Method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate
By co-production of sodium trifluoromethanesulfonate and sodium tetrafluoroborate, the preparation method of sodium trifluoromethanesulfonate in the prior art has solved the problems of high purity requirements, high cost and low raw material utilization rate, and achieved high purity and high yield product preparation, and the process is simple, safe and environmentally friendly, and is suitable for industrial production.
Patent Information
- Application Number
- CN202311366000.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-10-20
- Publication Date
- 2025-04-22
AI Technical Summary
The existing preparation methods for sodium triflate have high requirements for the purity of triflate, high overall cost, low raw material utilization, low product purity, and large amounts of impurities.
By co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate, a high-purity sodium trifluoromethanesulfonyl fluoride gas was passed into an aqueous alkaline sodium ion solution, and after the reaction, organic solvent and boron trifluoride complex were added, and the insulation reaction and filtration were carried out. Finally, high-purity sodium trifluoromethanesulfonate and sodium tetrafluoroborate were obtained by crystallization.
It has achieved high product purity, high yield, simple process route, high raw material utilization, mild reaction conditions, simple operation, simple equipment, and no hazardous waste generation. The process is safe and environmentally friendly, and suitable for industrial production.
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Figure CN119859114A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of preparation of additives in sodium ion battery electrolytes, and in particular to a method for preparing sodium trifluoromethanesulfonate. Background Art
[0002] With the development of science and technology, people have gradually deepened their research on sodium ion salts. Among them, sodium trifluoromethanesulfonate can be used in many fields, such as the pharmaceutical industry, material industry, and new energy industry, because of its good stability, lipophilicity and membrane permeability due to its anionic structure.
[0003] In the prior art, there are two main methods for preparing sodium trifluoromethanesulfonate: 1. Using sodium carbonate and trifluoromethanesulfonic acid as raw materials, water as solvent, reacting, and obtaining sodium trifluoromethanesulfonate by concentrating and drying. The disadvantage of this method is that the purity of trifluoromethanesulfonic acid is high and the overall cost is high. 2. Using sodium carbonate and trifluoromethanesulfonyl fluoride as raw materials, water as solvent, reacting, filtering to remove sodium fluoride, and then filtering out sodium sulfate through a modified polytetrafluoroethylene filter membrane filter element, and finally concentrating and drying to obtain the product. The disadvantage of this method is that the raw material utilization rate is low, the product purity is low, and there are a large number of impurities such as sodium fluoride and sodium carbonate. Summary of the invention
[0004] The technical problem to be solved by the present invention is to provide a method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate. The product obtained by the preparation method has high purity, a simple process route, high raw material utilization rate, high yield, and can obtain two products, sodium trifluoromethanesulfonate and sodium tetrafluoroborate.
[0005] To solve the above problems, the technical solution adopted by the present invention is: a method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate, comprising the following steps.
[0006] A method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate comprises the following steps: 1. Passing trifluoromethanesulfonyl fluoride gas into an alkaline sodium ion aqueous solution, wherein the molar ratio of trifluoromethanesulfonyl fluoride to sodium ion is 0.5:0.99-1.01, to obtain a mixture of sodium trifluoromethanesulfonate and sodium fluoride; 2. After the mixture of sodium trifluoromethanesulfonate and sodium fluoride is dried by rotation, the first organic solvent is added, and the boron trifluoride complex is added, and the mixture is kept at 20° C. to 60° C. for reaction for 2 to 6 hours, and the sodium tetrafluoroborate wet crystals and the sodium trifluoromethanesulfonate solution are filtered; 3. Add organic solvent to the wet crystals of sodium tetrafluoroborate to wash, filter and dry to obtain the finished sodium tetrafluoroborate; add crystallization solvent to the sodium trifluoromethanesulfonate solution to crystallize, filter and dry to obtain the finished sodium trifluoromethanesulfonate. The structure of sodium trifluoromethanesulfonate is as follows: ; The structure of sodium tetrafluoroborate is shown below: ; Furthermore, in the aforementioned method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate, in step 1, the alkaline sodium ion aqueous solution is selected from one of a sodium carbonate aqueous solution, a sodium hydroxide aqueous solution, and a sodium bicarbonate aqueous solution.
[0007] Furthermore, in the aforementioned method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate, in step 1, the reaction temperature is controlled to be 5°C to 20°C.
[0008] Furthermore, in the aforementioned method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate, in step 1, when the pH of the reaction solution is 6-8, it is determined to be the reaction endpoint.
[0009] Furthermore, in the aforementioned method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate, in step 2, the first organic solvent is selected from any one of acetonitrile, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and ethyl acetate.
[0010] Furthermore, in the aforementioned method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate, in step 2, the molar ratio of the amount of the boron trifluoride complex in step 2 to the amount of trifluoromethanesulfonyl fluoride in step 1 is 1:0.8~1.0.
[0011] Furthermore, in the aforementioned method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate, in step 2, the boron trifluoride complex is selected from one of boron trifluoride acetonitrile, boron trifluoride dimethyl carbonate, boron trifluoride diethyl carbonate, boron trifluoride methyl ethyl carbonate, and boron trifluoride ethyl acetate corresponding to the first organic solvent.
[0012] Furthermore, in the aforementioned method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate, in step three, the sodium tetrafluoroborate wet crystals are washed with the same first organic solvent as that in step two.
[0013] Furthermore, in the aforementioned method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate, in step three, the crystallization solvent added to the sodium trifluoromethanesulfonate solution is selected from any one of toluene, dichloromethane, carbon tetrachloride, and n-hexane.
[0014] Furthermore, in the aforementioned method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate, in step three, the mass of the crystallization solvent is 2 to 5 times that of the filtrate.
[0015] The advantages of the present invention are: the method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate of the present invention has a simple process route, high raw material utilization rate, mild reaction conditions, simple operation, simple equipment, no hazardous waste is generated in the entire reaction, and the process is safe and environmentally friendly; one production line prepares two products, and each product has high purity and high yield. Therefore, the method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate of the present invention is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 This is the F spectrum of the sodium trifluoromethanesulfonate product prepared in Example 1.
[0017] Figure 2 This is the F spectrum of the sodium tetrafluoroborate product prepared in Example 1.
[0018] Figure 3 This is the B spectrum of the sodium tetrafluoroborate product prepared in Example 1. Implementation
[0019] Example 1: First, 1 mol of sodium carbonate was dissolved in 500 g of water to prepare a sodium carbonate aqueous solution, and then trifluoromethylsulfonyl fluoride was introduced into the sodium carbonate aqueous solution. The reaction temperature was controlled to be 15° C., and when the pH of the solution was 6.8, the introduction of trifluoromethylsulfonyl fluoride was stopped. The amount of trifluoromethylsulfonyl fluoride introduced was 1.005 mol.
[0020] The aqueous solution mixed with solids was spin-dried and 500 g of dimethyl carbonate was added, stirred to dissolve (some solids would be insoluble), 1.1 mol of dimethyl boron trifluoride carbonate was added, the temperature was raised to 60°C, the reaction was performed for 4 h, and after the reaction was completed, the filtrate was a sodium trifluoromethanesulfonate solution, and the solid was a crude sodium tetrafluoroborate.
[0021] The crude sodium tetrafluoroborate was washed with 500 g of dimethyl carbonate, filtered and dried to obtain 105.7 g of finished sodium tetrafluoroborate. Figure 2 As shown, the sodium tetrafluoroborate B spectrum is shown in Figure 3 shown.
[0022] The sodium trifluoromethanesulfonate solution was added with 3 times the mass of toluene to crystallize, filtered and dried to obtain 162 g of sodium trifluoromethanesulfonate product. Figure 1 shown.
[0023] Finished sodium trifluoromethanesulfonate test: Anion chromatography test: yield 94.3%, purity 99.91%, free fluorine 8ppm, sulfate 15ppm; ICP test: K: 0.87ppm, Fe: 0.12ppm, Ca: 0.79ppm, Pb: 0.06ppm; Potentiometric titration: chloride ion 0.96ppm; Karl Fischer titration: water 74ppm Finished product testing of sodium tetrafluoroborate: Anion chromatography test: yield 96.4%, purity 99.93%, free fluorine 21ppm, sulfate 10ppm; ICP test: K: 0.95ppm, Fe: 0.05ppm, Ca: 0.89ppm, Pb: 0.03ppm; potentiometric titration: chloride ion 1.03ppm; Karl Fischer titration: water 251ppm.
[0024] Example 2: 2 mol of sodium hydroxide was dissolved in 400 g of water to prepare a sodium hydroxide aqueous solution, and then trifluoromethylsulfonyl fluoride was passed into the sodium hydroxide aqueous solution. The reaction solution temperature was controlled at 5°C until the pH of the solution was 7.2, and the introduction of trifluoromethylsulfonyl fluoride was stopped. The amount of trifluoromethylsulfonyl fluoride introduced was 1.002 mol.
[0025] The aqueous solution mixed with solids was spin-dried and 500 g of dimethyl carbonate was added, stirred to dissolve (some solids would be insoluble), 1.05 mol of dimethyl boron trifluoride carbonate was added, the temperature was raised to 60°C, the reaction was performed for 4 h, and after the reaction was completed, the filtrate was a sodium trifluoromethanesulfonate solution, and the solid was a crude sodium tetrafluoroborate.
[0026] The crude sodium tetrafluoroborate was added with 500 g of dimethyl carbonate, washed, filtered and dried to obtain 105 g of finished sodium tetrafluoroborate.
[0027] The sodium trifluoromethanesulfonate solution was added with 4 times the mass of dichloromethane for crystallization, and the solution was filtered and dried to obtain 161 g of finished sodium trifluoromethanesulfonate.
[0028] Finished product testing of sodium trifluoromethanesulfonate: Anion chromatography testing: yield 93.7%, purity 99.92%, free fluorine 8ppm, sulfate 15ppm; ICP test: K: 0.76ppm, Fe: 0.21ppm, Ca: 0.54ppm, Pb: 0.03ppm; Potentiometric titration: chloride ion 0.67ppm; Karl Fischer titration: water 79.4ppm.
[0029] Finished sodium tetrafluoroborate test: Anion chromatography test: yield 95.6%, purity 99.93%, free fluorine 21ppm, sulfate 10ppm; ICP test: K: 0.84ppm, Fe: 0.17ppm, Ca: 0.69ppm, Pb: 0.03ppm; By potentiometric titration: chloride ion 1.03ppm; Determined by Karl Fischer titration: water content 207ppm.
[0030] Example 3: First, 1 mol of sodium carbonate was dissolved in 500 g of water to prepare a solution, and then trifluoromethylsulfonyl fluoride was introduced into the aqueous solution, and the temperature of the reaction solution was controlled to be stable at 15° C. When the pH of the solution reached 7.1, the introduction of trifluoromethylsulfonyl fluoride was stopped. The amount of trifluoromethylsulfonyl fluoride introduced was 1.003 mol.
[0031] The aqueous solution mixed with solids was spin-dried and 500 g of ethyl acetate was added, stirred to dissolve (some solids would be insoluble), 1.12 mol of ethyl acetate of boron trifluoride was added, the temperature was raised to 60°C, the reaction was performed for 4 h, and after the reaction was completed, the filtrate was a sodium trifluoromethanesulfonate solution, and the solid was a crude sodium tetrafluoroborate.
[0032] The crude sodium tetrafluoroborate was washed with 500 g of ethyl acetate, filtered and dried to obtain 104.4 g of finished sodium tetrafluoroborate.
[0033] The sodium trifluoromethanesulfonate solution was added with 4 times the mass of dichloromethane for crystallization, and the solution was filtered and dried to obtain 164 g of finished sodium trifluoromethanesulfonate.
[0034] The finished product of sodium trifluoromethanesulfonate was tested as follows: anion chromatography test: yield 95.3%, purity 99.92%, free fluorine 13ppm, sulfate 10ppm; ICP test: K: 0.74ppm, Fe: 0.03ppm, Ca: 0.83ppm, Pb: 0.01ppm; potentiometric titration: chloride ion 0.41ppm; Karl Fischer titration: water 63ppm.
[0035] The finished product of sodium tetrafluoroborate was tested as follows: anion chromatography test: yield 95.1%, purity 99.89%, free fluorine 17ppm, sulfate 14ppm; ICP test: K: 0.57ppm, Fe: 0.04ppm, Ca: 0.75ppm, Pb: 0.09ppm; potentiometric titration: chloride ion 0.21ppm; Karl Fischer titration: water 231ppm.
[0036] Example 4: 2 mol of sodium hydroxide was dissolved in 400 g of water to prepare a sodium hydroxide aqueous solution, and then trifluoromethylsulfonyl fluoride was introduced into the aqueous solution. The reaction solution temperature was controlled to 5° C., and the solution pH was 7.4. The introduction of trifluoromethylsulfonyl fluoride was stopped. The amount of trifluoromethylsulfonyl fluoride introduced was about 1.001 mol.
[0037] The aqueous solution mixed with solids was spin-dried and 500 g of acetonitrile was added, stirred to dissolve (some solids would be insoluble), 1.1 mol of boron trifluoride acetonitrile was added, the temperature was raised to 60°C, the reaction was performed for 4 h, and after the reaction was completed, the filtrate was a sodium trifluoromethanesulfonate solution, and the solid was a crude sodium tetrafluoroborate.
[0038] The crude sodium tetrafluoroborate was added with 500 g of acetonitrile for washing, filtering and drying to obtain 104.4 g of finished sodium tetrafluoroborate.
[0039] The sodium trifluoromethanesulfonate solution was added with 3 times the amount of toluene for crystallization, and the solution was filtered and dried to obtain 161 g of finished sodium trifluoromethanesulfonate.
[0040] The finished product of sodium trifluoromethanesulfonate was tested as follows: anion chromatography test: yield 93.7%, purity 99.94%, free fluorine 25ppm, sulfate 10ppm; ICP test: K: 0.77ppm, Fe: 0.23ppm, Ca: 0.51ppm, Pb: 0.06ppm; potentiometric titration: chloride ion 0.75ppm; Karl Fischer titration: water 88ppm.
[0041] The finished product of sodium tetrafluoroborate was tested as follows: anion chromatography test: yield 95.1%, purity 99.91%, free fluorine 17ppm, sulfate 10ppm; ICP test: K: 0.47ppm, Fe: 0.09ppm, Ca: 0.71ppm, Pb: 0.01ppm; potentiometric titration: chloride ion 0.89ppm; Karl Fischer titration: water 187ppm.
[0042] Example 5: 2 mol of sodium bicarbonate was dissolved in 1600 g of water to prepare a sodium bicarbonate aqueous solution, and then trifluoromethylsulfonyl fluoride was introduced into the aqueous solution. The reaction solution temperature was controlled at 20° C. and the solution pH was 7.3. The introduction of trifluoromethylsulfonyl fluoride was stopped. The amount of trifluoromethylsulfonyl fluoride introduced was 1.002 mol.
[0043] The aqueous solution mixed with solids was spin-dried and 500 g of dimethyl carbonate was added, stirred to dissolve (some solids would be insoluble), 1.1 mol of dimethyl boron trifluoride carbonate was added, the temperature was raised to 50°C, the reaction was performed for 4 h, and after the reaction was completed, the filtrate was a sodium trifluoromethanesulfonate solution, and the solid was a crude sodium tetrafluoroborate.
[0044] The crude sodium tetrafluoroborate was added with 500 g of dimethyl carbonate, washed, filtered and dried to obtain 102.7 g of finished sodium tetrafluoroborate.
[0045] The sodium trifluoromethanesulfonate solution was added with 3 times the amount of toluene for crystallization, and the solution was filtered and dried to obtain 162 g of finished sodium trifluoromethanesulfonate.
[0046] The finished product of sodium trifluoromethanesulfonate was tested as follows: anion chromatography test: yield 94.2%, purity 99.91%, free fluorine 27ppm, sulfate 8ppm; ICP test: K: 0.63ppm, Fe: 0.51ppm, Ca: 0.26ppm, Pb: 0.01ppm; potentiometric titration: chloride ion 0.78ppm; Karl Fischer titration: water content 94ppm.
[0047] The finished product of sodium tetrafluoroborate was tested as follows: anion chromatography test: yield 93.5%, purity 99.90%, free fluorine 14ppm, sulfate 12ppm; ICP test: K: 0.52ppm, Fe: 0.09ppm, Ca: 0.86ppm, Pb: 0.01ppm; potentiometric titration: chloride ion 0.88ppm; Karl Fischer titration: water 169ppm.
[0048] From the above examples, it can be concluded that the method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate of the present invention has a simple process route, high raw material utilization rate, mild reaction conditions, simple operation, simple equipment, no hazardous waste generated in the entire reaction, and a safe and environmentally friendly process; one production line prepares two products, each of which has high purity and high yield. Therefore, the method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate of the present invention is suitable for industrial production.
Claims
1. A method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate, comprising the following steps:
1. Passing trifluoromethanesulfonyl fluoride gas into an alkaline sodium ion aqueous solution, wherein the molar ratio of trifluoromethanesulfonyl fluoride to sodium ion is 0.5:0.99-1.01, to obtain a mixture of sodium trifluoromethanesulfonate and sodium fluoride; 2. After the mixture of sodium trifluoromethanesulfonate and sodium fluoride is dried by rotation, the first organic solvent is added, and the boron trifluoride complex is added, and the mixture is kept at 20° C. to 60° C. for reaction for 2 to 6 hours, and the sodium tetrafluoroborate wet crystals and the sodium trifluoromethanesulfonate solution are filtered; 3. Add an organic solvent to the wet sodium tetrafluoroborate crystals for washing, filtering and drying to obtain a finished sodium tetrafluoroborate product; add a crystallization solvent to the sodium trifluoromethanesulfonate solution for crystallization, filter and dry to obtain a finished sodium trifluoromethanesulfonate product.
2. A method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate according to claim 1, characterized in that: In step 1, the alkaline sodium ion aqueous solution is selected from one of a sodium carbonate aqueous solution, a sodium hydroxide aqueous solution, and a sodium bicarbonate aqueous solution.
3. A method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate according to claim 1, characterized in that: In step 1, the reaction temperature is controlled at 5°C~20°C.
4. A method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate according to claim 1, characterized in that: In step 1, when the pH of the reaction solution is 6-8, it is determined to be the reaction endpoint.
5. A method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate according to claim 1, characterized in that: In step 2, the first organic solvent is selected from any one of acetonitrile, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and ethyl acetate.
6. A method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate according to claim 1, characterized in that: The molar ratio of the amount of the boron trifluoride complex in step 2 to the amount of trifluoromethylsulfonyl fluoride in step 1 is 1:0.8-1.
0.
7. A method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate according to claim 5, characterized in that: In step 2, the boron trifluoride complex is selected from one of boron trifluoride acetonitrile, boron trifluoride dimethyl carbonate, boron trifluoride diethyl carbonate, boron trifluoride methyl ethyl carbonate, and boron trifluoride ethyl acetate corresponding to the first organic solvent.
8. A method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate according to claim 1, characterized in that: In step 3, the sodium tetrafluoroborate wet crystals are washed using the same first organic solvent as in step 2.
9. A method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate according to claim 1, characterized in that: In step 3, the crystallization solvent added to the sodium trifluoromethanesulfonate solution is selected from any one of toluene, dichloromethane, carbon tetrachloride and n-hexane.
10. A method for co-producing sodium trifluoromethanesulfonate and sodium tetrafluoroborate according to claim 1, characterized in that: In step 3, the mass of the crystallization solvent is 2 to 5 times that of the filtrate.