CN115894308B - Technological method for preparing trifluoromethanesulfonic acid - Google Patents
Technological method for preparing trifluoromethanesulfonic acid Download PDFInfo
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- CN115894308B CN115894308B CN202211377991.6A CN202211377991A CN115894308B CN 115894308 B CN115894308 B CN 115894308B CN 202211377991 A CN202211377991 A CN 202211377991A CN 115894308 B CN115894308 B CN 115894308B
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- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 20
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims abstract description 20
- 238000004821 distillation Methods 0.000 claims abstract description 15
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- SLVAEVYIJHDKRO-UHFFFAOYSA-N trifluoromethanesulfonyl fluoride Chemical compound FC(F)(F)S(F)(=O)=O SLVAEVYIJHDKRO-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 11
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007787 solid Chemical group 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 125000002827 triflate group Chemical class FC(S(=O)(=O)O*)(F)F 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 238000004062 sedimentation Methods 0.000 abstract description 3
- 229910004261 CaF 2 Inorganic materials 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 6
- 229910000792 Monel Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910000856 hastalloy Inorganic materials 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- KNWQLFOXPQZGPX-UHFFFAOYSA-N methanesulfonyl fluoride Chemical compound CS(F)(=O)=O KNWQLFOXPQZGPX-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a process method for preparing trifluoromethanesulfonic acid, which comprises the following steps: firstly, hydrolyzing to generate aqueous solution of trifluoromethane sulfonate, then adding proper amount of calcium salt into the aqueous solution to make precipitation reaction to remove F ‑ Obtaining a mixed solution, and carrying out solid-liquid separation on the mixed solution to remove CaF 2 And (3) precipitating, wherein the prepared clear solution is directly subjected to acidolysis reaction with sulfuric acid to prepare a trifluoromethanesulfonic acid aqueous solution, carrying out secondary solid-liquid separation on the aqueous solution, then carrying out distillation separation on the clear solution trifluoromethanesulfonic acid aqueous solution, and finally purifying the trifluoromethanesulfonic acid by reduced pressure distillation. The process of the invention effectively reduces F in the trifluoromethanesulfonic acid by adding calcium salt for sedimentation in the early stage ‑ The content of (2) reduces the difficulty of subsequent purification; meanwhile, the process eliminates the drying process of preparing the triflate salt aqueous solution into the triflate salt powder in the conventional process, and greatly reduces the energy consumption.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a process method for preparing trifluoromethanesulfonic acid.
Background
The industrial production generally synthesizes the trifluoromethanesulfonic acid by an electrochemical fluorination method, which comprises the following steps: 1. preparing trifluoro methanesulfonyl fluoride by electrolysis of methanesulfonyl chloride or methanesulfonyl fluoride serving as a raw material in anhydrous hydrogen fluoride; 2. performing hydrolysis reaction on trifluoromethanesulfonyl fluoride in alkali metal or hydroxide of alkali metal to prepare aqueous solution of trifluoromethanesulfonic acid salt; 3. evaporating, concentrating or spray drying the aqueous solution of the triflate to obtain solid powder of the triflate; 4. carrying out acidolysis reaction on the solid powder of the triflate and 100% sulfuric acid with the equivalent weight of 5-7 times to obtain a crude triflate; 5. and distilling or rectifying and purifying the crude triflic acid to prepare the triflic acid. The defects of the process are that: 1. the triflate is evaporated, concentrated or sprayed to prepare solid powder, so that the energy consumption is high and the site 6S is poor; 2. the prepared triflate has higher F-content and higher purification difficulty for subsequent products; 3. the acidolysis reaction is carried out by using 5-7 times of 100% sulfuric acid, the raw material cost is relatively high, and meanwhile, the excessive concentrated sulfuric acid is difficult to treat as hazardous waste.
Accordingly, a process for preparing trifluoromethanesulfonic acid has been proposed to solve the above problems.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process for preparing trifluoromethanesulfonic acid, which effectively reduces F in the trifluoromethanesulfonic acid by adding calcium salt for sedimentation in the early stage - The content of (2) reduces the difficulty of subsequent purification; meanwhile, the process eliminates the drying process of preparing the triflate salt aqueous solution into the triflate salt powder in the conventional process, and greatly reduces the energy consumption.
In order to solve the technical problems, the invention adopts the following technical scheme: a process for preparing trifluoromethanesulfonic acid comprising the steps of:
s1, carrying out hydrolysis reaction on trifluoro methanesulfonyl fluoride gas in alkali metal hydroxide to prepare trifluoro methanesulfonate aqueous solution;
s2, adding calcium salt into the trifluoro methane sulfonate aqueous solution obtained in the step S1 under normal temperature and normal pressure, fully stirring to obtain mixed solution, and carrying out solid-liquid separation on the mixed solution once to obtain clear liquid;
s3, slowly dropwise adding sulfuric acid into the clear solution obtained in the step S2 under the conditions of normal temperature and normal pressure while stirring, and carrying out acidolysis reaction to obtain a trifluoro methane sulfonic acid aqueous solution;
s4, performing secondary solid-liquid separation on the aqueous solution of the trifluoromethanesulfonic acid obtained in the S3, and removing calcium sulfate and solid residues to obtain clear solution of the aqueous solution of the trifluoromethanesulfonic acid;
s5, gradually heating the clear solution of the trifluoromethanesulfonic acid water solution obtained in the step S4 to perform at least one purification, and collecting a front fraction when the temperature is 30-95 ℃; collecting the rear fraction when the temperature is 80-175 ℃ to obtain the essence of the triflic acid.
Preferably, the hydroxide of the alkali metal in S1 is potassium hydroxide, sodium hydroxide, calcium hydroxide or barium hydroxide; the molar ratio of the alkali metal hydroxide to the trifluoromethanesulfonyl fluoride gas is (1.0 to 1.15): 1.0.
preferably, the calcium salt in S2 is CaCl 2 The addition amount of the calcium salt is equal to F in the aqueous solution of the triflate - 1.2 to 2 times the equivalent weight required for complete reaction.
Preferably, in the step S3, the concentration of the sulfuric acid is 30% -100%, and the mass ratio of the sulfuric acid to the clear liquid is 1: (1.1-1.5).
Preferably, the acidolysis reaction in S3 takes 0.5 to 2 hours.
Preferably, the primary solid-liquid separation in S2 and the secondary solid-liquid separation in S4 are both centrifugal separation methods.
Preferably, the purification in S5 is reduced pressure distillation or rectification, and the pressure of the reduced pressure distillation is-0.1 MPa to-0.05 MPa.
Compared with the prior art, the invention has the following advantages:
the process of the invention effectively reduces F in the trifluoromethanesulfonic acid by adding calcium salt for sedimentation in the early stage - The content of (2) reduces the difficulty of subsequent purification; the solid components in the mixed liquid are further removed through secondary solid-liquid separation; at the same time, the process removes the drying of the aqueous solution of the trifluoromethane sulfonate prepared into the trifluoromethane sulfonate in the conventional processThe process greatly reduces the energy consumption, and the sulfuric acid used for acidolysis reaction can be dilute sulfuric acid, and the addition of the sulfuric acid is reduced from 5-7 times of equivalent of the conventional process to 1.1-1.5 times of equivalent, so that the production process is simplified, the energy consumption is reduced, the difficulty of three-waste treatment is reduced, and meanwhile, the production cost is reduced.
The invention is described in further detail below with reference to the drawings and examples.
Drawings
FIG. 1 is a schematic illustration of the process flow of the method of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments.
Example 1
The process for preparing trifluoromethanesulfonic acid in this example, as shown in fig. 1, comprises the following steps:
s1, carrying out hydrolysis reaction on trifluoromethanesulfonyl fluoride gas in potassium hydroxide to obtain 3kg of trifluoromethanesulfonic acid salt aqueous solution; the mass concentration of the trifluoromethanesulfonic acid in the aqueous solution of the trifluoromethanesulfonic acid salt is 30.5 percent, F - =1550 ppm; the molar ratio of the potassium hydroxide to the trifluoromethanesulfonyl fluoride gas is 1.0:1.0;
s2, 20g of CaCl was added to 3kg of the aqueous solution of trifluoromethane sulfonate obtained in S1 under normal temperature (25 ℃) and normal pressure (101 KPa) 2 Fully stirring the powder to obtain a mixed solution, and carrying out solid-liquid separation on the mixed solution once to obtain a clear solution; the addition amount of the calcium salt is equal to F in the aqueous solution of the triflate - 1.2 to 2 times of the equivalent weight required for complete reaction;
s3, slowly dropwise adding 0.28kg of 92% sulfuric acid into the clear liquid obtained in the step S2 under the conditions of normal temperature (25 ℃) and normal pressure (101 KPa) while stirring, and carrying out acidolysis reaction for 0.5h to obtain a trifluoro methane sulfonic acid aqueous solution;
the acidolysis reaction kettle adopted in acidolysis reaction is glass, glass lining, monel alloy, hastelloy, silicon carbide, steel lining or sprayed PVDF/PFA/PTFE;
s4, performing secondary solid-liquid separation on the aqueous solution of the trifluoromethanesulfonic acid obtained in the S3, and removing calcium sulfate and solid residues to obtain clear solution of the aqueous solution of the trifluoromethanesulfonic acid;
s5, carrying out reduced pressure distillation on the aqueous solution clear solution of the trifluoromethanesulfonic acid obtained in the step S4, wherein the pressure of the reduced pressure distillation is-0.1 MPa, and collecting a front cut fraction when the temperature is 750mmHg and is 30-80 ℃; at 750mmHg, collecting a rear fraction at the temperature of 80-166 ℃, wherein the rear fraction is a crude product of trifluoromethanesulfonic acid, the crude product of trifluoromethanesulfonic acid is 0.68kg, and the yield is 94.7%; the content of the components in the crude triflic acid product is detected as shown in table 1:
TABLE 1 component content of crude trifluoromethanesulfonic acid in example 1
| Component name | CF 3 SO 3 H | F - | SO 4 2- | H 2 O |
| Content of | About 88% | 12.5ppm | 18500 | 10.2％ |
Will be 0.68kg the crude triflic acid is distilled and purified under reduced pressure at the vacuum degree of 752mmHg, then the temperature is raised to 75-82 ℃, condensate water reflux is started for 4 hours, condensate water is gradually adjusted to control the distillation speed, a receiving bottle is replaced when 95g of distillate is received, distillation and collection are continued, when the temperature is 82-93 ℃, the rear fraction is collected, the mass of the rear fraction is 0.55kg, F in the rear fraction is detected - ＝6.5ppm，SO 4 2- ＝650ppm，H 2 O＝3500ppm；
Continuously distilling the rear fraction, namely 0.55kg of trifluoromethanesulfonic acid under reduced pressure, and obtaining 0.46kg of the fraction under the conditions of vacuum degree 742mmHg and temperature 75-85 ℃ to obtain a fine trifluoromethanesulfonic acid product, wherein the component content of the fine trifluoromethanesulfonic acid product is shown in the table 2 after detection:
table 2 the component content scale in triflic acid gives a fine triflic acid product;
| component name | CF 3 SO 3 H | F - | SO 4 2- | H 2 O |
| Content of | About 99.8% | 6.8ppm | 32ppm | 365ppm |
Example 2
The process for preparing trifluoromethanesulfonic acid in this example, as shown in fig. 1, comprises the following steps:
s1, carrying out hydrolysis reaction on trifluoromethanesulfonyl fluoride gas in sodium hydroxide to prepare 2.5kg of aqueous solution of trifluoromethanesulfonic acid salt; the mass concentration of the trifluoromethanesulfonic acid in the aqueous solution of the trifluoromethanesulfonic acid salt is 49.5 percent, F - =182 ppm; the molar ratio of the sodium hydroxide to the trifluoromethanesulfonyl fluoride gas is 1.15:1.0;
s2 to 2.5kg of the aqueous solution of trifluoromethane sulfonate obtained in S1 was added 2.5g of CaCl under normal temperature (23 ℃) and normal pressure (101 KPa) 2 Fully stirring the powder to obtain a mixed solution, and carrying out solid-liquid separation on the mixed solution once to obtain a clear solution; the addition amount of the calcium salt is as that F in the aqueous solution of the triflate - 1.2 to 2 times of the equivalent weight required for complete reaction;
s3, slowly dropwise adding 0.56kg of sulfuric acid with the mass fraction of 75% into the clear liquid obtained in the step S2 under the conditions of normal temperature (23 ℃) and normal pressure (101 KPa) while stirring, and carrying out acidolysis reaction for 1h to obtain a trifluoro methane sulfonic acid aqueous solution;
the acidolysis reaction kettle adopted in acidolysis reaction is glass, glass lining, monel alloy, hastelloy, silicon carbide, steel lining or sprayed PVDF/PFA/PTFE;
s4, performing secondary solid-liquid separation on the aqueous solution of the trifluoromethanesulfonic acid obtained in the S3, and removing calcium sulfate and solid residues to obtain clear solution of the aqueous solution of the trifluoromethanesulfonic acid;
s5, carrying out reduced pressure distillation on the aqueous solution clear solution of the trifluoromethanesulfonic acid obtained in the step S4, wherein the pressure of the reduced pressure distillation is-0.05 MPa, and collecting a front cut fraction when the temperature is between 35 and 83 ℃ at 750 mmHg; collecting a rear fraction at the temperature of 83-166 ℃ at 750mmHg, wherein the rear fraction is a crude triflic acid product, the crude triflic acid product is 0.82kg, and the yield is 95.3%; the content of the components in the crude triflic acid product is detected as shown in table 3:
TABLE 3 component content of crude trifluoromethanesulfonic acid in example 2
| Component name | CF 3 SO 3 H | F - | SO 4 2- | H 2 O |
| Content of | About 88% | 12.5ppm | 18500 | 10.2％ |
Performing reduced pressure distillation purification on 0.82kg of the crude triflic acid at a vacuum degree of 752mmHg, heating to 77-85 ℃, starting condensate water reflux for 6h, gradually adjusting condensate water to control the distillation speed, changing a receiving bottle when the distillate is received to 108g, continuously collecting by distillation, collecting a rear fraction at a temperature of 85-94 ℃, wherein the mass of the rear fraction (triflic acid) is 0.68kg, and detecting F in the rear fraction - ＝2.5ppm，SO 4 2- ＝247ppm，H 2 O＝4200ppm；
Continuously distilling the rear fraction, namely 0.68kg of trifluoromethanesulfonic acid, and obtaining 0.45kg of the fraction at the vacuum degree of 742mmHg and the temperature of 77-88 ℃ to obtain a fine trifluoromethanesulfonic acid product, wherein the component content of the fine trifluoromethanesulfonic acid product is shown in the table 4 after detection:
TABLE 4 component content of the essence of trifluoromethanesulfonic acid in example 2
| Component name | CF 3 SO 3 H | F - | SO 4 2- | H 2 O |
| Content of | About 99.9% | 1.2ppm | 16ppm | 285ppm |
Example 3
The process for preparing trifluoromethanesulfonic acid in this example, as shown in fig. 1, comprises the following steps:
s1, carrying out hydrolysis reaction on trifluoromethanesulfonyl fluoride gas in calcium hydroxide to obtain 3.8kg of aqueous solution of trifluoromethanesulfonic acid salt; the mass concentration of the trifluoromethanesulfonic acid in the aqueous solution of the trifluoromethanesulfonic acid salt is 47.8 percent, F - =685 ppm; the molar ratio of the alkaline earth metal to the trifluoromethanesulfonyl fluoride gas is 1.0:1.0; the molar ratio of the calcium hydroxide to the trifluoromethanesulfonyl fluoride gas is 1.13:1.0;
s2, 3.9g of CaCl was added to 3.8kg of the aqueous solution of trifluoromethane sulfonate obtained in S1 under normal temperature (20 ℃ C.) and normal pressure (101 KPa) 2 Fully stirring the powder to obtain a mixed solution, and carrying out solid-liquid separation on the mixed solution once to obtain a clear solution;the addition amount of the calcium salt is as that F in the aqueous solution of the triflate - 1.2 to 2 times of the equivalent weight required for complete reaction;
s3, slowly dropwise adding 0.80kg of 68% sulfuric acid in mass fraction into the clear liquid obtained in the step S2 under the conditions of normal temperature (20 ℃) and normal pressure (101 KPa) while stirring, and carrying out acidolysis reaction for 2 hours to obtain a trifluoro methane sulfonic acid aqueous solution;
the acidolysis reaction kettle adopted in acidolysis reaction is glass, glass lining, monel alloy, hastelloy, silicon carbide, steel lining or sprayed PVDF/PFA/PTFE;
s4, performing secondary solid-liquid separation on the aqueous solution of the trifluoromethanesulfonic acid obtained in the S3, and removing calcium sulfate and solid residues to obtain clear solution of the aqueous solution of the trifluoromethanesulfonic acid;
s5, rectifying the clear solution of the trifluoromethanesulfonic acid water solution obtained in the step S4, and collecting a front fraction at the temperature of 42-95 ℃ at 720 mmHg; collecting the middle distillate when the temperature is 95-128 ℃; collecting the rear fraction when the temperature is 128-175 ℃;
the middle distillate is essence of trifluoromethanesulfonic acid, the weight of the essence of trifluoromethanesulfonic acid is 0.98kg, and the yield is 39.2% (based on clear liquid); the component content of the triflic acid fine product is shown in table 5:
TABLE 5 component content of the essence of trifluoromethanesulfonic acid in example 3
| Component name | CF 3 SO 3 H | F - | SO 4 2- | H 2 O |
| Content of | About 99.9% | 3.1ppm | 9ppm | 146ppm |
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (3)
1. A process for preparing trifluoromethanesulfonic acid, comprising the steps of:
s1, carrying out hydrolysis reaction on trifluoromethanesulfonyl fluoride gas in sodium hydroxide, calcium hydroxide or barium hydroxide to obtain aqueous solution of trifluoromethanesulfonic acid salt;
the molar ratio of the sodium hydroxide to the trifluoromethanesulfonyl fluoride gas is (1.0-1.15): 1.0; the molar ratio of the calcium hydroxide to the trifluoromethanesulfonyl fluoride gas is (1.0-1.15): 1.0, wherein the molar ratio of the barium hydroxide to the trifluoromethanesulfonyl fluoride gas is (1.0 to 1.15): 1.0;
s2, adding calcium salt into the trifluoro methane sulfonate aqueous solution obtained in the step S1 under normal temperature and normal pressure, fully stirring to obtain mixed solution, and carrying out solid-liquid separation on the mixed solution once to obtain clear liquid; the calcium salt is CaCl 2 The addition amount of the calcium salt is 1.2-2 times of the equivalent weight required by complete reaction with F-in the trifluoro methane sulfonate aqueous solution;
s3, slowly dropwise adding sulfuric acid into the clear solution obtained in the step S2 under the conditions of normal temperature and normal pressure while stirring, and carrying out acidolysis reaction to obtain a trifluoro methane sulfonic acid aqueous solution;
the concentration of sulfuric acid is 30% -100%, and the mass ratio of sulfuric acid to clear liquid is 1: (1.1-1.5); the acidolysis reaction time is 0.5-2 h;
s4, performing secondary solid-liquid separation on the aqueous solution of the trifluoromethanesulfonic acid obtained in the S3, and removing calcium sulfate and solid residues to obtain clear solution of the aqueous solution of the trifluoromethanesulfonic acid;
s5, gradually heating the clear solution of the trifluoromethanesulfonic acid water solution obtained in the step S4 to perform at least one purification, and collecting a front fraction when the temperature is 30-95 ℃; collecting the rear fraction when the temperature is 80-175 ℃ to obtain the essence of the triflic acid.
2. The process for preparing trifluoromethanesulfonic acid according to claim 1, wherein the primary solid-liquid separation in S2 and the secondary solid-liquid separation in S4 are both centrifugal separation methods.
3. The process for preparing trifluoromethanesulfonic acid according to claim 1, wherein the purification in S5 is reduced pressure distillation or rectification, and the pressure of the reduced pressure distillation is-0.1 MPa to-0.05 MPa.
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