CN115894308A - Process for preparing trifluoromethanesulfonic acid - Google Patents
Process for preparing trifluoromethanesulfonic acid Download PDFInfo
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- CN115894308A CN115894308A CN202211377991.6A CN202211377991A CN115894308A CN 115894308 A CN115894308 A CN 115894308A CN 202211377991 A CN202211377991 A CN 202211377991A CN 115894308 A CN115894308 A CN 115894308A
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- trifluoromethanesulfonic acid
- aqueous solution
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- triflate
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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 74
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 44
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000004821 distillation Methods 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 16
- SLVAEVYIJHDKRO-UHFFFAOYSA-N trifluoromethanesulfonyl fluoride Chemical compound FC(F)(F)S(F)(=O)=O SLVAEVYIJHDKRO-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 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
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 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
- 238000001035 drying 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
- 239000007789 gas Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000792 Monel Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 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
- 238000001514 detection method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 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
- 238000010586 diagram Methods 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
- 238000002360 preparation method Methods 0.000 description 1
- 238000001694 spray drying Methods 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 a triflate aqueous solution, then adding a proper amount of calcium salt into the aqueous solution to carry out precipitation reaction to remove F ‑ Obtaining a mixed solution, and performing solid-liquid separation on the mixed solution to remove CaF 2 Precipitating, directly carrying out acidolysis reaction on the prepared clear liquid and sulfuric acid to prepare trifluoromethanesulfonic acid aqueous solution, carrying out secondary solid-liquid separation on the aqueous solution, then carrying out distillation separation on the clear liquid trifluoromethanesulfonic acid aqueous solution, and finally purifying trifluoromethanesulfonic acid by reduced pressure distillation. The process effectively reduces F in the trifluoromethanesulfonic acid by adding calcium salt to settle in the early stage ‑ The content of (A) reduces the difficulty of subsequent purification; meanwhile, the process removes the conventional process of preparing the triflate powder from the triflate aqueous solutionThe drying process of the body 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
Industrial production trifluoromethanesulfonic acid is generally synthesized by an electrochemical fluorination process comprising the following steps: 1. using methylsulfonyl chloride or methylsulfonyl fluoride as a raw material to prepare trifluoromethanesulfonyl fluoride in anhydrous hydrogen fluoride through electrolysis; 2. carrying out hydrolysis reaction on trifluoromethanesulfonyl fluoride in alkali metal or hydroxide of alkali metal to prepare a trifluoromethanesulfonate aqueous solution; 3. evaporating, concentrating or spray drying the triflate aqueous solution to obtain triflate solid powder; 4. carrying out acidolysis reaction on the triflate solid powder and 100% sulfuric acid with 5-7 times equivalent weight to prepare a crude triflate; 5. and (3) distilling or rectifying and purifying the crude trifluoromethanesulfonic acid to prepare trifluoromethanesulfonic acid. The disadvantages of the process are as follows: 1. the triflate is evaporated, concentrated or sprayed to prepare solid powder, so that the energy consumption is high, and the field 6S is poor; 2. the prepared triflate has high F-content and high difficulty in purifying subsequent products; 3. the acidolysis reaction is carried out by using 5-7 times of 100% sulfuric acid, the cost of raw materials is relatively high, and excessive concentrated sulfuric acid is difficult to treat as hazardous waste.
Therefore, a process for preparing trifluoromethanesulfonic acid was 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, aiming at the defects of the prior art, wherein the process effectively reduces F in the trifluoromethanesulfonic acid by adding calcium salt to settle in the early stage - The content of (A) reduces the difficulty of subsequent purification; at the same time the process is removedThe drying process of preparing the triflate powder from the triflate aqueous solution in the conventional process is adopted, so that the energy consumption is greatly reduced.
In order to solve the technical problems, the invention adopts the technical scheme that: a process for the preparation of trifluoromethanesulfonic acid, which process comprises the steps of:
s1, carrying out hydrolysis reaction on trifluoromethanesulfonyl fluoride gas in an alkali metal hydroxide to prepare a trifluoromethanesulfonate aqueous solution;
s2, adding a calcium salt into the triflate aqueous solution obtained in the S1 under the conditions of normal temperature and normal pressure, fully stirring to obtain a mixed solution, and carrying out primary solid-liquid separation on the mixed solution to obtain a clear solution;
s3, slowly dropwise adding sulfuric acid into the clear liquid obtained in the S2 while stirring under the conditions of normal temperature and normal pressure, and carrying out acidolysis reaction to obtain a trifluoromethanesulfonic acid aqueous solution;
s4, carrying out secondary solid-liquid separation on the trifluoromethanesulfonic acid aqueous solution obtained in S3, and removing calcium sulfate and solid residues to obtain a trifluoromethanesulfonic acid aqueous solution clear solution;
s5, gradually heating the clear liquid of the aqueous solution of the trifluoromethanesulfonic acid obtained in S4 to perform at least one purification, and collecting front fractions at the temperature of 30-95 ℃; when the temperature is 80-175 ℃, collecting the later fraction to obtain the refined trifluoromethanesulfonic 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 (1.0-1.15): 1.0.
preferably, the calcium salt in S2 is CaCl 2 The calcium salt is added in an amount of F in the aqueous solution of the triflate - 1.2 to 2 times the equivalent required to carry out the complete reaction.
Preferably, the concentration of the sulfuric acid in the S3 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 is performed for 0.5h to 2h.
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 vacuum distillation or rectification, and the pressure of the vacuum distillation is-0.1 MPa to-0.05 MPa.
Compared with the prior art, the invention has the following advantages:
the process effectively reduces F in the trifluoromethanesulfonic acid by adding calcium salt to settle in the early stage - The content of (2) reduces the difficulty of subsequent purification; solid components in the mixed liquid are further removed through secondary solid-liquid separation; meanwhile, the process eliminates the drying process of preparing the triflate from the triflate aqueous solution into the triflate in the conventional process, so that the energy consumption is greatly reduced, dilute sulfuric acid can be selected as sulfuric acid for acidolysis reaction, and the addition of the sulfuric acid is reduced to 1.1-1.5 times of equivalent from 5-7 times of equivalent in the conventional process, so that the production process is simplified, the energy consumption is reduced, the difficulty in treating three wastes is reduced, and the production cost is reduced.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic process flow diagram of the process of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
In this example, the process for preparing trifluoromethanesulfonic acid, as shown in fig. 1, includes the following steps:
s1, performing hydrolysis reaction on trifluoromethanesulfonyl fluoride gas in potassium hydroxide to obtain 3kg of trifluoromethanesulfonate aqueous solution; the mass concentration of the trifluoromethanesulfonic acid in the trifluoromethanesulfonate aqueous solution is 30.5%, and F - =1550ppm; the molar ratio of the potassium hydroxide to the trifluoromethanesulfonyl fluoride gas is 1.0:1.0;
s2, at normal temperature(25 ℃ C.) under normal pressure (101 KPa), to 3kg of the aqueous trifluoromethanesulfonate solution obtained in S1 was added 20g of CaCl 2 Fully stirring the powder to obtain a mixed solution, and carrying out primary solid-liquid separation on the mixed solution to obtain a clear solution; the calcium salt is added into the triflate aqueous solution in an amount of F - 1.2-2 times of equivalent weight required for complete reaction;
s3, slowly dropwise adding 0.28kg of sulfuric acid with the mass fraction of 92% into the clear liquid obtained in the S2 while stirring under the conditions of normal temperature (25 ℃) and normal pressure (101 KPa), and performing acidolysis reaction for 0.5h to obtain a trifluoromethanesulfonic acid aqueous solution;
the acidolysis reaction kettle adopted by the acidolysis reaction is glass, glass lining, monel alloy, hastelloy alloy, silicon carbide, a steel lining or sprayed with PVDF/PFA/PTFE;
s4, carrying out secondary solid-liquid separation on the trifluoromethanesulfonic acid aqueous solution obtained in S3, and removing calcium sulfate and solid residues to obtain a trifluoromethanesulfonic acid aqueous solution clear solution;
s5, carrying out reduced pressure distillation on the trifluoromethanesulfonic acid aqueous solution clear liquid obtained in the step S4, wherein the pressure of the reduced pressure distillation is-0.1 MPa, and the front fraction is collected at 750mmHg and the temperature of 30-80 ℃; collecting a post-fraction at 750mmHg at the temperature of 80-166 ℃, wherein the post-fraction is a crude trifluoromethanesulfonic acid product, the crude trifluoromethanesulfonic acid product is 0.68kg, and the yield is 94.7%; the content of the components in the crude trifluoromethanesulfonic acid product is shown in table 1:
TABLE 1 ingredient content in crude trifluoromethanesulfonic acid in example 1
| Component name | CF 3 SO 3 H | F - | SO 4 2- | H 2 O |
| Content (wt.) | About 88 percent | 12.5ppm | 18500 | 10.2％ |
Distilling and purifying 0.68kg of crude trifluoromethanesulfonic acid product under reduced pressure at a vacuum degree of 752mmHg, heating to 75-82 ℃, starting condensed water to reflux for 4h, gradually adjusting the condensed water to control the distillation rate, replacing a receiving bottle when receiving 95g of distillate, continuing distillation and collection, collecting the post-distillate when the temperature is 82-93 ℃, wherein the mass of the post-distillate is 0.55kg, and detecting F in the post-distillate - ＝6.5ppm，SO 4 2- ＝650ppm，H 2 O＝3500ppm；
And (2) continuously distilling the post-fraction, namely 0.55kg of trifluoromethanesulfonic acid under reduced pressure, and discharging 0.46kg of fraction under the conditions of a vacuum degree of 742mmHg and a temperature of 75-85 ℃ to obtain a trifluoromethanesulfonic acid refined product, wherein the components of the trifluoromethanesulfonic acid refined product are shown in Table 2 through detection:
table 2 shows the content of the components in the trifluoromethanesulfonic acid to obtain a refined trifluoromethanesulfonic acid;
| component name | CF 3 SO 3 H | F - | SO 4 2- | H 2 O |
| Content (wt.) | About 99.8% | 6.8ppm | 32ppm | 365ppm |
Example 2
In this example, the process for preparing trifluoromethanesulfonic acid, as shown in fig. 1, includes the following steps:
s1, carrying out hydrolysis reaction on trifluoromethanesulfonyl fluoride gas in sodium hydroxide to obtain 2.5kg of trifluoromethanesulfonate aqueous solution; the mass concentration of the trifluoromethanesulfonic acid in the trifluoromethanesulfonate aqueous solution is 49.5%, and F - =182ppm; the molar ratio of the sodium hydroxide to the trifluoromethanesulfonyl fluoride gas is 1.15:1.0;
s2, 2.5g of CaCl was added to 2.5kg of the aqueous trifluoromethanesulfonate solution obtained in S1 at room temperature (23 ℃) and under normal pressure (101 KPa) 2 Fully stirring the powder to obtain a mixed solution, and carrying out solid-liquid separation on the mixed solution for the first time to obtain a clear solution; the calcium salt is added into the triflate aqueous solution in an amount of F - 1.2-2 times of equivalent needed 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 S2 while stirring under the conditions of normal temperature (23 ℃) and normal pressure (101 KPa), and carrying out acidolysis reaction for 1h to obtain a trifluoromethanesulfonic acid aqueous solution;
the acidolysis reaction kettle adopted by the acidolysis reaction is glass, glass lining, monel alloy, hastelloy, silicon carbide, steel lining or sprayed with PVDF/PFA/PTFE;
s4, carrying out secondary solid-liquid separation on the trifluoromethanesulfonic acid aqueous solution obtained in S3, and removing calcium sulfate and solid residues to obtain a trifluoromethanesulfonic acid aqueous solution clear solution;
s5, carrying out reduced pressure distillation on the clear liquid of the aqueous solution of the trifluoromethanesulfonic acid obtained in the step S4, wherein the pressure of the reduced pressure distillation is-0.05 MPa, and the front fraction is collected at the temperature of 35-83 ℃ under 750 mmHg; collecting a post-fraction at the temperature of 83-166 ℃ under 750mmHg, wherein the post-fraction is a crude trifluoromethanesulfonic acid product, the crude trifluoromethanesulfonic acid product is 0.82kg, and the yield is 95.3%; the content of the components in the crude trifluoromethanesulfonic acid product is shown in Table 3:
TABLE 3 ingredient content of crude trifluoromethanesulfonic acid in example 2
| Component name | CF 3 SO 3 H | F - | SO 4 2- | H 2 O |
| Content (wt.) | About 88 percent | 12.5ppm | 18500 | 10.2％ |
Distilling and purifying 0.82kg of crude trifluoromethanesulfonic acid product under vacuum degree of 752mmHg, heating to 77-85 deg.C, starting condensed water reflux for 6h, gradually adjusting the condensed water to control distillationAt the speed of changing the receiving bottle when the distillate is received to 108g, continuing to distill and collect, collecting the post-distillate when the temperature is 85-94 ℃, wherein the mass of the post-distillate (trifluoromethanesulfonic acid) is 0.68kg, and detecting F in the post-distillate - ＝2.5ppm，SO 4 2- ＝247ppm，H 2 O＝4200ppm；
Continuously distilling the post-fraction, namely 0.68kg of trifluoromethanesulfonic acid, and discharging 0.45kg of fraction at the vacuum degree of 742mmHg and the temperature of 77-88 ℃ to obtain a trifluoromethanesulfonic acid refined product, wherein the components of the trifluoromethanesulfonic acid refined product are shown in Table 4 through detection:
table 4 component content of the refined trifluoromethanesulfonic acid product of example 2
| Component name | CF 3 SO 3 H | F - | SO 4 2- | H 2 O |
| Content (wt.) | About 99.9% | 1.2ppm | 16ppm | 285ppm |
Example 3
In this example, the process for preparing trifluoromethanesulfonic acid, as shown in fig. 1, includes the following steps:
s1, carrying out hydrolysis reaction on trifluoromethanesulfonyl fluoride gas in calcium hydroxide to obtain 3.8kg of trifluoromethanesulfonate aqueous solution; the mass concentration of the trifluoromethanesulfonic acid in the trifluoromethanesulfonate aqueous solution is 47.8%, and F - =685ppm; 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 trifluoromethanesulfonate solution obtained in S1 at normal temperature (20 ℃ C.) and normal pressure (101 KPa) 2 Fully stirring the powder to obtain a mixed solution, and carrying out primary solid-liquid separation on the mixed solution to obtain a clear solution; the calcium salt is added in an amount of F in the aqueous solution of the triflate - 1.2-2 times of equivalent needed for complete reaction;
s3, slowly dripping 0.80kg of sulfuric acid with the mass fraction of 68% into the clear liquid obtained in the S2 while stirring under the conditions of normal temperature (20 ℃) and normal pressure (101 KPa), and performing acidolysis reaction for 2 hours to obtain trifluoromethanesulfonic acid aqueous solution;
the acidolysis reaction kettle adopted by the acidolysis reaction is glass, glass lining, monel alloy, hastelloy, silicon carbide, steel lining or sprayed with PVDF/PFA/PTFE;
s4, carrying out secondary solid-liquid separation on the trifluoromethanesulfonic acid aqueous solution obtained in S3, and removing calcium sulfate and solid residues to obtain a trifluoromethanesulfonic acid aqueous solution clear solution;
s5, rectifying the clear liquid of the aqueous solution of the trifluoromethanesulfonic acid obtained in the step S4, and collecting front fractions at the temperature of 42-95 ℃ under the condition of 720 mmHg; when the temperature is 95-128 ℃, collecting middle distillate; collecting the fractions at the temperature of 128-175 ℃;
the middle distillate is a fine trifluoromethanesulfonic acid product, the weight of the fine trifluoromethanesulfonic acid product is 0.98kg, and the yield is 39.2% (based on a clear liquid); the component content of the refined trifluoromethanesulfonic acid product is shown in table 5:
TABLE 5 compositional content of the fine trifluoromethanesulfonic acid product of example 3
| Component name | CF 3 SO 3 H | F - | SO 4 2- | H 2 O |
| Content (wt.) | About 99.9% | 3.1ppm | 9ppm | 146ppm |
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (7)
1. A process for preparing trifluoromethanesulfonic acid, comprising the steps of:
s1, carrying out hydrolysis reaction on trifluoromethanesulfonyl fluoride gas in an alkali metal hydroxide to prepare a trifluoromethanesulfonate aqueous solution;
s2, adding a calcium salt into the triflate aqueous solution obtained in the S1 under the conditions of normal temperature and normal pressure, fully stirring to obtain a mixed solution, and carrying out primary solid-liquid separation on the mixed solution to obtain a clear solution;
s3, slowly dropwise adding sulfuric acid into the clear liquid obtained in the S2 while stirring under the conditions of normal temperature and normal pressure, and carrying out acidolysis reaction to obtain a trifluoromethanesulfonic acid aqueous solution;
s4, carrying out secondary solid-liquid separation on the trifluoromethanesulfonic acid aqueous solution obtained in S3, and removing calcium sulfate and solid residues to obtain a trifluoromethanesulfonic acid aqueous solution clear solution;
s5, gradually heating the clear liquid of the aqueous solution of the trifluoromethanesulfonic acid obtained in S4 to perform at least one purification, and collecting front fraction at the temperature of 30-95 ℃; when the temperature is 80-175 ℃, collecting the fractions to obtain the refined trifluoromethanesulfonic acid.
2. The process for preparing trifluoromethanesulfonic acid according to claim 1, wherein 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 (1.0-1.15): 1.0.
3. the process of claim 1, wherein the calcium salt in S2 is CaCl 2 The calcium salt is added in an amount of F in the aqueous solution of the triflate - 1.2 to 2 times the equivalent required to carry out the complete reaction.
4. The process method for preparing trifluoromethanesulfonic acid according to claim 1, wherein the concentration of sulfuric acid in S3 is 30% -100%, and the mass ratio of sulfuric acid to the clear solution is 1: (1.1-1.5).
5. The process for preparing trifluoromethanesulfonic acid according to claim 1, wherein the acidolysis reaction time in S3 is 0.5h to 2h.
6. The process for preparing trifluoromethanesulfonic acid according to claim 1, wherein both of the primary solid-liquid separation in S2 and the secondary solid-liquid separation in S4 are centrifugal separation methods.
7. The process for preparing trifluoromethanesulfonic acid according to claim 1, wherein the purification in S5 is distillation under reduced pressure or rectification, and the pressure of the distillation under reduced pressure is-0.1 MPa to-0.05 MPa.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS505325A (en) * | 1973-04-16 | 1975-01-21 | ||
| JPS6461452A (en) * | 1987-08-31 | 1989-03-08 | Central Glass Co Ltd | Production of fluorocarbonsulfonic acid |
| JPH03209359A (en) * | 1990-01-10 | 1991-09-12 | Sumikin Chem Co Ltd | Production of naphthalene sulfonic acid salt |
| JP2007119458A (en) * | 2005-09-30 | 2007-05-17 | Mitsubishi Materials Corp | Potassium perfluoroalkane sulfonate and process for production thereof |
| CN101402591A (en) * | 2008-11-09 | 2009-04-08 | 中国船舶重工集团公司第七一八研究所 | Process for preparing high-purity trifluoromethyl sulphonic acid |
| CN101747240A (en) * | 2008-12-11 | 2010-06-23 | 张家港市国泰华荣化工新材料有限公司 | Method for preparing trifluoromethyl sulfonic acid CF3SO3H by electrochemical fluorination gas-phase product of methanesulfonyl fluoride CH3SO2F |
| CN102272096A (en) * | 2009-01-05 | 2011-12-07 | 三菱综合材料株式会社 | Process for producing perfluoroalkylsulfonic acid salt |
| JP2013100240A (en) * | 2011-11-08 | 2013-05-23 | Hokko Chem Ind Co Ltd | Method for producing metal salt of perfluoroalkyl sulfonic acid |
| CN105693561A (en) * | 2016-03-18 | 2016-06-22 | 江苏国泰超威新材料有限公司 | Preparation method of trifluoromethane sulfonic acid |
| CN111116429A (en) * | 2019-12-29 | 2020-05-08 | 中船重工（邯郸）派瑞特种气体有限公司 | Method for synthesizing alkali metal trifluoromethanesulfonate |
| CN111116424A (en) * | 2019-12-28 | 2020-05-08 | 中船重工（邯郸）派瑞特种气体有限公司 | Method for preparing trifluoromethanesulfonic acid by continuous hydrolysis |
| CN113845446A (en) * | 2021-10-26 | 2021-12-28 | 中船重工（邯郸）派瑞特种气体有限公司 | Preparation method of trifluoromethanesulfonic acid |
-
2022
- 2022-11-04 CN CN202211377991.6A patent/CN115894308B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS505325A (en) * | 1973-04-16 | 1975-01-21 | ||
| US3919295A (en) * | 1973-04-16 | 1975-11-11 | Bayer Ag | Preparation of inorganic fluoride-free perfluoroalkane sulphonates |
| JPS6461452A (en) * | 1987-08-31 | 1989-03-08 | Central Glass Co Ltd | Production of fluorocarbonsulfonic acid |
| JPH03209359A (en) * | 1990-01-10 | 1991-09-12 | Sumikin Chem Co Ltd | Production of naphthalene sulfonic acid salt |
| JP2007119458A (en) * | 2005-09-30 | 2007-05-17 | Mitsubishi Materials Corp | Potassium perfluoroalkane sulfonate and process for production thereof |
| CN101402591A (en) * | 2008-11-09 | 2009-04-08 | 中国船舶重工集团公司第七一八研究所 | Process for preparing high-purity trifluoromethyl sulphonic acid |
| CN101747240A (en) * | 2008-12-11 | 2010-06-23 | 张家港市国泰华荣化工新材料有限公司 | Method for preparing trifluoromethyl sulfonic acid CF3SO3H by electrochemical fluorination gas-phase product of methanesulfonyl fluoride CH3SO2F |
| CN102272096A (en) * | 2009-01-05 | 2011-12-07 | 三菱综合材料株式会社 | Process for producing perfluoroalkylsulfonic acid salt |
| JP2013100240A (en) * | 2011-11-08 | 2013-05-23 | Hokko Chem Ind Co Ltd | Method for producing metal salt of perfluoroalkyl sulfonic acid |
| CN105693561A (en) * | 2016-03-18 | 2016-06-22 | 江苏国泰超威新材料有限公司 | Preparation method of trifluoromethane sulfonic acid |
| CN111116424A (en) * | 2019-12-28 | 2020-05-08 | 中船重工（邯郸）派瑞特种气体有限公司 | Method for preparing trifluoromethanesulfonic acid by continuous hydrolysis |
| CN111116429A (en) * | 2019-12-29 | 2020-05-08 | 中船重工（邯郸）派瑞特种气体有限公司 | Method for synthesizing alkali metal trifluoromethanesulfonate |
| CN113845446A (en) * | 2021-10-26 | 2021-12-28 | 中船重工（邯郸）派瑞特种气体有限公司 | Preparation method of trifluoromethanesulfonic acid |
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