Preparation method of sodium fluoborate
Sodium fluoroborate was prepared by reacting boron trifluoride-11 methyl ether complex with sodium fluoride, which solved the problem of processing boron trifluoride-11 methyl ether complex and achieved the preparation of high-purity sodium fluoroborate and improved its economic efficiency.
Patent Information
- Application Number
- CN202511798038.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-02
- Publication Date
- 2026-03-17
AI Technical Summary
Existing technologies are unable to effectively process boron trifluoride-11 methyl ether complex byproducts, leading to reduced safety risks and economic efficiency, and making it impossible to convert them into high-value sodium fluoroborate.
High-purity sodium fluoroborate was prepared by reacting boron trifluoride-11 methyl ether complex with sodium fluoride. The byproducts were utilized through a multi-step process including hydrolysis, filtration, evaporation, crystallization, and recycling.
The preparation of high-purity sodium fluoroborate has been achieved, which improves the utilization rate of raw materials and the economic efficiency of the reaction, reduces safety risks, and enhances the comprehensive utilization value of by-products.
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of nuclear chemical technology, in particular to a preparation method of sodium fluoroborate. BACKGROUND
[0002] Nuclear grade boron-10 acid is a high-performance chemical material with high abundance, high purity and high performance that can meet the use in the field of nuclear industry. It is important in the fields of nuclear industry, national defense industry, medical treatment and the like. In the enrichment process of the raw material boron trifluoride-10 methyl ether complex of nuclear grade boron-10 acid, a large amount of boron trifluoride-11 methyl ether complex is produced. The enrichment degree of boron-11 in the by-product is mostly 80-95%, which is difficult to utilize. Moreover, the by-product is a dangerous chemical product, and long-term storage will bring great safety risks. In order to reduce the safety risks, the common method at present is to dispose the by-product as a dangerous chemical waste product by a third party, thereby generating liquid waste treatment costs, and greatly reducing the economic efficiency of the production line of nuclear grade boron-10 acid. How to effectively dispose of the large amount of boron trifluoride-11 methyl ether complex produced in the enrichment process of boron trifluoride-10, reduce the great safety risks brought by long-term storage, and realize the goal of recycling the boron trifluoride-11 methyl ether complex waste, has become a key link of the production line of nuclear grade boron-10 acid.
[0003] According to the investigation, the application range of sodium fluoroborate is very wide, including the fields of catalysts, electronic devices, liquid crystal displays and the like. For example, sodium fluoroborate can be used as a catalyst for organic synthesis reactions, such as olefin addition and oxidation reactions; in electronic devices, sodium fluoroborate can be used as an ionic liquid for the electrolyte of batteries and supercapacitors; in liquid crystal displays, sodium fluoroborate can be used as a ligand of liquid crystal molecules to control the orientation and arrangement of the liquid crystal molecules. In addition to having a wide market, the annual consumption of sodium fluoroborate is huge, and the market price is about 10-20 thousand yuan / ton, which has high economic value. Therefore, through the development of sodium fluoroborate from boron trifluoride-11 methyl ether complex, the economic efficiency of the comprehensive utilization of by-products can be greatly improved. SUMMARY
[0004] The purpose of the present application is to provide a preparation method of sodium fluoroborate, which uses boron trifluoride-11 methyl ether complex as a raw material, and develops high-purity sodium fluoroborate by reacting with sodium fluoride.
[0005] The technical solution of the present application is as follows: a preparation method of sodium fluoroborate, comprising the following steps:
[0006] Step a: Dissolve the sodium fluoride and sodium sulfate solid residue generated during the production of nuclear-grade boron-10 acid in a certain amount of deionized water, stir at a certain temperature T1, then centrifuge and filter to obtain raw material sodium fluoride. Then add boron trifluoride methyl ether complex and sodium fluoride to the reaction in a certain proportion. After the reaction is completed, add a certain amount of deionized water, then heat and stir at a certain temperature T2, and finally filter.
[0007] Step b: Evaporate the filtered solution. When the remaining volume of the solution after evaporation reaches a certain level, crystallize it at a certain temperature T3, and then filter it again.
[0008] Step c: Dissolve the filtered sodium fluoroborate-10 in a certain amount of ultrapure water, react at a certain temperature T4, then cool to a certain temperature T5, filter and dry to obtain high-purity sodium fluoroborate.
[0009] In step a, the mass ratio of sodium fluoride, sodium sulfate solid residue and deionized water is 1:2 to 1:10, and the reaction temperature T1 is 60 to 100℃.
[0010] The molar ratio of boron trifluoride-10 methyl ether complex to sodium fluoride is 1:0.9 to 1:2, the mass ratio of sodium fluoride to deionized water is 1:2 to 1:20, and the reaction temperature T2 is 50 to 90℃.
[0011] In step b, the remaining volume of the solution after evaporation is 1 / 6 to 1 / 2 of the volume before evaporation, and the crystallization temperature T3 is 25 to 40°C.
[0012] In step c, the mass ratio of ultrapure water to sodium fluoroborate is 1:1 to 1:3, the heating and dissolving temperature T4 is 60 to 80°C, and the cooling and filtration temperature T5 is 20 to 30°C.
[0013] In step c, the reaction time is 30 minutes.
[0014] It also includes step d, in which the filtered solution from step b is reused in step a to replenish deionized water, and the solution from step c is reused in step (b), and the reaction continues according to steps a to c.
[0015] The significant advantages of this invention are as follows: By using boron trifluoride-11 complex as raw material, sodium fluoroborate is directly prepared, eliminating the step of first converting it to boric acid in the traditional process. This optimizes the process steps, reduces reaction time, shortens the reaction flow, improves raw material utilization, and enhances the economic efficiency of the reaction.
[0016] Based on the different solubilities of sodium fluoride, sodium fluoroborate, and impurity ion fluoride salts, the content of each ion in the solution was cleverly set in different reactions. During the production process, the removal of impurity ions was automatically achieved, resulting in the development of high-purity (≥99%) sodium fluoroborate. Furthermore, through cyclic reactions, the product yield was achieved to reach a target of no less than 90%.
[0017] The raw materials used are all byproducts from the production process of nuclear-grade boron-10 acid. One of the raw materials, boron trifluoride-11 methyl ether complex, is liquid waste generated during the enrichment process. The other raw material, sodium fluoride, is a solid waste byproduct generated during the hydrolysis of boron trifluoride-10 methyl ether complex. By comprehensively utilizing the byproducts from the production process of nuclear-grade boron-10 acid, they are converted into sodium fluoroborate, which is in huge domestic demand. This maximizes the resource utilization of waste, achieves the goal of reducing costs and increasing efficiency in the production line, and provides strong technical support for the green and sustainable development of the production line. Detailed Implementation
[0018] Many specific details are set forth in the following description to provide a full understanding of this application. However, this application can be implemented in many other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of this application; therefore, this application is not limited to the specific embodiments disclosed below.
[0019] The terminology used in one or more embodiments of this application is for the purpose of describing particular embodiments only and is not intended to limit the scope of one or more embodiments of this application. The singular forms “a,” “the,” and “the” used in one or more embodiments of this application and in the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise. It should also be understood that the term “and / or” used in one or more embodiments of this application refers to and includes any or all possible combinations of one or more associated listed items.
[0020] It should be understood that although the terms first, second, etc., may be used to describe various information in one or more embodiments of this application, such information should not be limited to these terms. These terms are only used to distinguish information of the same type from one another. For example, first may also be referred to as second without departing from the scope of one or more embodiments of this application, and similarly, second may also be referred to as first.
[0021] A method for preparing sodium fluoroborate includes the following steps:
[0022] (a) Hydrolysis filtration: Sodium fluoride and sodium sulfate solid residue generated during the production of nuclear-grade boron-10 acid are dissolved in a certain amount of deionized water and stirred at a certain temperature T1 for 60 min. Then, the mixture is centrifuged and filtered to obtain raw material sodium fluoride. Then, boron trifluoride methyl ether complex and sodium fluoride are gradually added to the reactor in a certain proportion. After the reaction is completed, a certain amount of deionized water is added, and the mixture is heated and stirred at a certain temperature T2 for 2 h. Finally, the mixture is filtered.
[0023] Specifically, the mass ratio of sodium fluoride, sodium sulfate solid residue to deionized water is 1:2 to 1:10, and the reaction temperature T1 is 60 to 100℃.
[0024] Specifically, the molar ratio of boron trifluoride-10 methyl ether complex to sodium fluoride is 1:0.9 to 1:2, the mass ratio of sodium fluoride to deionized water is 1:2 to 1:20, and the reaction temperature T2 is 50 to 90℃.
[0025] Specifically, stir for 60 minutes.
[0026] (b) Evaporation crystallization: The filtered solution is evaporated. When the remaining volume of the solution after evaporation reaches a certain level, crystallization is carried out at a certain temperature T3, and then filtered again.
[0027] Specifically, the volume of the solution remaining after evaporation is 1 / 6 to 1 / 2 of the volume before initial evaporation, and the crystallization temperature T3 is 25 to 40°C.
[0028] (c) Washing and purification: Dissolve the filtered sodium fluoroborate-10 in a certain amount of ultrapure water, react at a certain temperature T4 for 30 min, then cool to a certain temperature T5, filter and dry to obtain high-purity sodium fluoroborate.
[0029] Specifically, the mass ratio of ultrapure water to sodium fluoroborate is 1:1 to 1:3, the heating and dissolving temperature T4 is 60 to 80°C, and the cooling and filtration temperature T5 is 20 to 30°C.
[0030] (d) A cyclical reaction is carried out, in which the filtered solution from step (b) is reused in step (a) to replenish deionized water, and the solution from step (c) is reused in step (b). This process is repeated from step (a) to (c) to achieve the cyclical preparation of sodium fluoroborate.
[0031] Several specific embodiments are given below.
[0032] Example 1
[0033] (a) Hydrolysis and filtration: 1 kg of sodium fluoride and sodium sulfate solid residue generated during the production of nuclear-grade boron-10 acid were dissolved in 2 L of deionized water and stirred at 80 °C for 60 min. Then, the mixture was centrifuged and filtered to obtain 786 g of sodium fluoride product with a water content of 11.99%. 1711 g of boron trifluoride methyl ether complex and 786 g of sodium fluoride were gradually added to the reaction vessel. After the reaction was completed, 1.6 L of deionized water was added, and the mixture was heated and stirred at 75 °C for 2 h. Then, the mixture was filtered to obtain 1.9 L of solution.
[0034] (b) Evaporation crystallization: The filtered solution was evaporated. When the solution was evaporated to 500 mL, crystallization was carried out at 28 °C. The solution was then filtered to obtain 1708 g of wet sodium fluoroborate with a water content of 12.98%.
[0035] (c) Washing and purification: 1708g of sodium fluoroborate obtained after filtration was dissolved in 900mL of ultrapure water, reacted at 60℃ for 30min, then cooled to 25℃, filtered and dried to obtain 1036g of sodium fluoroborate with a purity of 99.86%.
[0036] (d) Mother liquor reuse: The filtered solution from step (b) is reused in step (a) to replenish deionized water. The solution from step (c) is then reused in step (b), and the reaction is continued according to steps 1 to 4 to obtain 1669g of sodium fluoroborate with a purity of 99.52%. The product yield after recycling is 92.53%.
[0037] Example 2
[0038] (a) Hydrolysis and filtration: 1 kg of sodium fluoride and sodium sulfate solid residue generated during the production of nuclear-grade boron-10 acid were dissolved in 10 L of deionized water and stirred at 80 °C for 60 min. Then, the mixture was centrifuged and filtered to obtain 685 g of sodium fluoride product with a water content of 10.57%. 1659 g of boron trifluoride methyl ether complex and 685 g of sodium fluoride were gradually added to the reaction vessel. After the reaction was completed, 3 L of deionized water was added, and the mixture was heated and stirred at 75 °C for 2 h. Then, the mixture was filtered to obtain 3.6 L of solution.
[0039] (b) Evaporation crystallization: The filtered solution was evaporated. When the solution was evaporated to 600 mL, crystallization was carried out at 25 °C. The solution was then filtered to obtain 1538 g of wet sodium fluoroborate with a water content of 11.58%.
[0040] (c) Washing and purification: 1538g of sodium fluoroborate obtained after filtration was dissolved in 800mL of ultrapure water, reacted at 60℃ for 30min, then cooled to 25℃, filtered and dried to obtain 986g of sodium fluoroborate with a purity of 99.91%.
[0041] (d) Mother liquor reuse: The filtered solution from step (b) is reused in step (a) to replenish deionized water. The solution from step (c) is then reused in step (b), and the reaction is continued according to steps 1 to 4 to obtain 1472g of sodium fluoroborate with a purity of 99.52%. The yield of the batch product after recycling is 91.83%.
[0042] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
[0043] It should be noted that, for the sake of simplicity, the foregoing method embodiments are all described as a series of actions. However, those skilled in the art should understand that this application is not limited to the described order of actions, as some steps may be performed in other orders or simultaneously according to this application. Furthermore, those skilled in the art should also understand that the embodiments described in the specification are preferred embodiments, and the actions and modules involved are not necessarily essential to this application.
[0044] In the above embodiments, the descriptions of each embodiment have different focuses. For parts not described in detail in a certain embodiment, please refer to the relevant descriptions in other embodiments.
[0045] The preferred embodiments disclosed above are merely illustrative of this application. The optional embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this application. These embodiments are selected and specifically described in this application to better explain the principles and practical applications of this application, thereby enabling those skilled in the art to better understand and utilize this application.
Claims
1. A process for the preparation of sodium fluoborate, characterized in that: The method comprises the following steps: Step a: dissolve the sodium fluoride and sodium sulfate solid residue produced in the production process of nuclear grade boron-10 acid in a certain amount of deionized water, stir at a certain temperature T1, then centrifugal filtration to obtain raw material sodium fluoride, then add boron trifluoride methyl ether complex and sodium fluoride to the reaction according to a certain proportion, after the reaction is completed, add a certain amount of deionized water, then heat and stir at a certain temperature T2, and finally filter; Step b: evaporate the filtered solution, when the remaining volume of the solution after evaporation reaches a certain degree, crystallize at a certain temperature T3, then filter again; Step c: dissolve the filtered sodium fluoroborate-10 in a certain amount of ultrapure water, react at a certain temperature T4, then cool to a certain temperature T5, filter and dry to obtain high-purity sodium fluoroborate.
2. The method of claim 1, wherein: In step a, the mass ratio of sodium fluoride and sodium sulfate solid residue to deionized water is 1:2-1:10, and the reaction temperature T1 is 60-100℃.
3. The method for preparing sodium fluoroborate according to claim 2, characterized in that: The molar ratio of boron trifluoride-10 methyl ether complex to sodium fluoride is 1:0.9-1:2, the mass ratio of sodium fluoride to deionized water is 1:2-1:20, and the reaction temperature T2 is 50-90℃.
4. The method for preparing sodium fluoroborate according to claim 1, characterized in that: In step b, the remaining volume of the solution after evaporation is 1 / 6-1 / 2 of the volume before evaporation, and the crystallization temperature T3 is 25-40℃.
5. The method for preparing sodium fluoroborate according to claim 1, characterized in that: In step c, the mass ratio of ultrapure water to sodium fluoroborate is 1:1-1:3, the heating and dissolving temperature T4 is 60-80℃, and the cooling and filtering temperature T5 is 20-30℃.
6. The method for preparing sodium fluoroborate according to claim 5, characterized in that: In step c, the reaction time is 30 minutes.
7. The method for preparing sodium fluoroborate according to claim 1, characterized in that: It also includes step d, returning the filtered solution in step b to step a for deionized water replenishment, and returning the solution in step c to step b, and continuing the reaction according to steps a-c.