method.

[0083] Aspect 5 is the method according to any one of aspects 1 to 4, wherein the solvent comprises at least one selected from the group consisting of bis(fluorosulfonyl)imide, sulfolane, and dimethylformamide.

[0084] Aspect 6 is the method according to aspects 1 to 5, wherein the concentration of the aminosulfonyl fluoride in the aminosulfonyl fluoride composition is about 1 mol% to about 10 mol% of the combination of the aminosulfonyl fluoride and bis(fluorosulfonyl)imide.

[0085] Aspect 7 is the method according to any one of aspects 1 to 6, wherein in the providing step, the molar ratio of the fluorosulfonic acid to the urea is from about 1.80:1 to about 1.90:1; and in the step of separating the mixture into the aminosulfonyl fluoride composition and the recycling composition, the concentration of the aminosulfonyl fluoride in the aminosulfonyl fluoride composition is from about 4 mol% to about 8 mol% of the combination of the aminosulfonyl fluoride and the bis(fluorosulfonyl)imide.

[0086] Aspect 8 is the method according to any one of aspects 1 to 7, wherein separating the ammonium fluorosulfate from the mixture comprises evaporating the mixture to form the aminosulfonyl fluoride composition.

[0087] Aspect 9 is the method according to any one of aspects 1 to 10, wherein separating the mixture into an aminosulfonyl fluoride composition and a recycling composition comprises distilling the mixture.

[0088] Aspect 10 is the method according to any one of aspects 1 to 9, further comprising separating the aminosulfonyl fluoride from the aminosulfonyl fluoride composition to form a concentrated aminosulfonyl fluoride composition, wherein the concentration of aminosulfonyl fluoride in the concentrated aminosulfonyl fluoride composition is about 50% by weight to about 99.9% by weight of the concentrated aminosulfonyl fluoride composition.

[0089] Aspect 11 is the method according to any one of Aspects 1 to 11, further comprising mixing the aminosulfonyl fluoride composition with an additional fluorosulfonic acid; reacting the mixture of the aminosulfonyl fluoride composition and the additional fluorosulfonic acid in a reactor at a reaction temperature of about 80°C to about 170°C to produce a crude HFSI product composition and a volatile composition, the volatile composition comprising fluorosulfonic acid and water, and the crude HFSI product composition comprising bis(fluorosulfonyl)imide, ammonium fluorosulfate, unreacted fluorosulfonic acid and unreacted aminosulfonyl fluoride, wherein the concentration of unreacted aminosulfonyl fluoride in the crude HFSI product composition is less than 0.5 mol% of the combination of aminosulfonyl fluoride and bis(fluorosulfonyl)imide; separating the ammonium fluorosulfate from the crude HFSI product composition to produce the HFSI product composition; and separating the HFSI product composition into a concentrated HFSI product composition and a topstream composition, the concentrated HFSI product composition comprising a higher concentration of bis(fluorosulfonyl)imide than the topstream composition.

[0090] Aspect 12 is the method according to aspect 11, further comprising separating the topstream composition into an aqueous composition and an FSA-rich composition, the FSA-rich composition containing a higher concentration of fluorosulfonic acid than the aqueous composition.

[0091] Aspect 13 is the method according to aspect 12, further comprising recycling the FSA-rich composition back to the step of mixing the aminosulfonyl fluoride composition with the additional fluorosulfonic acid or back to the step of providing the solution comprising fluorosulfonic acid, urea and the solvent.

[0092] Aspect 14 is the method according to any one of aspects 11 to 13, wherein the method is a continuous method.

[0093] Aspect 15 is the method according to any one of aspects 11 to 13, wherein the method is a semi-intermittent method.

[0094] Aspect 16 is the method according to any one of aspects 11 to 15, further comprising separating the volatile composition into an aqueous composition and an FSA-rich composition, the FSA-rich composition comprising a higher concentration of fluorosulfonic acid than the aqueous composition.

[0095] Aspect 17 is the method according to aspect 16, further comprising recycling the FSA-rich composition back to the step of mixing the aminosulfonyl fluoride composition with the additional fluorosulfonic acid or back to the step of providing the solution comprising fluorosulfonic acid, urea and the solvent.

[0096] Aspect 18 is the method according to aspect 17, wherein the method is a continuous method.

[0097] Aspect 19 is the method according to aspect 17, wherein the method is a semi-intermittent method.

[0098] Aspect 20 is a composition comprising aminosulfonyl fluoride and bis(fluorosulfonyl)imide, wherein the concentration of said aminosulfonyl fluoride is about 1 mol% to about 10 mol% of the combination of said aminosulfonyl fluoride and said bis(fluorosulfonyl)imide.

[0099] Aspect 21 is the composition according to aspect 20, wherein the concentration of the aminosulfonyl fluoride is about 2 mol% to about 9 mol% of the combination of the aminosulfonyl fluoride and the bis(fluorosulfonyl)imide.

[0100] Aspect 22 is the composition according to aspect 20, wherein the concentration of the aminosulfonyl fluoride is about 3 mol% to about 8 mol% of the combination of the aminosulfonyl fluoride and the bis(fluorosulfonyl)imide.

[0101] Aspect 23 is the composition according to aspect 20, wherein the concentration of the aminosulfonyl fluoride is about 4 mol% to about 8 mol% of the combination of the aminosulfonyl fluoride and the bis(fluorosulfonyl)imide.

[0102] Aspect 24 is a composition comprising aminosulfonyl fluoride and bis(fluorosulfonyl)imide, wherein the concentration of said aminosulfonyl fluoride is from about 50% by weight to about 99.9% by weight of said composition.

[0103] Aspect 25 is the composition according to aspect 24, wherein the concentration of the aminosulfonyl fluoride is about 90% by weight to about 99.9% by weight of the composition.

[0104] Aspect 26 is the composition according to aspect 24, wherein the concentration of the aminosulfonyl fluoride is about 95% by weight to about 99.9% by weight of the composition.

[0105] Aspect 27 is the composition according to aspect 25, wherein the concentration of the aminosulfonyl fluoride is about 99.5% to about 99.9% by weight of the composition.

Claims

1. A method for producing an aminosulfonyl fluoride composition, the method comprising: A solution comprising fluorosulfonic acid, urea, and a solvent is provided, wherein the molar ratio of fluorosulfonic acid to urea is from 1.80:1 to 2.00:1; The solution is reacted at a reaction temperature of 80°C to 170°C to produce a mixture comprising aminosulfonyl fluoride, bis(fluorosulfonyl)imide, ammonium fluorosulfate and the solvent; Separate the ammonium fluorosulfate from the mixture; and The mixture is separated into the aminosulfonyl fluoride composition and the recycling composition, the aminosulfonyl fluoride composition containing a higher concentration of aminosulfonyl fluoride and bis(fluorosulfonyl)imide than the recycling composition.

2. The method of claim 1, further comprising recycling the recycled composition back to the reaction step.

3. The method according to claim 2, wherein the method is a continuous method.

4. The method according to claim 1, wherein the method is a semi-intermittent method.

5. The method of claim 1, wherein the solvent comprises at least one selected from the group consisting of bis(fluorosulfonyl)imide, sulfolane, and dimethylformamide.

6. The method according to claim 1, wherein the concentration of the aminosulfonyl fluoride in the aminosulfonyl fluoride composition is from 1 mol% to 10 mol% of the combination of the aminosulfonyl fluoride and bis(fluorosulfonyl)imide.

7. The method according to claim 1, wherein in the providing step, the molar ratio of the fluorosulfonic acid to the urea is 1.80:1 to 1.90:1; and in the step of separating the mixture into the aminosulfonyl fluoride composition and the recycling composition, the concentration of the aminosulfonyl fluoride in the aminosulfonyl fluoride composition is 4 mol% to 8 mol% of the combination of the aminosulfonyl fluoride and bis(fluorosulfonyl)imide.

8. The method of claim 1, wherein separating the ammonium fluorosulfate from the mixture comprises evaporating the mixture to form the aminosulfonyl fluoride composition.

9. The method of claim 1, wherein separating the mixture into an aminosulfonyl fluoride composition and a recycling composition comprises distilling the mixture.

10. The method according to claim 1, further comprising: The aminosulfonyl fluoride is separated from the aminosulfonyl fluoride composition to form a concentrated aminosulfonyl fluoride composition, wherein the concentration of aminosulfonyl fluoride in the concentrated aminosulfonyl fluoride composition is from 50% by weight to 99.9% by weight of the concentrated aminosulfonyl fluoride composition.

11. The method according to claim 1, further comprising: The aminosulfonyl fluoride composition is mixed with an additional fluorosulfonic acid; The ammonia sulfonyl fluoride composition is reacted with the mixture of the additional fluorosulfonic acid in a reactor at a reaction temperature of 80°C to 170°C to produce a crude HFSI product composition and a volatile composition comprising fluorosulfonic acid and water. The crude HFSI product composition comprises bis(fluorosulfonyl)imide, ammonium fluorosulfate, unreacted fluorosulfonic acid, and unreacted ammonia sulfonyl fluoride, wherein the concentration of unreacted ammonia sulfonyl fluoride in the crude HFSI product composition is less than 0.5 mol% of the combination of ammonia sulfonyl fluoride and the bis(fluorosulfonyl)imide. The ammonium fluorosulfate is separated from the crude HFSI product composition to produce the HFSI product composition; as well as The HFSI product composition is separated into a concentrated HFSI product composition and a topstream composition, wherein the concentrated HFSI product composition contains a higher concentration of bis(fluorosulfonyl)imide than the topstream composition.

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