Preparation method of sulfuryl fluoride and sulfuryl fluoride
The preparation process of sulfuryl fluoride was simplified by using liquid-solid reaction and thermal decomposition of liquid sulfur oxides with fluoride salts, which improved the purity and yield of sulfuryl fluoride and reduced production costs.
Patent Information
- Application Number
- CN202410911047.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-08
- Publication Date
- 2026-01-09
AI Technical Summary
Existing methods for preparing thioyl chloride are relatively complex, and the yield of thioyl fluoride needs to be further improved.
The preparation of sulfuryl fluoride involves mixing liquid sulfur-containing oxides with fluoride salts, followed by a liquid-solid reaction and thermal decomposition. The specific steps include mixing, heating to recover unreacted substances, thermal decomposition, and acid washing purification.
The preparation process was simplified, the purity and yield of thiosulfate were improved, and the production cost was reduced.
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Figure CN121292369A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of battery technology, specifically to a method for preparing sulfuryl fluoride and sulfuryl fluoride. Background Technology
[0002] Thionyl fluoride is an inorganic compound with the chemical formula SO₂F₂. As an important intermediate in the fluorochemical industry, it is increasingly being used in more and more fields. However, the current preparation methods for thioyl chloride are relatively complex, and the yield of thioyl fluoride needs further improvement. Summary of the Invention
[0003] This application is made in view of the above-mentioned issues, and its purpose is to provide a method for preparing thioyl fluoride and thioyl fluoride, which simplifies the preparation process and improves the yield of thioyl fluoride.
[0004] In a first aspect, this application provides a method for preparing thioyl fluoride, comprising the following steps:
[0005] Liquid sulfur-containing oxides are mixed with fluoride salts to undergo a liquid-solid reaction, yielding fluorosulfonic acid compounds.
[0006] The fluorosulfonic acid compound is thermally decomposed to prepare thioyl fluoride;
[0007] The chemical formula of the fluorosulfonic acid compound is M(SO3F). X Where M represents a metal cation or ammonium ion, and x represents the valence of the metal cation or ammonium ion.
[0008] The technical solution of this application uses a mixture of liquid sulfur-containing oxides and fluoride salts, and thermally decomposes the product after the liquid-solid reaction between the two to prepare sulfuryl fluoride. This method is simple to operate and has high purity and yield of the target product.
[0009] In any embodiment, the sulfur-containing oxide includes at least one of sulfur trioxide, sulfur dioxide, sulfuryl chloride, and pyrosulfuric acid. These sulfur-containing oxide raw materials are readily available and widely sourced, which helps to reduce production costs.
[0010] In any embodiment, the fluoride salt includes at least one selected from barium fluoride, sodium fluoride, iron fluoride, magnesium fluoride, potassium fluoride, calcium fluoride, and ammonium fluoride. These fluoride salt raw materials are readily available and widely sourced, which helps to reduce production costs.
[0011] In any embodiment, the molar ratio between the sulfur-containing oxide and the fluoride salt is (2-5):1. Within this suitable range, the use of an excess of sulfur-containing oxide facilitates a more complete conversion of the sulfur-containing oxide into a fluorosulfonic acid compound.
[0012] In any embodiment, the average particle size Dv50 of the fluoride salt is 50–200 μm; and / or, the water content of the fluoride salt is less than or equal to 0.01%; and / or, the purity of the fluoride salt is 98%–100%. An average particle size Dv50 within a suitable range is beneficial for increasing the contact area between the solid and liquid in the solid-liquid reaction, thereby improving reaction efficiency. Since sulfur oxides readily react with water, such as sulfur trioxide, sulfur dioxide, and sulfuryl chloride, which readily react with water to form acids, controlling the water content of the fluoride salt within a suitable range helps avoid side reactions and improves the purity of the target product. Controlling impurities inherent in the fluoride salt within a suitable range is beneficial for improving the yield of the target product.
[0013] In any embodiment, in the step of mixing a liquid sulfur-containing oxide with a fluoride salt to undergo a liquid-solid reaction and obtain a fluorosulfonic acid compound, the mixing temperature is between the melting point and boiling point of the liquid sulfur-containing oxide. A mixing temperature between the melting point and boiling point of the liquid sulfur-containing oxide is advantageous because the sulfur-containing oxide and the fluoride salt are in a liquid state when mixed, thus facilitating the liquid-solid reaction.
[0014] In any embodiment, the mixing temperature in the step of mixing liquid sulfur-containing oxides with fluoride salts to undergo a liquid-solid reaction and obtain fluorosulfonic acid compounds is -15 to 180°C. A suitable mixing temperature is beneficial for promoting the liquid-solid reaction.
[0015] In any embodiment, the step of mixing liquid sulfur-containing oxides with fluoride salts to undergo a liquid-solid reaction to obtain a fluorosulfonic acid compound includes: mixing liquid sulfur-containing oxides with fluoride salts to undergo a liquid-solid reaction to obtain a fluorosulfonic acid compound; heating to vaporize and recover any unreacted sulfur-containing oxides; wherein the heating temperature is lower than the decomposition temperature of the fluorosulfonic acid compound. Therefore, this application can separate the raw materials and intermediate products solely by heating, a simple and efficient separation method that avoids premature thermal decomposition of the intermediate products during the separation process.
[0016] In any embodiment, the step of heating to vaporize and recover the unreacted sulfur-containing oxides includes recovery using a vacuum method. Using a vacuum method facilitates the separation of the vaporized raw materials from the intermediate products, and the separation method is simple and efficient.
[0017] In any embodiment, the step of thermally decomposing the fluorosulfonic acid compound to prepare sulfuryl fluoride occurs at a temperature of 500–1200°C; and / or, the thermal decomposition is carried out under vacuum. Maintaining the thermal decomposition temperature within this suitable range is beneficial for increasing the decomposition rate and improving production efficiency. It also helps to further increase the yield of the target product.
[0018] In any embodiment, the step of preparing thioyl fluoride by thermal decomposition of the fluorosulfonic acid compound includes: thermally decomposing the fluorosulfonic acid compound to obtain a gaseous product; and purifying the gaseous product by acid washing to obtain thioyl fluoride. The post-treatment acid washing and purification step is beneficial for improving the purity of the target product.
[0019] In any embodiment, the step of purifying the gaseous product by acid washing to obtain thioyl fluoride uses an acid washing solution comprising at least one of citric acid, sulfurous acid, and concentrated sulfuric acid with a concentration of 70–98 wt.%. These acid washing solutions are widely available, which helps reduce production costs.
[0020] Secondly, this application provides a thioyl fluoride prepared by the preparation method provided in the first aspect. Attached Figure Description
[0021] Figure 1 This is an ion chromatogram of a sample taken from a reactor section in Example 1 of the present invention. Detailed Implementation
[0022] The following provides a detailed description of the preparation method and embodiments of the thioyl fluoride of this application. However, unnecessary details may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided for the purpose of enabling those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.
[0023] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values of 1 and 2 are listed, and if maximum range values of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
[0024] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.
[0025] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.
[0026] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.
[0027] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.
[0028] Thionyl fluoride is an inorganic compound with the chemical formula SO₂F₂. As an important intermediate in the fluorochemical industry, it is increasingly being used in more and more fields. However, the current preparation methods for thioyl chloride are relatively complex, and the yield of thioyl fluoride needs further improvement.
[0029] To adopt a simpler preparation method, existing technologies include reacting sulfur trioxide vapor with barium fluoride to obtain a mixed gas of barium sulfate and sulfuryl fluoride. However, subsequent purification requires multiple acid washings before passing the gas through a distillation column for separation, resulting in high energy consumption and low yield.
[0030] In view of this, in a first aspect, embodiments of this application provide a method for preparing thioyl fluoride, comprising the following steps:
[0031] Liquid sulfur-containing oxides are mixed with fluoride salts to undergo a liquid-solid reaction, yielding fluorosulfonic acid compounds.
[0032] The fluorosulfonic acid compound is thermally decomposed to prepare thioyl fluoride;
[0033] The chemical formula of the fluorosulfonic acid compound is M(SO3F). X Where M represents a metal cation or ammonium ion, and x represents the valence of the metal cation or ammonium ion.
[0034] In this article, "fluoride salts" can refer to a class of salts containing fluoride ions (F). - ) compounds are usually formed by the combination of metal elements, ammonium ions or organic groups with fluoride ions.
[0035] In this article, "sulfur-containing oxides" can refer to compounds that contain both sulfur and oxygen elements, in order to provide sulfur and oxygen elements for fluorosulfonic acid compounds.
[0036] In this article, "thermal decomposition" can refer to the process in which a substance undergoes a self-decomposition reaction after being heated, breaking down into smaller compounds or elements.
[0037] The technical solution of this application uses a mixture of liquid sulfur-containing oxides and fluoride salts, and thermally decomposes the product after the liquid-solid reaction between the two to prepare sulfuryl fluoride. This method is simple to operate and has high purity and yield of the target product.
[0038] In some embodiments, the sulfur-containing oxides include at least one of sulfur trioxide, sulfur dioxide, sulfuryl chloride, and pyrosulfuric acid. These sulfur-containing oxide raw materials are readily available and widely sourced, which helps to reduce production costs.
[0039] In some embodiments, the fluoride salt includes at least one selected from barium fluoride, sodium fluoride, iron fluoride, magnesium fluoride, potassium fluoride, calcium fluoride, and ammonium fluoride. These fluoride salt raw materials are readily available and widely sourced, which helps to reduce production costs.
[0040] To better understand the preparation method of sulfuryl fluoride described above, the following uses sulfur trioxide as the sulfur-containing oxide and barium fluoride as the fluoride salt as an example, and provides a simple explanation through chemical reaction equations. The preparation method of sulfuryl fluoride mainly includes the following reaction processes:
[0041] SO3 + BaF2 → Ba(SO3F)2
[0042]
[0043] In some embodiments, the molar ratio between the sulfur oxide and the fluoride salt is (2–5):1. Within this suitable range, the use of an excess of sulfur oxide facilitates a more complete conversion of the sulfur oxide into a fluorosulfonic acid compound. The molar ratio between sulfur oxides and fluoride salts can be 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7:1, 4.8:1, 4.9:1, 5:1, or any range of two values.
[0044] In some embodiments, the average particle size Dv50 of the fluoride salt is 50–200 μm. A suitable average particle size Dv50 range is beneficial for increasing the contact area between the solid and liquid in the solid-liquid reaction, thereby improving reaction efficiency. The water content of the fluoride salt is less than or equal to 0.01%. Since sulfur oxides readily react with water, such as sulfur trioxide, sulfur dioxide, sulfuryl chloride, and pyrosulfuric acid, and fluorides readily react with acids (e.g., barium fluoride readily reacts with acids to form barium sulfate and hydrogen fluoride), controlling the water content of the fluoride salt within a suitable range helps avoid side reactions and improves the purity of the target product. The purity of the fluoride salt is 98%–100%. Controlling the impurities inherent in the fluoride salt within a suitable range is beneficial for improving the yield of the target product. The average particle size Dv50 of the fluoride salt can be 50 μm, 80 μm, 100 μm, 120 μm, 150 μm, 180 μm, 200 μm, or any combination of two values. The purity of the fluoride salt can be 98%, 99%, 100%, or any combination of two values.
[0045] In some embodiments, in the step of mixing liquid sulfur-containing oxides with fluoride salts to undergo a liquid-solid reaction and obtain fluorosulfonic acid compounds, the mixing temperature is between the melting point and boiling point of the liquid sulfur-containing oxides. A mixing temperature between the melting point and boiling point of the liquid sulfur-containing oxides is advantageous because the sulfur-containing oxides and fluoride salts are in a liquid state when mixed, thus facilitating the liquid-solid reaction.
[0046] In some embodiments, in the step of mixing liquid sulfur-containing oxides with fluoride salts to undergo a liquid-solid reaction to obtain fluorosulfonic acid compounds, the mixing temperature is -15 to 180°C. A suitable mixing temperature is beneficial for promoting the liquid-solid reaction. Since different sulfur-containing oxides have different boiling points, the mixing temperature varies, but it is sufficient that the mixing temperature is between the melting point and boiling point of the liquid sulfur-containing oxides. The mixing temperature can be -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, or any combination of two values. For example, sulfur dioxide has a boiling point of approximately -10°C, so the mixing temperature could be, for example, -15°C; sulfur trioxide has a boiling point of approximately 44°C, so the mixing temperature could be below 44°C. As for pyrosulfuric acid, its melting point is approximately 36°C. Therefore, to achieve the mixing of liquid pyrosulfuric acid with fluoride salts, the mixing temperature could be between its melting point and boiling point, such as 36°C, 40°C, etc.
[0047] In some embodiments, the step of mixing liquid sulfur-containing oxides with fluoride salts to undergo a liquid-solid reaction to obtain fluorosulfonic acid compounds includes: mixing liquid sulfur-containing oxides with fluoride salts to undergo a liquid-solid reaction to obtain fluorosulfonic acid compounds; heating to vaporize unreacted sulfur-containing oxides and recovering them; wherein the heating temperature is lower than the decomposition temperature of the fluorosulfonic acid compounds. Therefore, this application can separate raw materials and intermediate products solely by heating, a simple and efficient separation method that avoids premature thermal decomposition of intermediate products during the separation process.
[0048] In some embodiments, the step of heating to vaporize and recover the unreacted sulfur-containing oxides includes recovery using a vacuum method. Using a vacuum method facilitates the separation of the vaporized raw material from the intermediate product, and the separation method is simple and efficient. The vaporized raw material can be extracted using a vacuum method, and the negative pressure created by the vacuum method can be, for example, -300 to -50 Pa.
[0049] In some embodiments, the thermal decomposition of the fluorosulfonic acid compound to prepare sulfuryl fluoride occurs at a temperature of 500–1200°C, and is carried out under vacuum. Maintaining the thermal decomposition temperature within this suitable range is beneficial for increasing the decomposition rate and improving production efficiency. It also helps to further increase the yield of the target product. The thermal decomposition temperature can be 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C, 850°C, 900°C, 950°C, 1000°C, 1050°C, 1100°C, 1150°C, 1200°C, or any combination of two values. Conducting the thermal decomposition under vacuum facilitates the timely extraction of the product; the negative pressure created during the vacuum process can be -300 to 0 Pa.
[0050] In some embodiments, the step of thermally decomposing the fluorosulfonic acid compound to prepare sulfuryl fluoride includes: thermally decomposing the fluorosulfonic acid compound to obtain a gaseous product; and purifying the gaseous product by acid washing to obtain sulfuryl fluoride. The post-treatment acid washing and purification step is beneficial for improving the purity of the target product.
[0051] In some embodiments, the step of purifying the gaseous product by acid washing to obtain thioyl fluoride uses an acid washing solution comprising at least one of citric acid, sulfurous acid, and concentrated sulfuric acid with a concentration of 70–98 wt.%. These acid washing solutions are widely available, which helps reduce production costs.
[0052] Secondly, embodiments of this application provide a thioyl fluoride prepared by the preparation method provided in the first aspect.
[0053] The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.
[0054] Example 1
[0055] In a primary reactor at 38°C, 26.489 g (0.33 mol) of liquid sulfur trioxide and 28.972 g (0.165 mol) of barium fluoride were added. The molar ratio of sulfur trioxide to barium fluoride was 2:1. The mixing time was 1-3 minutes, and the mixture was stirred to ensure thorough mixing. After the reaction was completed, the reactor temperature was raised to 120°C and the pressure was set to -210 Pa. The reactor exhaust gas was connected to a cooling system to recover sulfur trioxide. The mixture was stirred for 3 hours, and the solid material was discharged into the next reactor (second-stage reactor). The solid material was barium fluorosulfonate. In this embodiment, the average particle size Dv50 of barium fluoride was 100 micrometers, the water content of barium fluoride was 0.01%, and the purity of barium fluoride was 99%.
[0056] The two-stage reactor was stirred at 500℃ for 4 hours, and the pressure was controlled at -153Pa. After the tail gas passed through a dust collector and a heat exchanger, it was washed with 80wt% concentrated sulfuric acid to obtain 37.44g of barium sulfate solid with a purity of 99% and a yield of 97%.
[0057] After washing, 15.378 g of sulfuryl fluoride gas with a purity of 99% and a yield of 92% was obtained.
[0058] Examples 2 to 15 are prepared using the same method as Example 1, except that the preparation parameters are different. Please refer to Table 1 for details of the preparation parameters.
[0059] Comparative Example 1
[0060] 28.972 g of barium fluoride was placed in a reaction vessel, and the apparatus was heated to 580 °C using an electric heater. Sulfur trioxide vapor was passed through the barium fluoride at a rate of 440 ml / min, with a molar ratio of sulfur trioxide to barium fluoride of 2:1. The reaction was carried out for 0.5 hours to obtain a sulfuryl fluoride mixed gas. The obtained mixed gas was then acid-washed with an 80% concentrated sulfuric acid solution in an acid washing tank to obtain sulfuryl fluoride gas.
[0061] Performance testing:
[0062] (1) Purity: The purity of thioyl fluoride was determined by gas chromatography.
[0063] Equipment model: Agilent 8860 gas chromatograph.
[0064] Detector type: FID.
[0065] Column type: HP-5.
[0066] Test method: Heating program: Initial temperature: 50℃, hold for 1 min, rate 15℃ / min, increase to 240℃, hold for 5 min.
[0067] Detector temperature: 280℃, injection port temperature: 280℃, column flow rate: 1ml / min.
[0068] (2) Yield:
[0069] Yield refers to the ratio of the actual product output obtained from a unit quantity of raw materials input in a chemical reaction to the theoretically calculated product output.
[0070] Yield = Actual yield of target product / Theoretical yield of target product × 100%.
[0071] Taking Example 1 as an example, an alkaline solution was used to absorb sulfuryl fluoride. The alkaline solution was 25% sodium hydroxide. The alkaline solutions before and after absorption were weighed.
[0072] Thionyl fluoride yield = mass of thioyl fluoride absorbed / theoretical weight of thioyl fluoride = weight change before and after alkali absorption ΔQ / (barium fluoride feed rate / 175 * 10²)
[0073] The weight change of the alkali solution before and after absorption, ΔQ = mass of the alkali solution after absorbing sulfuryl fluoride - mass of the alkali solution before absorbing sulfuryl fluoride.
[0074] (3) Detection of barium fluorosulfonate:
[0075] The method involves sampling within a single reactor section and performing anion testing on the samples.
[0076] Column type: Ion chromatography parameters
[0077] Equipment: ShengHan IC-D120
[0078] Column: SH-AC-3
[0079] Suppressor: Membrane suppressor
[0080] Detector: Conductivity detector
[0081] Mobile phase: deionized water
[0082] Pump flow rate: 1 ml / min
[0083] Column temperature: 35℃
[0084] Conductivity cell temperature: 35℃
[0085] Suppressor current: 75mA
[0086] External rinsing solution generator: 30mM (KOH system) with high viscosity.
[0087]
[0088] As can be seen from the results in Table 1, Examples 1-16 of this application use liquid sulfur-containing oxides and fluoride salts to carry out solid-liquid reactions to obtain fluorosulfonic acid compounds, which are then thermally decomposed to prepare sulfuryl fluoride with high purity and high yield.
[0089] Compared to Comparative Example 1, the yield of sulfuryl fluoride in this embodiment is relatively higher. Comparative Example 1 uses gaseous sulfur trioxide, which requires a higher reaction temperature, greater energy consumption, and a longer reaction time. This embodiment uses liquid sulfur-containing oxides, resulting in a milder reaction temperature, shorter reaction time, and a simpler raw material separation process, thus facilitating raw material separation.
[0090] As can be seen from Examples 1-4, adjusting the molar ratio of liquid sulfur oxides to fluoride salts can better promote the formation of fluorosulfonic acid compounds. When the molar ratio of sulfur oxides to fluoride salts is (3.8-5):1, it is more conducive to improving the yield of sulfuryl fluoride.
[0091] As can be seen from Examples 5-6, changing the average particle size Dv50 of the fluoride salt or changing the mixing temperature can result in high purity and high yield of thioacryl fluoride.
[0092] As can be seen from Examples 2 and 8-10, adjusting the thermal decomposition temperature of the fluorosulfonic acid compound can further improve the yield of sulfuryl fluoride. The thermal decomposition temperature of the fluorosulfonic acid compound is 500-1200℃, which is more conducive to improving the yield of sulfuryl fluoride.
[0093] As can be seen from Examples 2 and 11-12, using different pickling solutions can further improve the purity of sulfuryl fluoride. When the pickling solution is 80wt% concentrated sulfuric acid, it is more conducive to improving the purity of sulfuryl fluoride.
[0094] As can be seen from Examples 7 and 13-15, the preparation of sulfuryl fluoride in this application can be achieved by using different raw materials, different liquid sulfur-containing oxides or different fluoride salts, and the prepared sulfuryl fluoride has high purity and high yield.
[0095] See Figure 1 , Figure 1 The figure shows the ion chromatogram of a sample taken from a reactor section in Example 1. As can be seen from the figure, the elution times for the three ions are 2.3 min, 2.5 min, and 3.5 min, respectively. This confirms that the sample taken from the reactor section in Example 1 contains fluorosulfonate ions. Therefore, it is clear that the mixture of sulfur trioxide liquid and barium fluoride in Example 1 yielded barium fluorosulfonate.
[0096] Among them, FSO3 - F-, SO4 2- The method for configuring the markings is as follows:
[0097] FSO3 - Marking preparation: Take 0.2g of fluorosulfonic acid or fluorosulfonate sample, add a certain amount of deionized water to dilute to FSO3. -The concentrations of 5 ppm, 25 ppm, 50 ppm, 75 ppm, and 100 ppm were sonicated for 10 min (until no solid was visible to the naked eye), filtered through a sintered funnel, and 10 mL of the filtrate was analyzed by ion chromatography to obtain FSO3. - External standard curve.
[0098] F-mark preparation: Take 0.2g of sodium fluoride sample and dilute it with a certain amount of deionized water to F. - The concentrations of 5 ppm, 15 ppm, 25 ppm, 35 ppm, and 45 ppm were sonicated for 10 min (until no solid was visible to the naked eye), filtered through a sand core funnel, and 10 mL of the filtrate was taken for ion chromatography analysis to obtain the external standard curve of F-.
[0099] SO4 2- Marker preparation: Take 0.2g of fluorosulfonic acid or fluorosulfonate sample, add a certain amount of deionized water to dilute to SO42- content of 1ppm, 10ppm, 20ppm, 30ppm, and 40ppm, respectively, sonicate for 10min (until no solid is visible to the naked eye), filter through a sintered glass funnel, and take 10mL of the filtrate for ion chromatography analysis to obtain SO42-. 2- External standard curve.
[0100] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.
Claims
1. A method for preparing thioyl fluoride, characterized in that, Includes the following steps: Liquid sulfur-containing oxides are mixed with fluoride salts to undergo a liquid-solid reaction, yielding fluorosulfonic acid compounds. The fluorosulfonic acid compound is thermally decomposed to prepare thioyl fluoride; The chemical formula of the fluorosulfonic acid compound is M(SO3F). X Where M represents a metal cation or ammonium ion, and x represents the valence of the metal cation or ammonium ion.
2. The preparation method according to claim 1, characterized in that, The sulfur-containing oxides include at least one of sulfur trioxide, sulfur dioxide, sulfuryl chloride, and pyrosulfuric acid.
3. The preparation method according to claim 1 or 2, characterized in that, The fluoride salt includes at least one of barium fluoride, sodium fluoride, iron fluoride, magnesium fluoride, potassium fluoride, calcium fluoride, and ammonium fluoride.
4. The preparation method according to any one of claims 1 to 3, characterized in that, The molar ratio between the sulfur-containing oxide and the fluoride salt is (2-5):
1.
5. The preparation method according to any one of claims 1 to 4, characterized in that, The average particle size Dv50 of the fluoride salt is 50–200 μm; and / or, The water content of the fluoride salt is less than or equal to 0.01%; and / or, The purity of the fluoride salt is 98% to 100%.
6. The preparation method according to any one of claims 1 to 5, characterized in that, In the step of mixing liquid sulfur-containing oxides with fluoride salts to undergo a liquid-solid reaction and obtain fluorosulfonic acid compounds, The mixing temperature is between the melting point and boiling point of the liquid sulfur-containing oxide.
7. The preparation method according to claim 6, characterized in that, In the step of mixing liquid sulfur-containing oxides with fluoride salts to undergo a liquid-solid reaction and obtain fluorosulfonic acid compounds, The mixing temperature is -15 to 180℃.
8. The preparation method according to any one of claims 1 to 7, characterized in that, The step of mixing liquid sulfur-containing oxides with fluoride salts to undergo a liquid-solid reaction to obtain fluorosulfonic acid compounds includes: Liquid sulfur-containing oxides are mixed with fluoride salts to undergo a liquid-solid reaction, yielding fluorosulfonic acid compounds. The temperature is increased to vaporize and recover the unreacted sulfur-containing oxides; wherein the temperature of the increase is lower than the decomposition temperature of the fluorosulfonic acid compound.
9. The preparation method according to claim 8, characterized in that, In the step of heating to vaporize and recover unreacted sulfur-containing oxides, The recycling includes recycling using a vacuum method.
10. The preparation method according to any one of claims 1 to 9, characterized in that, In the step of thermally decomposing the fluorosulfonic acid compound to prepare thioyl fluoride... The temperature of the thermal decomposition is 500–1200°C; and / or, The thermal decomposition is carried out in a vacuum environment.
11. The preparation method according to any one of claims 1 to 10, characterized in that, The step of preparing thioyl fluoride by thermal decomposition of the fluorosulfonic acid compound includes: The fluorosulfonic acid compound was thermally decomposed to obtain gaseous products. The gaseous product was purified by acid washing to obtain thioyl fluoride.
12. The preparation method according to claim 11, characterized in that, In the step of purifying the gaseous product by acid washing to obtain thioyl fluoride... The acid washing and purification process uses an acid washing solution that includes at least one of citric acid, sulfurous acid, and concentrated sulfuric acid with a concentration of 70–98 wt.%.
13. A thioyl fluoride prepared by the preparation method according to any one of claims 1-12.