Integrated process for the treatment of ammonium fluorosulfate byproducts in the production of bis(fluorosulfonyl)imides

Abstract

This invention provides an integrated process for processing ammonium fluorosulfate, a by-product generated in the production of bis(fluorosulfonyl)imides. [Solution] A process for processing ammonium fluorosulfate byproducts includes providing an ammonium fluorosulfate byproduct mainly comprising ammonium fluorosulfate and smaller amounts of fluorosulfonic acid and bis(fluorosulfonyl)imide; mixing the ammonium fluorosulfate byproduct with water; reacting the mixture of ammonium fluorosulfate byproducts and water at a hydrolysis reaction temperature to hydrolyze ammonium fluorosulfate, fluorosulfonic acid and bis(fluorosulfonyl)imide to form ammonium bicarbonate and an aqueous hydrogen fluoride solution; and separating ammonium bicarbonate from the aqueous hydrogen fluoride solution.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims priority to U.S. Patent Application No. 17 / 554,977, filed on December 17, 2021 and claims the benefit of U.S. Provisional Patent Application No. 63 / 134,883, filed on January 7, 2021, which is hereby incorporated by reference in its entirety into this specification.

[0002] (Field of the Invention) This disclosure relates to a process for treating ammonium fluorosulfate by - products. In particular the disclosure relates to an integrated process for treating ammonium fluorosulfate by - products of the formation of bis(fluorosulfonyl)imide.

Background Art

[0003] Bis(fluorosulfonyl)imide (HFSI) is an important raw material in the production of lithium bis(fluorosulfonyl)imide (LiFSI) used in lithium - ion batteries . HFSI (HN(SO2F)2) can be prepared by several methods . For example, HFSI can be prepared by the reaction of urea (CO(NH2)2) and fluorosulfonic acid (HSO3F) as shown in Equation 1: Equation 1 5HSO3F + 2CO(NH2)2→HN(SO2F)2 + 2CO2+3NH4 SO_{3}F.

[0004] U.S. Patent No. 8,337,797 to Honda et al. discloses a two - step batch process for producing HFSI from urea and fluorosulfonic acid. In the first step At a temperature low enough to prevent the reaction between urea and fluorosulfonic acid shown in Equation 1, the urea is... Dissolve in fluorosulfonic acid. In the second step, the urea / fluorosulfonic acid solution Slowly add to separate reaction vessels containing a reaction medium that has been heated sufficiently for the reaction of Equation 1 to proceed. The batch process disclosed in U.S. Patent No. 8,337,797 is an efficient commercial process. It's not enough to generate HFSIs on an industry scale.

[0005] As expected, Honda et al.'s international publication No. 2011 / 111780 is an overflow outlet. The reaction solution is continuously removed from the reaction vessel via a fertilizer, resulting in a slurry state (ammonium fluorosulfate). Further disclosures a recovery process for continuously discharging the reaction mixture (including nium by-products). The disclosed process is carried out in a batch, and the product HFSI is converted in the next batch. It is added back into the reaction vessel before the reaction.

[0006] Therefore, a more efficient process that can be scaled up to produce commercial quantities of HFSI is needed. We need to develop a process. [Overview of the Initiative]

[0007] This disclosure relates to a by-product generated in the production of bis(fluorosulfonyl)imides. This provides an integrated process for processing ammonium fluorosulfate.

[0008] In one embodiment, the present invention provides a method for processing ammonium fluorosulfate byproducts. The process provides a solution. The process mainly involves ammonium fluorosulfate and a smaller amount of fluorine Ammonium fluorosulfate containing rosulfonic acid and bis(fluorosulfonyl)imide To provide a by-product, and to mix the ammonium fluorosulfate by-product with water, The mixture of ammonium fluorosulfate byproduct and water is reacted at the hydrolysis reaction temperature, Ammonium fluorosulfate, fluorosulfonic acid, and bis(fluorosulfonyl)imide Hydrolysis forms ammonium bicarbonate and hydrogen fluoride aqueous solution, and hydrogen fluoride This includes separating ammonium bicarbonate from an aqueous solution.

[0009] In another embodiment, the present invention provides a method for processing ammonium fluorosulfate by-products. The process provides a solution. The process mainly involves ammonium fluorosulfate and a smaller amount of ful Ammonium fluorosulfate containing orosulfonic acid and bis(fluorosulfonyl)imide To provide a by-product and to mix the ammonium fluorosulfate by-product with water and a base. This involves a hydrolysis reaction between the ammonium fluorosulfate byproduct, water, and a base. By reacting with temperature, ammonium fluorosulfate, fluorosulfonic acid, and bis(fluoro) Hydrolysis and neutralization of sulfonyl imides yield fluorides, sulfates, and ammonium bicarbonate. Forming a mixture containing mu, and including.

[0010] Considering the attached drawings and referring to the following description of the embodiment, this invention The above-mentioned and other characteristics, as well as the methods for achieving them, will become clearer and better understood. It will be understood. [Brief explanation of the drawing]

[0011] [Figure 1]A process flow diagram showing an integrated process for the continuous treatment of ammonium fluorosulfate by-products formed in the production of bis(fluorosulfonyl)imide according to some embodiments of the present disclosure. [Figure 2] A process flow diagram showing another integrated process for the continuous treatment of ammonium fluorosulfate by-products formed in the production of bis(fluorosulfonyl)imide according to some embodiments of the present disclosure.

Mode for Carrying Out the Invention

[0012] The present disclosure relates to an integrated process that can be scaled to treat ammonium fluorosulfate by-products formed in the production of commercial quantities of bis(fluorosulfonyl)imide (HFSI). HFSI can be produced by the reaction of urea with fluorosulfonic acid (FSA) as described above in Formula 1. The ammonium fluorosulfate by-products formed in such production of HFSI mainly contain ammonium fluorosulfate (NH4SO3F), and smaller amounts of HFSI and FSA. After concentrating the HFSI, the resulting ammonium fluorosulfate by-product is typically solid, but may also be in the form of a slurry of ammonium fluorosulfate with residual HFSI and FSA. The ammonium fluorosulfate by-product is a potentially dangerous substance that reacts with water to produce hydrofluoric acid. The disposal of the harmful ammonium fluorosulfate by-product is dangerous and costly, and may limit the overall efficiency of HFSI production. An integrated process is provided that efficiently treats the ammonium fluorosulfate by-product to improve the overall efficiency of HFSI production. As disclosed herein, the ammonium fluorosulfate by-product formed in the production of HFSI mainly contains ammonium fluorosulfate (NH4SO3F), and smaller amounts of HFSI and FSA. After concentrating the HFSI, the resulting ammonium fluorosulfate by-product is typically solid, but may also be in the form of a slurry of ammonium fluorosulfate with residual HFSI and FSA. The ammonium fluorosulfate by-product is a potentially dangerous substance that reacts with water to produce hydrofluoric acid. The disposal of the harmful ammonium fluorosulfate by-product is dangerous and costly, and may limit the overall efficiency of HFSI production. The present invention provides an integrated process for efficiently treating ammonium fluorosulfate by-products to improve the overall efficiency of HFSI production. As disclosed herein, the ammonium fluorosulfate by-product formed in the production of HFSI mainly contains ammonium fluorosulfate (NH4SO3F), and smaller amounts of HFSI and FSA. After concentrating the HFSI, the resulting ammonium fluorosulfate by-product is typically solid, but may also be in the form of a slurry of ammonium fluorosulfate with residual HFSI and FSA. The ammonium fluorosulfate by-product is a potentially dangerous substance that reacts with water to produce hydrofluoric acid. The disposal of the harmful ammonium fluorosulfate by-product is dangerous and costly, and may limit the overall efficiency of HFSI production. ammonium fluorosulfate by-product formed in the production of HFSI mainly contains ammonium fluorosulfate (NH4SO3F), and smaller amounts of HFSI and FSA. After concentrating the HFSI, the resulting ammonium fluorosulfate by-product is typically solid, but may also be in the form of a slurry of ammonium fluorosulfate with residual HFSI and FSA. The ammonium fluorosulfate by-product is a potentially dangerous substance that reacts with water to produce hydrofluoric acid. The disposal of the harmful ammonium fluorosulfate by-product is dangerous and costly, and may limit the overall efficiency of HFSI production. After concentrating the HFSI, the resulting ammonium fluorosulfate by-product is typically solid, but may also be in the form of a slurry of ammonium fluorosulfate with residual HFSI and FSA. The ammonium fluorosulfate by-product is a potentially dangerous substance that reacts with water to produce hydrofluoric acid. The disposal of the harmful ammonium fluorosulfate by-product is dangerous and costly, and may limit the overall efficiency of HFSI production. After concentrating the HFSI, the resulting ammonium fluorosulfate by-product is typically solid, but may also be in the form of a slurry of ammonium fluorosulfate with residual HFSI and FSA. The ammonium fluorosulfate by-product is a potentially dangerous substance that reacts with water to produce hydrofluoric acid. The disposal of the harmful ammonium fluorosulfate by-product is dangerous and costly, and may limit the overall efficiency of HFSI production. The ammonium fluorosulfate by-product is a potentially dangerous substance that reacts with water to produce hydrofluoric acid. The disposal of the harmful ammonium fluorosulfate by-product is dangerous and costly, and may limit the overall efficiency of HFSI production. The ammonium fluorosulfate by-product is a potentially dangerous substance that reacts with water to produce hydrofluoric acid. The disposal of the harmful ammonium fluorosulfate by-product is dangerous and costly, and may limit the overall efficiency of HFSI production. The present invention provides an integrated process for efficiently treating ammonium fluorosulfate by-products to improve the overall efficiency of HFSI production. As disclosed herein, the

[0013] The present invention provides an integrated process for efficiently treating ammonium fluorosulfate by-products to improve the overall efficiency of HFSI production. As disclosed herein, the ammonium fluorosulfate by-product formed in the production of HFSI mainly contains ammonium fluorosulfate (NH4SO3F), and smaller amounts of HFSI and FSA. After concentrating the HFSI, the resulting ammonium fluorosulfate by-product is typically solid, but may also be in the form of a slurry of ammonium fluorosulfate with residual HFSI and FSA. The ammonium fluorosulfate by-product is a potentially dangerous substance that reacts with water to produce hydrofluoric acid. The disposal of the harmful ammonium fluorosulfate by-product is dangerous and costly, and may limit the overall efficiency of HFSI production. Processing ammonium ruorosulfate by-products is an environmentally friendly waste and / or commercial waste treatment. It can produce by-products that are particularly useful.

[0014] As disclosed herein, HFSI is produced from a solution of urea and fluorosulfonic acid. It is done. A solution of urea and fluorosulfonic acid is made by combining urea and fluorosulfonic acid. Formed by mixing. A solution of urea and fluorosulfonic acid is reacted at the reaction temperature. When added to a medium, fluorosulfonic acid and urea react to form HFS as shown in Formula 1. This produces a crude product containing I and ammonium fluorosulfate. The carbon dioxide produced is then... The gas may be aerated or captured for other uses. The reaction medium contains fluorosulfonic acid. It can include HFSI further.

[0015] The reaction temperature is approximately 80°C, 90°C, 100°C, 110°C, or 120°C. Low, or high, such as around 130°C, 140°C, 150°C, 160°C, or 170°C. i, or any range defined between any two of the aforementioned values, for example, approximately 80°C ~170℃, 90℃~160℃, 100℃~150℃, 110℃~140℃ °C, approximately 120°C to 130°C, approximately 130°C to 150°C, or approximately 110°C to 120°C It can be any of the above. Preferably, the reaction temperature is about 110°C to about 140°C. More preferably The reaction temperature is approximately 120°C to 140°C. Most preferably, the reaction temperature is approximately 12 The temperature range is from 0°C to approximately 130°C.

[0016] The crude product is separated into an intermediate product and an ammonium fluorosulfate byproduct. The material is dried by, for example, vacuum drying, evaporation, spray drying, filtration, or any combination thereof. The mixture can then be separated into an intermediate product and an ammonium fluorosulfate by-product.

[0017] The intermediate product is separated into a concentrated product and an FSA recycled product. The concentrated product is It contains HFSI at a higher concentration than the FSA recycling product. In some embodiments, F The SA recycling product is recycled back into the reaction medium. In some embodiments, FSA recycled products are stored in storage tanks, either as an alternative or additional means, for later use. It can be directed. Separation may occur, for example, by distillation.

[0018] The by-products of ammonium fluorosulfate are mainly ammonium fluorosulfate and less Includes amounts of HFSI and FSA. Where used herein, the term “primarily” means This means 50% by weight (wt%) or more of the by-product. Ammonium fluorosulfate by-product The product is typically a solid, but contains ammonium fluorosulfate and residual HFSI and FS. It may also be in the form of a slurry with A.

[0019] The concentration of ammonium fluorosulfate in the ammonium fluorosulfate byproduct is 50 by weight. %, 60% by weight, 70% by weight, 80% by weight, 85% by weight, 87% by weight, 90% by weight, 92 Low levels of approximately 94% by weight, 95% by weight, or 95.5% by weight, 96% by weight , 96.5% by weight, 97% by weight, 97.5% by weight, 98% by weight, 98.5% by weight, 99% by weight A height of approximately 99.5% by weight, or 99.9% by weight, or for example, 50% by weight to 9% by weight. 9.9wt%, 60wt%~99.5wt%, 70wt%~99wt%, 80wt%~9 8.5wt%, 85wt%~98wt%, 87wt%~97.5wt%, 90wt%~9 7% by weight, 92% to 96.5% by weight, 94% to 96% by weight, 95% to 95% by weight. 5% by weight, 50% to 95% by weight, 90% to 99.9% by weight, 95% to 99% by weight. 9% by weight, or any two of the aforementioned values ​​such as 98% to 99.5% by weight It can be within any range defined between them.

[0020] In some embodiments, the ammonium fluorosulfate byproduct stream is ammonium fluorosulfate. The monium byproduct is mixed with water, and then the ammonium fluorosulfate byproduct and water are added. The reaction is carried out at the water splitting temperature, and ammonium fluorosulfate, FSA, and HFSI are added to the water. So, according to equations 2-4, ammonium bicarbonate (NH4HSO4) and hydrogen fluoride (HF4HSO4) are used. It can be treated by forming a mixture of an aqueous solution and sulfuric acid (H2SO4): Formula 2 NH4SO3F+H2O→NH4HSO4+HF, Formula 3 HSO3F+H2O→H2SO4+HF, Formula 4 HN(SO2F)2+4H2O→NH4HSO4+2 HF+H2SO4.

[0021] The hydrolysis reaction temperatures are approximately 20°C, 25°C, 30°C, 35°C, 40°C, and 45°C. Or a low temperature like around 50°C, or around 60°C, 70°C, 80°C, 90°C, 10°C 0°C, approximately 150°C, or high temperatures such as approximately 200°C, or approximately 20°C to approximately 200°C, approximately 2 5℃ to approximately 150℃, approximately 30℃ to approximately 100℃, approximately 35℃ to approximately 90℃, approximately 40℃ to approximately 80℃, Approximately 45°C to 70°C, approximately 50°C to 60°C, approximately 35°C to 90°C, approximately 40°C to 80°C, Either two of the aforementioned values, such as approximately 20°C to approximately 100°C, or approximately 60°C to approximately 80°C. It can be any range defined between the two. Preferably, the reaction temperature is about 25°C to about 8°C. The temperature is 0°C. More preferably, the reaction temperature is about 30°C to about 70°C. Most preferably, The reaction temperature is approximately 40°C to 60°C. At temperatures above approximately 100°C, hydrolysis occurs. It is above atmospheric pressure.

[0022] The ammonium bisulfate mixture can be dried, for example, by vacuum drying, evaporation, spray drying, or any of the above. The combination of these factors separates it from the HF aqueous solution. Next, the ammonium bicarbonate mixture Neutralize with ammonia and convert sulfuric acid to additional ammonium bisulfate according to formula 5: Equation 5: H2SO4 + NH3 → NH4HSO4.

[0023] The neutralized ammonium bicarbonate is dried by, for example, vacuum drying, evaporation, spray drying, or similar methods. It can be dried by any combination. Neutralized ammonium bicarbonate can be used in other reactions. It can be used in, or is suitable for sale and use in applications requiring a weak acid, for example. This is possible. Alternatively, ammonium biphosphate can be reacted with additional ammonia according to formula 6. By doing so, ammonium sulfate can be produced: Formula 6 NH4HSO4+NH3→(NH 42 SO4.

[0024] Ammonium sulfate can be dried, for example, by vacuum drying, evaporation, spray drying, or any combination thereof. It can be dried by drying. The resulting solid ammonium sulfate can be sold, for example, as a fertilizer. It may be suitable for sale and use.

[0025] Water can be separated from the HF aqueous solution to produce a concentrated HF aqueous solution. As is known in the art, by distillation, pressure swing distillation, and / or diffusion dialysis It can be separated. Concentrated HF aqueous solution is a valuable raw material in many industrial processes. The removed water can be stored. Preferably, the ammonium fluorosulfate byproduct is added to the removed water. It is recycled to the water splitting step. Alternatively or additionally, the water is treated as wastewater. obtain.

[0026] In some embodiments, a concentrated HF aqueous solution is concentrated to form anhydrous hydrogen fluoride. It is possible. The term "anhydrous hydrogen fluoride" means hydrogen fluoride that contains virtually no water. In other words, any water in anhydrous hydrogen fluoride is approximately 500 ppm and approximately 300 ppm by weight. , about 200ppm, about 100ppm, about 50ppm, about 30ppm, about 20ppm, about 1 Is the amount 0 ppm, approximately 5 ppm, approximately 3 ppm, approximately 2 ppm, or less than approximately 1 ppm? or a quantity less than any value defined between any two of the aforementioned values. More preferably, the anhydrous hydrogen fluoride contains less than approximately 100 ppm by weight of water. Hydrogen fluoride contains less than approximately 10 ppm by weight of water. Most preferably, anhydrous water iodide is used. The base contains less than approximately 1 ppm by weight of water.

[0027] In some other embodiments, the ammonium fluorosulfate byproduct stream is fluorosulfate The ammonium by-product can be treated by mixing it with water and a base. The base is particularly limited. Not specified. For clarity, the following description uses calcium hydroxide, but the embodiments This includes, for example, the use of sodium hydroxide, potassium hydroxide, or ammonium hydroxide. It is understood that this is possible.

[0028] According to formulas 2-4 and 6-9 (below), prepare ammonium fluorosulfate by-products, water, and salt The group (calcium hydroxide) is reacted at the reaction temperature to produce ammonium fluorosulfate, FSA and By hydrolyzing and neutralizing HFSI, ammonia, calcium fluoride, and calcium sulfate are obtained. Forms a mixture containing ammonium, ammonium bicarbonate, and ammonium sulfate: Formula 2 NH4SO3F+H2O→NH4HSO4+HF, Formula 3 HSO3F+H2O→H2SO4+HF, Formula 4 HN(SO2F)2+4H2O→NH4HSO4+2HF+H2SO4, Formula 6 NH4HSO4+NH3→(NH 42 SO4, Formula 7 2HF+Ca(OH)2→CaF2+2H2O, Formula 8 NH4HSO4+Ca(OH)2→CaSO4+2H2O+NH3, Formula 9 H2SO4+Ca(OH)2→CaSO4+2H2O.

[0029] The ammonia released by the conversion of ammonium bisulfate to calcium sulfate (Equation 8) A part of A leads to the conversion of some ammonium bicarbonate to ammonium sulfate (Equation 6). Obtain. Any ammonia that is not consumed is obtained as acidic sucrose, as is known in the art. It can be treated with rubber.

[0030] The hydrolysis reaction temperatures are approximately 20°C, 25°C, 30°C, 35°C, 40°C, and 45°C. , or low temperatures such as around 50°C, or around 60°C, around 70°C, around 80°C, around 90°C, around 1 High temperatures such as 00°C, approximately 150°C, or approximately 200°C, or approximately 20°C to approximately 200°C. 25℃ to approximately 150℃, approximately 30℃ to approximately 100℃, approximately 35℃ to approximately 90℃, approximately 40℃ to approximately 80℃ Approximately 45°C to 70°C, approximately 50°C to 60°C, approximately 35°C to 90°C, approximately 40°C to 80°C or one of the aforementioned values, such as approximately 20°C to approximately 100°C, or approximately 60°C to approximately 80°C. It can be any range defined between the two. Preferably, the reaction temperature is about 25°C to about The temperature is 80°C. More preferably, the reaction temperature is about 30°C to about 70°C. Most preferably, The reaction temperature is approximately 40°C to 60°C. At temperatures above approximately 100°C, hydrolysis occurs. The pressure is above atmospheric pressure.

[0031] A mixture containing calcium fluoride, calcium sulfate, and ammonium bicarbonate is safe for landfills. It can be deposited entirely. Alternatively, the compound can be separated for further use. For example, fluoride Calcium is used in the production of hydrogen fluoride, or as an optical lens or optical window. It can be used for purposes such as soil conditioners or cement additives. Calcium sulfate can be used, for example, as a soil conditioner or cement additive. It can be used as a fertilizer. Ammonium sulfate can be used as a fertilizer, as mentioned above. Ammonium acid can be used in other reactions, or for example, in applications requiring a weak acid. It may be suitable for sale and use along the way. Alternatively, ammonium bicarbonate may be used as shown in formula 6. As described above, it is treated with ammonia to produce further ammonium sulfate. It is possible.

[0032] In some embodiments, the above process is a continuous process. In some other embodiments... Morphologically, the above process is a half-batch process. A half-batch process is one in which a significant portion of the process is performed sequentially. It is continuous, but the entire process is not continuous. For example, several half-ba In this embodiment, a crude product is produced, stored continuously for a certain period of time, and then stored thereafter. The stored crude product is treated through a separation step to extract ammonium fluorosulfate from the crude product. The by-products are separated, and intermediate and recycled products are continuously generated, and the above process According to one of the ses, intermediate products and recycled products are stored for later use. The ammonium fluorosulfate by-product can be stored for later processing.

[0033] Figure 1 shows the production of bis(fluorosulfonyl)imide according to some embodiments of the present disclosure. Integrated for continuous processing of ammonium fluorosulfate by-products formed in production This is a process flow diagram showing process 10. As shown in Figure 1, process 10 is urea Reactor 12 is configured to connect to inlet flow 14 and fluorosulfonic acid inlet flow 16. It contains. The fluorosulfonic acid in the first fluorosulfonic acid inlet stream 16 is in liquid form. It can be continuously pumped into reactor 12. Alternatively, the fluorosulfonic acid inlet stream 16 The fluorosulfonic acid inside can be added in batches. The urea in the urea inlet stream 14 is solid. This configuration involves, for example, continuously supplying the material to the reactor 12 by a solid transport system (not shown). Alternatively, the urea in the inlet flow 14 can be added to the reactor 12 in batches.

[0034] Reactor 12 can contain a reaction medium to which urea and fluorosulfonic acid are added. The reaction medium may include fluorosulfonic acid. Urea, fluorosulfonic acid, and reactor The reaction medium in 12 is heated to the reaction temperature as described above, and the reaction follows the reaction of Equation 1, HFSI This generates a crude product stream 18 containing carbon dioxide. Carbon dioxide enters the reactor 12 through the reactor vent 20. It can be vented from there. The vented carbon dioxide can be released into the atmosphere or used in subsequent applications. It can be recovered for this purpose. Reactor 12 is, for example, a heat exchanger or a jacketed reactor (Figure The reaction occurs through a fluid flowing through (not shown) or through an electric heating coil (not shown). It is configured to maintain the temperature. In this way, reactor 12 is HFSI, full To produce crude product stream 18 containing ammonium orosulfate and fluorosulfonic acid It is composed of.

[0035] The crude product flow 18 fluidly connects the reactor 12 to the first separator 22. This separates ammonium fluorosulfate from the crude product stream 18, and then separates it from the intermediate product stream 24 and the fluorine sulfate. The first separator is configured to produce an ammonium ruorosulfate byproduct stream 26. 22 is, for example, an evaporator, vacuum dryer, spray dryer, filter, centrifuge, or the like. It can be any combination of the above.

[0036] The intermediate product flow 24 fluidly connects the first separator 22 to the second separator 28. The separator 28 is configured to generate a concentrated product stream 30 and a recycled stream 32. The second separator 28 may be, for example, a distillation column. The concentrated product stream 30 is recycled. It contains a higher concentration of HFSI than the concentration of HFSI in stream 32. Recycled stream 32 is It is fluidically coupled to reactor 12. Alternatively or additionally, the recycle flow 32 is reversed It can be fluidly connected to a fluid-recycling storage tank (not shown) for the fluid-recycling medium. The recycling flow 32 is Afterward, the reaction medium is either sent to reactor 12 for continuous operation or recycled for half-batch operation. It can be directed to the storage tank.

[0037] In the embodiment shown in Figure 1, the ammonium fluorosulfate byproduct stream 26 is the first fraction The separator 22 is fluidly connected to the hydrolysis tank 34, and the ammonium fluorosulfate byproduct is water It is mixed with water supplied by the input flow 36. Fluorosulfate in hydrolysis tank 34 The mixture of monium by-products and water is heated to the hydrolysis reaction temperature as described above. Ammonium fluorosulfate, FSA, and HFSI are hydrolyzed to perform the reactions shown in formulas 2-4 above. Accordingly, an intermediate byproduct stream 38 containing ammonium bicarbonate and an aqueous solution of hydrogen fluoride is formed. ru.

[0038] The hydrolysis tank 34 passes through, for example, a heat exchanger or a jacketed reactor (not shown). The reaction temperature is maintained by the flowing fluid or by an electric heating coil (not shown). It is configured in this way. In this manner, the hydrolysis tank 34 is configured to process ammonium bicarbonate. It is also configured to generate an intermediate byproduct stream 38 containing an aqueous solution of hydrogen fluoride.

[0039] The intermediate byproduct flow 38 fluidly connects the hydrolysis tank 34 to the byproduct separator 40. The product separator 40 separates ammonium bicarbonate from the hydrogen fluoride aqueous solution. It is configured to produce a mononium stream 42 and a hydrogen fluoride aqueous solution stream 44. By-products The separator 40 is, for example, an evaporator, a vacuum dryer, a spray dryer, a filter, a centrifuge, or Any combination of these is possible. Alternatively, in some embodiments, hydrolysis The 34 and the by-product separator 40 can be combined into a single unit.

[0040] The hydrogen fluoride aqueous solution stream 44 fluidly connects the by-product separator 40 to the HF concentrator 46. The F concentrator 46 separates water from the hydrogen fluoride aqueous solution to produce a concentrated hydrogen fluoride stream 48 and a wastewater stream. It is configured to form 50. The HF concentrator 46 includes, for example, a pair of distillation columns. It could be a pressure swing distillation system. The concentrated hydrogen fluoride from the concentrated hydrogen fluoride stream 48 is It can be stored or supplied to another process that requires concentrated hydrogen fluoride. Wastewater flow 5 0 can be recycled to a hydrolysis tank 34 (not shown) or to a wastewater treatment facility (Figure (Unable to show) it can be directed towards.

[0041] The ammonium bisulfate flow 42 is fluidly connected to the byproduct separator 40 and the neutralization tank 52. Ammonium sulfate is mixed with ammonia supplied by ammonia input stream 54. Ammonia reacts with ammonium bisulfate to form ammonium sulfate according to the reaction in formula 5 above. It forms an ammonium sulfate solution containing ammonium sulfate. It is a solution.

[0042] The ammonium sulfate stream 56 is transferred from the neutralization tank 52 to the ammonium sulfate dryer / concentrator 58. Fluid connection. The ammonium sulfate dryer / concentrator 58 converts ammonium sulfate aqueous solution to water The mixture is separated to produce concentrated ammonium sulfate stream 60 and wastewater stream 62. The dryer / concentrator 58 includes, for example, an evaporator, a vacuum dryer, a spray dryer, a filter, and a centrifugal separator. It may be a container, or any combination thereof. Concentrated sulfur in a stream of 60 concentrated ammonium sulfate Ammonium ammonium acid may be suitable for sale and use, for example, as a fertilizer. In the application form, concentrated ammonium sulfate may be in solid form. The wastewater flow 62 is hydrolyzed ammonium sulfate. It can be recycled to (not shown) or directed to a wastewater treatment facility (not shown). It is possible.

[0043] Therefore, the integrated process 10 shown in Figure 1 is a secondary process of ammonium fluorosulfate. An integrated process to efficiently process the product and improve the overall efficiency of HFSI generation. The ammonium fluorosulfate byproduct is treated as shown in Figure 1. This means providing commercially useful by-products and / or environmentally friendly waste.

[0044] Figure 2 shows the production of bis(fluorosulfonyl)imide according to some embodiments of the present disclosure. Another integration for the continuous processing of ammonium fluorosulfate by-products formed in production. This is a process flow diagram showing process 100. As shown in Figure 2, process 10 0 is configured to connect to the urea inlet flow 14 and the fluorosulfonic acid inlet flow 16. Includes receiver 12. The fluorosulfonic acid in the first fluorosulfonic acid inlet stream 16 is liquid. It is a form that can be continuously pumped into reactor 12. Alternatively, fluorosulfonic acid Fluorosulfonic acid can be added in batches to the inlet stream 16. Urine in the urea inlet stream 14 The element is in solid form and is connected to the reactor 12 by, for example, a solid transport system (not shown). It can be supplied continuously. Alternatively, the urea in the inlet flow 14 can be added to the reactor 12 in batches. obtain.

[0045] Reactor 12 can contain a reaction medium to which urea and fluorosulfonic acid are added. The reaction medium may include fluorosulfonic acid. Urea, fluorosulfonic acid, and reactor The reaction medium in 12 is heated to the reaction temperature as described above, and the reaction follows the reaction of Equation 1, HFSI This generates a crude product stream 18 containing carbon dioxide. Carbon dioxide enters the reactor 12 through the reactor vent 20. It can be vented from there. Reactor 12 is, for example, a heat exchanger or a jacketed reactor (not shown) The reaction temperature is controlled by the fluid flowing through the (s) or by an electric heating coil (not shown). It is configured to maintain the following. In this way, reactor 12 is HFSI, fluoro The system is configured to produce a crude product stream 18 containing ammonium sulfate and fluorosulfonic acid. It is being done.

[0046] The crude product flow 18 fluidly connects the reactor 12 to the first separator 22. This separates ammonium fluorosulfate from the crude product stream 18, and then separates it from the intermediate product stream 24 and the fluorine sulfate. The first separator is configured to produce an ammonium ruorosulfate byproduct stream 26. 22 is, for example, an evaporator, vacuum dryer, spray dryer, filter, centrifuge, or the like. It can be any combination of the above.

[0047] The intermediate product flow 24 fluidly connects the first separator 22 to the second separator 28. The separator 28 is configured to generate a concentrated product stream 30 and a recycled stream 32. The second separator 28 may be, for example, a distillation column. The concentrated product stream 30 is recycled. It contains a higher concentration of HFSI than the concentration of HFSI in stream 32. Recycled stream 32 is It is fluidically coupled to reactor 12. Alternatively or additionally, the recycle flow 32 is reversed It can be fluidly connected to a fluid-recycling storage tank (not shown) for the fluid-recycling medium. The recycling flow 32 is Afterward, the reaction medium is either sent to reactor 12 for continuous operation or recycled for half-batch operation. It can be directed to the storage tank.

[0048] In the embodiment shown in Figure 2, the ammonium fluorosulfate byproduct stream 26 is the first fraction The separator 22 is fluidly connected to the hydrolysis / neutralization tank 102, and ammonium fluorosulfate is produced as a by-product. The material is supplied by water input stream 104 and calcium hydroxide input stream 106. It is mixed with the provided calcium hydroxide. Fluorosulfate in hydrolysis neutralization tank 102. The mixture of ammonium by-products, water, and calcium hydroxide undergoes hydrolysis as described above. When heated to a certain temperature, ammonium fluorosulfate, FSA, and HFSI are hydrolyzed and neutralized. Then, according to the reactions of equations 2-4 and 6-9 above, calcium fluoride, calcium sulfate, A waste stream 108 containing ammonium sulfate and ammonium binitrate, and a vent 110 To form. Any ammonia in the vent 110 is, as is known in the art, It can be directed to a scrubber (not shown) for summation.

[0049] Waste stream 108, containing only environmentally acceptable waste, is economically deposited in a landfill. Alternatively, the waste stream 108 can be separated for further use, as described above. Therefore, the integrated process 100 shown in Figure 2 uses ammonium fluorosulfate as a secondary component. An integrated process to efficiently process the product and improve the overall efficiency of HFSI generation. The ammonium fluorosulfate byproduct is treated as shown in Figure 2. This means providing commercially useful by-products and / or environmentally friendly waste.

[0050] System 10 in Figure 1 and System 100 in Figure 2 operate in continuous mode or semi-batch mode. It can be done.

[0051] As used herein, "any range defined between any two of the aforementioned values" The phrase "within the enumeration" means that the values ​​are in the lower part of the enumeration or the higher part of the enumeration Whether or not, any range is any two of the values ​​listed before such a clause. This means that there can be two options to choose from. For example, a pair of values ​​could be two lower values, or two lower values. A higher value, or a lower and higher value may be selected. In this case, the singular forms "a," "an," and "the" are used when the context clearly indicates otherwise. Unless otherwise specified, it includes plural forms.

[0052] Regarding the term "inaccurate," the terms "about" and "approximately" may be used interchangeably in descriptions. This refers to measurements that include the stated measurements, and also includes any measurements that are reasonably close to the stated measurements. Measurement values ​​that are reasonably close to the stated measurements are understandable and easily verifiable by those skilled in the art. Such deviations deviate from measurements that describe only reasonably small quantities. For example, this may be due to measurement errors or fine-tuning performed to optimize performance. If it is determined that the value of a reasonably small difference, such as "approximately", cannot be easily confirmed, then "approximately" and " The term "approximately" can be understood to mean plus or minus 10% of the stated value. .

[0053] It should be understood that the above explanation is merely illustrative of the present disclosure. Without departing from this, various alternative and modified forms can be devised by those skilled in the art. Therefore, this disclosure covers all such alternative forms included in the attached claims. This is intended to include modified forms and variations.

[0054] manner Embodiment 1 is a process for treating ammonium fluorosulfate byproducts. Seth is mainly composed of ammonium fluorosulfate and smaller amounts of fluorosulfonic acid and bisulfate. This provides an ammonium fluorosulfate by-product containing (fluorosulfonyl)imide. Furthermore, mixing the ammonium fluorosulfate byproduct with water, and ammonium fluorosulfate The mixture of ammonium by-products and water is reacted at the hydrolysis reaction temperature to produce ammonium fluorosulfate. Hydrolyzing sulfur dioxide, fluorosulfonic acid, and bis(fluorosulfonyl)imide yields heavy sulfur dioxide. This includes forming aqueous solutions of ammonium acid and hydrogen fluoride.

[0055] Embodiment 2 further involves separating water from an aqueous solution of hydrogen fluoride to form concentrated hydrogen fluoride. This includes the process described in Embodiment 1.

[0056] Embodiment 3 involves separating water from an aqueous solution of hydrogen fluoride to form concentrated hydrogen fluoride, under pressure The process according to embodiment 2 includes force swing distillation.

[0057] Embodiment 4 is the process according to Embodiment 2 or Embodiment 3, wherein the concentrated hydrogen fluoride is anhydrous hydrogen fluoride. It is S.

[0058] Embodiment 5 is a case in which the concentration of ammonium fluorosulfate in the ammonium fluorosulfate byproduct is , 50% to 99.9% by weight of ammonium fluorosulfate by-products, as in embodiments 1 to 4 This is the process described in one of the following.

[0059] Embodiment 6 is a case in which the concentration of ammonium fluorosulfate in the ammonium fluorosulfate byproduct is , 90% to 99.9% by weight of ammonium fluorosulfate by-products, as in embodiments 1 to 4. This is the process described in one of the following.

[0060] Embodiment 7 is a by-product of ammonium fluorosulfate, ammonium fluorosulfate, fluor Essentially consisting of rosulfonic acid and bis(fluorosulfonyl)imide, according to embodiments 1 to 6 This is the process described elsewhere.

[0061] Embodiment 8 is any of Embodiments 1 to 7, wherein the hydrolysis reaction temperature is approximately 20°C to approximately 200°C. This is the process described in [the document].

[0062] Embodiment 9 is one of Embodiments 1 to 7, wherein the hydrolysis reaction temperature is approximately 40°C to approximately 60°C. The process is as described.

[0063] Embodiment 10 describes how ammonium bicarbonate can be separated from an aqueous solution of hydrogen fluoride by vacuum drying. The process includes, but is not limited to, the process described in any of embodiments 1 to 9.

[0064] Embodiment 11 involves reacting ammonium bicarbonate with ammonia to form ammonium sulfate. The process according to any one of embodiments 1 to 10, further comprising the following:

[0065] Embodiment 12 is the process of Embodiment 11, further comprising drying the ammonium sulfate. ru.

[0066] Embodiment 13 is a process described in any of Embodiments 1 to 12, and the process is a continuous process It's Seth.

[0067] Embodiment 14 is a process according to any one of Embodiments 1 to 12, and the process is a half-batch process. It is a process.

[0068] Embodiment 15 is the process described in any of Embodiments 1 to 14, and the process is fluoro To provide a solution containing sulfonic acid and urea, and a solution containing fluorosulfonic acid and urea The liquid is reacted at a reaction temperature of 80°C to approximately 170°C to produce bis(fluorosulfonyl)imide. To produce a crude product containing fluorosulfonic acid and ammonium fluorosulfate, Ammonium fluorosulfate is separated from the crude product, and bis(f)(f) is obtained at a higher concentration than the crude product. An intermediate product having luorosulfonyl)imide and an ammonium fluorosulfate byproduct This process generates ammonium fluorosulfate byproducts, which have a higher concentration than the crude product. It has a degree of ammonium fluorosulfate, and the intermediate product is concentrated and the product is The process involves separating the cycle product from the concentrated product, which is more concentrated than the recycled product. A concentration of bis(fluorosulfonyl)imide, separated and further integrated This is the process.

[0069] Embodiment 16 involves reacting the recycled product with a solution containing fluorosulfonic acid and urea. The process according to embodiment 15 further includes recycling and returning to the step.

[0070] Embodiment 17 separates the intermediate product stream into concentrated product and recycled product, The process according to embodiment 15 or embodiment 16, comprising distillation of the product.

[0071] Embodiment 18 is a process for treating ammonium fluorosulfate byproducts. Rothes is mainly composed of ammonium fluorosulfate and less fluorosulfonic acid and phenylalanine. This provides an ammonium fluorosulfate by-product containing su(fluorosulfonyl)imide. This involves mixing the ammonium fluorosulfate by-product with water and a base, and fluorosulfate A mixture of ammonium ammonium byproducts, water, and a base is reacted at the hydrolysis reaction temperature. Ammonium fluorosulfate, fluorosulfonic acid, and bis(fluorosulfonyl)imide Hydrolysis and neutralization form a mixture containing fluoride, sulfate, and ammonium bisulfate. This includes doing something.

[0072] Embodiment 19 involves reacting a mixture of ammonium fluorosulfate byproducts with water and a base. The process described in embodiment 18 also involves the formation of ammonia.

[0073] Embodiment 20 is a base comprising calcium hydroxide, and the fluoride formed is calcium fluoride The description in Embodiment 18 or Embodiment 19, wherein the sulfate formed contains um and contains calcium sulfate. This is the process.

[0074] Embodiment 21 is a base containing sodium hydroxide, and the fluoride formed is sodium fluoride The sulfate formed contains , and the sulfate contained contains sodium sulfate, as described in Embodiment 18 or Embodiment 19. Includes the process.

[0075] Embodiment 22 is a base comprising potassium hydroxide, and the fluoride formed is potassium fluoride. The product according to embodiment 18 or embodiment 19, which contains and forms a sulfate containing potassium sulfate. Includes Seth.

[0076] Embodiment 23 is a base comprising ammonium hydroxide, and the fluoride formed is ammonium hydroxide Embodiment 18 or Embodiment 19, which contains monium and the sulfate formed contains ammonium sulfate. This includes the process described above.

[0077] Embodiment 24 shows the concentration of ammonium fluorosulfate in the ammonium fluorosulfate by-product. However, the ammonium fluorosulfate by-product is 50% to 99.9% by weight, as in Embodiment 18. The process is one of the steps described in any of the following 23.

[0078] Embodiment 25 shows the concentration of ammonium fluorosulfate in the ammonium fluorosulfate byproduct. However, the by-product of ammonium fluorosulfate is 90% to 99.9% by weight, as in Embodiment 18. The process is one of the steps described in any of the following 23.

[0079] Embodiment 26 is a by-product of ammonium fluorosulfate, ammonium fluorosulfate, ful Embodiments 18-2, essentially consisting of orosulfonic acid and bis(fluorosulfonyl)imide. This is the process described in one of item 5.

[0080] Embodiment 27 is an embodiment of Embodiments 18 to 26 in which the hydrolysis reaction temperature is approximately 20°C to approximately 200°C. This is the process described elsewhere.

[0081] Embodiment 28 is a hydrolysis reaction temperature of approximately 40°C to approximately 60°C, one of embodiments 18 to 26. It is the process described in one of the following.

[0082] Embodiment 29 is a process described in any of Embodiments 18 to 28, and the process is a continuous process It is Rothes.

[0083] Embodiment 30 is a process described in any of Embodiments 18 to 28, and the process is a half-batch process. It is a process.

[0084] Embodiment 31 is a process according to any of Embodiments 18 to 30, and the process is fluorescein. To provide a solution containing fluorosulfonic acid and urea, and a solution containing fluorosulfonic acid and urea The solution is reacted at a reaction temperature of 80°C to approximately 170°C to produce bis(fluorosulfonyl)imide. To produce a crude product containing fluorosulfonic acid and ammonium fluorosulfate. , ammonium fluorosulfate is separated from the crude product to obtain bis( Intermediate product containing fluorosulfonyl)imide and ammonium fluorosulfate byproduct This process generates ammonium fluorosulfate byproducts, which are more expensive than the crude product. Having a concentration of ammonium fluorosulfate, it is produced, and the intermediate product is concentrated into the product. The process involves separating the recycled product from the concentrated product, which is more concentrated than the recycled product. A separation and integration of a high concentration of bis(fluorosulfonyl)imide is further included. This is a process.

[0085] Embodiment 32 involves reacting the recycled product with a solution containing fluorosulfonic acid and urea. The process according to embodiment 31 further includes recycling and returning to the step.

[0086] Embodiment 33 separates the intermediate product into a concentrated product and a recycled product, The process according to either embodiment 31 or embodiment 32, comprising distilling the product.

Claims

1. A process for processing ammonium fluorosulfate byproducts, Mainly ammonium fluorosulfate, and smaller amounts of fluorosulfonic acid and bis(flu) To provide an ammonium fluorosulfate by-product containing orosulfonyl)imide, The ammonium fluorosulfate by-product is mixed with water, The mixture of the ammonium fluorosulfate by-product and the water is reacted at the hydrolysis reaction temperature. The ammonium fluorosulfate, the fluorosulfonic acid and the bis(fluorine) Hydrolysis of rosulfonyl imide forms ammonium bicarbonate and hydrogen fluoride aqueous solutions. To do, The process includes separating the ammonium bicarbonate from the aqueous hydrogen fluoride solution. vinegar.

2. The process further includes separating the water from the aqueous hydrogen fluoride solution to form concentrated hydrogen fluoride. The process described in claim 1.

3. Separating the water from the aforementioned hydrogen fluoride aqueous solution to form concentrated hydrogen fluoride is performed under pressure. The process according to claim 2, comprising swing distillation.

4. The process according to claim 2 or 3, wherein the concentrated hydrogen fluoride is anhydrous hydrogen fluoride.

5. The concentration of the ammonium fluorosulfate in the ammonium fluorosulfate by-product is Claim 1, which is 50% to 99.9% by weight of the ammonium fluorosulfate by-product. The process described in any one of items ~4.

6. The aforementioned process, To provide a solution containing fluorosulfonic acid and urea, The solution containing the aforementioned fluorosulfonic acid and urea is reacted at a reaction temperature of 80°C to approximately 170°C. Furthermore, bis(fluorosulfonyl)imide, fluorosulfonic acid, and fluorosulfate To produce a crude product containing monoium, The ammonium fluorosulfate is separated from the crude product and obtained from the crude product which is of a higher quality than the crude product. An intermediate product having a concentration of bis(fluorosulfonyl)imide, and the fluorosulfate ammonium The process involves generating a monium byproduct, wherein the ammonium fluorosulfate byproduct is , and the formation of a product having a higher concentration of ammonium fluorosulfate than the crude product, The intermediate product is separated into a concentrated product and a recycled product, and the concentrated The product contains a higher concentration of bis(fluorosulfonyl)imide than the recycled product. Any of claims 1 to 5, an integrated process that further includes, separating, and The process described in item 1.

7. A process for processing ammonium fluorosulfate byproducts, Mainly ammonium fluorosulfate, and smaller amounts of fluorosulfonic acid and bis(flu) To provide an ammonium fluorosulfate by-product containing orosulfonyl)imide, The ammonium fluorosulfate by-product is mixed with water and a base, The mixture of the ammonium fluorosulfate by-product, water, and the base is hydrolyzed. The reaction is carried out at the reaction temperature, and the ammonium fluorosulfate, the fluorosulfonic acid and the The bis(fluorosulfonyl)imide is hydrolyzed and neutralized to obtain fluoride, sulfate, and A process comprising forming a mixture containing ammonium bisulfate.

8. The mixture of the ammonium fluorosulfate by-product, water, and the base is reacted. The process according to claim 7, wherein the process also forms ammonia.

9. The base contains calcium hydroxide, and the fluoride formed is calcium fluoride. The product according to claim 7 or 8, comprising, and the sulfate formed comprises calcium sulfate. Seth.

10. The base contains sodium hydroxide, and the fluoride formed is sodium fluoride. The product according to claim 7 or 8, comprising, and the sulfate formed comprises sodium sulfate. Seth.

11. The base contains potassium hydroxide, and the fluoride formed contains potassium fluoride. The process according to claim 7 or 8, wherein the sulfate formed comprises potassium sulfate.

12. The base contains ammonium hydroxide, and the fluoride formed is ammonium fluoride The claim 7 or 8, wherein the sulfate formed contains ammonium sulfate. The process.

13. The aforementioned ammonium fluorosulfate by-product is ammonium fluorosulfate, fluorosulfate Any of claims 7 to 12, which essentially consists of fluorosulfonyl acid and bis(fluorosulfonyl)imide The process described in any one of the items.

14. The aforementioned process, To provide a solution containing fluorosulfonic acid and urea, The solution containing the aforementioned fluorosulfonic acid and urea is reacted at a reaction temperature of 80°C to approximately 170°C. Furthermore, bis(fluorosulfonyl)imide, fluorosulfonic acid, and fluorosulfate To produce a crude product containing monoium, The ammonium fluorosulfate is separated from the crude product and obtained from the crude product which is of a higher quality than the crude product. An intermediate product having a concentration of bis(fluorosulfonyl)imide, and the fluorosulfate ammonium The process involves generating a monium byproduct, wherein the ammonium fluorosulfate byproduct is , and the formation of a product having a higher concentration of ammonium fluorosulfate than the crude product, The intermediate product is separated into a concentrated product and a recycled product, and the concentrated The product contains a higher concentration of bis(fluorosulfonyl)imide than the recycled product. Any of claims 7 to 13 is an integrated process that further includes, separating, and The process described in item 1.

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