CN111116424A - Method for preparing trifluoromethanesulfonic acid by continuous hydrolysis - Google Patents
Method for preparing trifluoromethanesulfonic acid by continuous hydrolysis Download PDFInfo
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- CN111116424A CN111116424A CN201911384957.XA CN201911384957A CN111116424A CN 111116424 A CN111116424 A CN 111116424A CN 201911384957 A CN201911384957 A CN 201911384957A CN 111116424 A CN111116424 A CN 111116424A
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
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Abstract
The invention relates to a method for preparing trifluoromethanesulfonic acid by continuous hydrolysis, and belongs to the technical field of fine chemical engineering. Firstly, feeding trifluoromethanesulfonyl fluoride gas and an alkali metal hydroxide solution into a falling film reactor from a feeding hole to perform continuous neutralization hydrolysis reaction, and obtaining a reaction solution at a discharging hole of the falling film reactor; pumping the reaction liquid into a drying tower for drying, initially dissolving the dried solid by a solvent, feeding the initially dissolved liquid into an extraction tower through a diaphragm pump for extraction by an extractant, and obtaining alkali metal trifluoromethanesulfonate; and adding alkali metal trifluoromethanesulfonate and concentrated sulfuric acid into an acidification tower for acidification reaction to obtain a crude trifluoromethanesulfonic acid product, and purifying to obtain high-purity trifluoromethanesulfonic acid. The method realizes the continuous production of the trifluoromethanesulfonic acid, avoids the generation of byproducts in the traditional preparation process for producing the trifluoromethanesulfonic acid, has low energy consumption by the continuous hydrolysis method, and can effectively save the cost.
Description
Technical Field
The invention relates to a method for preparing trifluoromethanesulfonic acid by continuous hydrolysis, and belongs to the technical field of fine chemical engineering.
Background
Triflic acid is one of the strongest known organic acids, and the triflate ion contained therein has extremely strong thermodynamic and chemical stability, and will not free fluoride ion even in the presence of strong nucleophilic reagent, and this property makes triflic acid play an important role in the field of organic chemical reaction.
In the preparation method of trifluoromethanesulfonic acid in chinese patent application 201510173116.X, halogenated trifluoromethane is used as a raw material, zinc powder and tetrahydrofuran are added in an environment protected by nitrogen, trifluorobromomethane gas is introduced, a catalytic amount of elemental iodine is added, a temperature-controlled reaction is performed to obtain a trifluoromethyl zinc halide reagent, sulfur trioxide is added for continuous reaction to generate halogenated zinc trifluoromethanesulfonate, a reaction solution is added into an alkali solution for neutralization, filtrate is evaporated to dryness to obtain solid sodium trifluoromethanesulfonate, and then acidification and rectification are performed to obtain trifluoromethanesulfonic acid; the production of by-products in the production process is effectively reduced, the situation that the generated trifluoromethanesulfonic acid product is relatively high in fluoride ions, chloride ions and sulfate ions in the traditional process is avoided, the purity of the trifluoromethanesulfonic acid obtained by rectification and purification is up to more than 99.95%, and the yield can reach 83%.
Although the preparation method of the trifluoromethanesulfonic acid can obtain the trifluoromethanesulfonic acid with high purity, the preparation cost of the trifluoromethanesulfonic acid is high due to high energy consumption in the preparation process, and economic benefits are affected.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing trifluoromethanesulfonic acid by continuous hydrolysis.
In order to achieve the above object, the technical solution of the present invention is as follows.
A process for the continuous hydrolysis preparation of trifluoromethanesulfonic acid, the process steps being as follows:
(1) feeding the trifluoromethanesulfonyl fluoride gas and an alkali metal hydroxide solution into a falling film reactor from a feeding hole, controlling the absolute pressure to be 0.1-0.2MPa and the temperature to be 40-50 ℃, carrying out continuous neutralization hydrolysis reaction, and obtaining a reaction solution at a discharge hole of the falling film reactor; wherein the molar ratio of the trifluoromethanesulfonyl fluoride to the alkali metal hydroxide is 1: 1.05-1.2;
preferably, the mass fraction of the alkali metal hydroxide in the alkali metal hydroxide solution in the step (1) is 5 to 40%.
Preferably, in the step (1), the alkali metal hydroxide is one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide.
Preferably, the trifluoromethanesulfonyl fluoride gas in step (1) flows in parallel with the alkali metal hydroxide solution in the falling film reactor.
Preferably, the falling film reactor in the step (1) is a falling film tubular reactor, a redistributor is arranged at the top of the falling film tubular reactor, trifluoromethanesulfonyl fluoride gas enters from the middle of each tubular reactor, and alkali metal hydroxide solution flows in along the inner wall surface of each tubular reactor.
(2) Pumping the reaction liquid into a drying tower for drying, initially dissolving the dried solid by a solvent, and introducing the initially dissolved liquid into an extraction tower through a diaphragm pump for extraction by an extractant to obtain alkali metal trifluoromethanesulfonate;
preferably, the solvent and the extractant in the step (2) are absolute ethyl alcohol.
(3) Adding alkali metal trifluoromethanesulfonate and concentrated sulfuric acid into an acidification tower for acidification reaction to obtain a crude trifluoromethanesulfonic acid product; wherein the mass fraction of the concentrated sulfuric acid is 98-105%; the molar ratio of the alkali metal trifluoromethanesulfonate to the concentrated sulfuric acid is 1: 3-5;
(4) and purifying the crude trifluoromethanesulfonic acid to obtain high-purity trifluoromethanesulfonic acid, wherein the purity of the trifluoromethanesulfonic acid is more than or equal to 99.5%.
Preferably, when purifying in the step (4), the low-purity trifluoromethanesulfonic acid is pumped into a distillation column for distillation.
Preferably, when purifying in the step (4), the low-purity trifluoromethanesulfonic acid is pumped into a rectifying tower for rectification.
Advantageous effects
According to the method, the trifluoromethanesulfonic acid fluoride gas and the alkali metal hydroxide solution are subjected to gas-liquid reaction in the falling film reactor, then the alkali metal trifluoromethanesulfonate is obtained after drying and extraction, and the alkali metal trifluoromethanesulfonate is subjected to acidification reaction with concentrated sulfuric acid and then distillation or rectification, so that high-purity trifluoromethanesulfonic acid is obtained, the generation of byproducts in the traditional production process of trifluoromethanesulfonic acid is avoided, meanwhile, the continuous hydrolysis method is low in energy consumption, too high reaction temperature and pressure are not needed, the preparation cost can be effectively saved, the preparation method is simple and convenient, and high-quality trifluoromethanesulfonic acid can be prepared efficiently at low cost.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1:
(1) selecting a sodium hydroxide solution with the mass fraction of 35% as a raw material for a neutralization hydrolysis reaction, injecting trifluoromethanesulfonyl fluoride gas and the sodium hydroxide solution into a falling film reactor through a feed inlet, wherein a falling film tubular reactor is adopted in the falling film reactor, a redistributor is arranged at the top of the falling film tubular reactor, the trifluoromethanesulfonyl fluoride gas enters from the middle of each tubular column, and an alkali metal hydroxide solution flows in along the inner wall surface of each tubular column; the feeding molar ratio of the trifluoromethanesulfonyl fluoride gas to the sodium hydroxide is 1: 1.1, controlling the pressure in the falling film tubular reactor to be 0.15MPa absolute, controlling the temperature to be 45 ℃, and enabling the trifluoromethanesulfonyl fluoride gas and the sodium hydroxide solution to flow in parallel in a pipeline in the falling film tubular reactor, so that the trifluoromethanesulfonyl fluoride gas and the sodium hydroxide solution are subjected to sufficient gas-liquid neutralization hydrolysis reaction, and a reaction solution after neutralization hydrolysis is obtained;
(2) pumping the reaction liquid into a drying tower for drying, primarily dissolving the dried solid by absolute ethyl alcohol, pumping the primarily dissolved liquid into an extraction tower by a diaphragm pump, and extracting by absolute ethyl alcohol in the extraction tower to obtain alkali metal trifluoromethanesulfonate;
(3) selecting concentrated sulfuric acid with the mass fraction of 99% as a raw material for acidification reaction, and mixing alkali metal trifluoromethanesulfonate and concentrated sulfuric acid according to a feeding molar ratio of 1:3, injecting the mixture into an acidification tower for acidification, thereby obtaining a crude product of trifluoromethanesulfonic acid;
(4) and pumping the crude trifluoromethanesulfonic acid into a rectifying tower for rectification, thereby obtaining trifluoromethanesulfonic acid with the purity of 99.5%.
Example 2:
(1) selecting a potassium hydroxide solution with the mass fraction of 30% as a raw material for a neutralization hydrolysis reaction, injecting trifluoromethanesulfonyl fluoride gas and the potassium hydroxide solution into a falling film reactor through inlets, wherein a falling film tubular reactor is adopted in the falling film reactor, a redistributor is arranged at the top of the falling film tubular reactor, the trifluoromethanesulfonyl fluoride gas enters from the middle of each tubular column, and an alkali metal hydroxide solution flows in along the inner wall surface of each tubular column; the molar ratio of the trifluoromethanesulfonyl fluoride gas to the potassium hydroxide solution is 1: 1.12, controlling the pressure in the falling film tubular reactor to be 0.18MPa absolute, and controlling the temperature to be 47 ℃, wherein the trifluoromethanesulfonyl fluoride gas and the potassium hydroxide solution flow in parallel in a pipeline in the falling film tubular reactor, so that the trifluoromethanesulfonyl fluoride gas and the potassium hydroxide solution are subjected to sufficient gas-liquid neutralization hydrolysis reaction, and a reaction solution after neutralization hydrolysis is obtained;
(2) pumping the reaction liquid into a drying tower for drying, primarily dissolving the dried solid by absolute ethyl alcohol, pumping the primarily dissolved liquid into an extraction tower by a diaphragm pump, and extracting by absolute ethyl alcohol in the extraction tower to obtain alkali metal trifluoromethanesulfonate;
(3) selecting concentrated sulfuric acid with the mass fraction of 101% as a raw material for acidification reaction, and mixing alkali metal trifluoromethanesulfonate and concentrated sulfuric acid according to a feeding molar ratio of 1: 4.2 injecting the mixture into an acidification tower for acidification, thereby obtaining a crude product of the trifluoromethanesulfonic acid;
(4) pumping the crude trifluoromethanesulfonic acid into a distillation tower for distillation, thereby obtaining trifluoromethanesulfonic acid with the purity of 99.7%.
Example 3:
(1) selecting a potassium hydroxide solution with the mass fraction of 40% as a raw material for a neutralization hydrolysis reaction, injecting trifluoromethanesulfonyl fluoride gas and the potassium hydroxide solution into a falling film reactor through inlets, wherein a falling film tubular reactor is adopted in the falling film reactor, a redistributor is arranged at the top of the falling film tubular reactor, the trifluoromethanesulfonyl fluoride gas enters from the middle of each tubular column, and an alkali metal hydroxide solution flows in along the inner wall surface of each tubular column; the molar ratio of the trifluoromethanesulfonyl fluoride gas to the potassium hydroxide solution is 1: 1.15, controlling the pressure in the falling film tubular reactor to be 0.20MPa absolute pressure, and controlling the temperature to be 50 ℃, wherein the trifluoromethanesulfonyl fluoride gas and the potassium hydroxide solution flow in parallel in a pipeline in the falling film tubular reactor, so that the trifluoromethanesulfonyl fluoride gas and the potassium hydroxide solution are subjected to sufficient gas-liquid neutralization hydrolysis reaction, and a reaction solution after neutralization hydrolysis is obtained;
(2) pumping the reaction liquid into a drying tower for drying, primarily dissolving the dried solid by absolute ethyl alcohol, pumping the primarily dissolved liquid into an extraction tower by a diaphragm pump, and extracting by absolute ethyl alcohol in the extraction tower to obtain alkali metal trifluoromethanesulfonate;
(3) selecting 105% concentrated sulfuric acid by mass as a raw material for an acidification reaction, and injecting alkali metal trifluoromethanesulfonate and the concentrated sulfuric acid into an acidification tower according to a feeding molar ratio of 1:5 for acidification, so as to obtain a crude trifluoromethanesulfonic acid product;
(4) pumping the crude trifluoromethanesulfonic acid into a distillation tower for distillation, thereby obtaining trifluoromethanesulfonic acid with the purity of 99.6%.
In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.
Claims (8)
1. A method for preparing trifluoromethanesulfonic acid by continuous hydrolysis is characterized in that: the method comprises the following steps:
(1) feeding the trifluoromethanesulfonyl fluoride gas and an alkali metal hydroxide solution into a falling film reactor from a feeding hole, controlling the absolute pressure to be 0.1-0.2MPa and the temperature to be 40-50 ℃, carrying out continuous neutralization hydrolysis reaction, and obtaining a reaction solution at a discharge hole of the falling film reactor; wherein the molar ratio of the trifluoromethanesulfonyl fluoride to the alkali metal hydroxide is 1: 1.05-1.2;
(2) pumping the reaction liquid into a drying tower for drying, initially dissolving the dried solid by a solvent, and introducing the initially dissolved liquid into an extraction tower through a diaphragm pump for extraction by an extractant to obtain alkali metal trifluoromethanesulfonate;
(3) adding alkali metal trifluoromethanesulfonate and concentrated sulfuric acid into an acidification tower for acidification reaction to obtain a crude trifluoromethanesulfonic acid product; wherein the mass fraction of the concentrated sulfuric acid is 98-105%; the molar ratio of the alkali metal trifluoromethanesulfonate to the concentrated sulfuric acid is 1: 3-5;
(4) and purifying the crude trifluoromethanesulfonic acid to obtain high-purity trifluoromethanesulfonic acid, wherein the purity of the trifluoromethanesulfonic acid is more than or equal to 99.5%.
2. A process for the continuous hydrolysis preparation of trifluoromethanesulfonic acid according to claim 1, characterized in that: the mass fraction of the alkali metal hydroxide in the alkali metal hydroxide solution in the step (1) is 5-40%.
3. A process for the continuous hydrolysis preparation of trifluoromethanesulfonic acid according to claim 1, characterized in that: in the step (1), the alkali metal hydroxide is more than one of lithium hydroxide, sodium hydroxide and potassium hydroxide.
4. A process for the continuous hydrolysis preparation of trifluoromethanesulfonic acid according to claim 1, characterized in that: and (2) enabling the trifluoromethanesulfonyl fluoride gas and the alkali metal hydroxide solution to flow in parallel in the falling film reactor in the step (1).
5. A process for the continuous hydrolysis preparation of trifluoromethanesulfonic acid according to claim 1, characterized in that: the falling film reactor in the step (1) is a falling film tubular reactor, a redistributor is arranged at the top of the falling film tubular reactor, trifluoromethanesulfonyl fluoride gas enters from the middle of each tubular reactor, and alkali metal hydroxide solution flows in along the inner wall surface of each tubular reactor.
6. A process for the continuous hydrolysis preparation of trifluoromethanesulfonic acid according to claim 1, characterized in that: in the step (2), the solvent and the extractant are absolute ethyl alcohol.
7. A process for the continuous hydrolysis preparation of trifluoromethanesulfonic acid according to claim 1, characterized in that: and (4) pumping the low-purity trifluoromethanesulfonic acid into a distillation column for distillation during purification in the step (4).
8. A process for the continuous hydrolysis preparation of trifluoromethanesulfonic acid according to claim 1, characterized in that: and (4) pumping the low-purity trifluoromethanesulfonic acid into a rectifying tower for rectification during purification in the step (4).
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| CN201911384957.XA CN111116424B (en) | 2019-12-28 | 2019-12-28 | Method for preparing trifluoromethanesulfonic acid by continuous hydrolysis |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679392A (en) * | 2020-12-30 | 2021-04-20 | 中船重工（邯郸）派瑞特种气体有限公司 | Production device and method of trifluoromethanesulfonic acid |
| CN115894308A (en) * | 2022-11-04 | 2023-04-04 | 中船(邯郸)派瑞特种气体股份有限公司 | Process for preparing trifluoromethanesulfonic acid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 李忠铭等: "《现代工业化学》", 31 August 2018, 华中科技大学出版社(中国·武汉) * |
| 王灿等: "《环境工程反应动力学和反应器的设计与操作》", 31 October 2018, 天津大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679392A (en) * | 2020-12-30 | 2021-04-20 | 中船重工（邯郸）派瑞特种气体有限公司 | Production device and method of trifluoromethanesulfonic acid |
| CN115894308A (en) * | 2022-11-04 | 2023-04-04 | 中船(邯郸)派瑞特种气体股份有限公司 | Process for preparing trifluoromethanesulfonic acid |
| CN115894308B (en) * | 2022-11-04 | 2024-04-05 | 中船(邯郸)派瑞特种气体股份有限公司 | Technological method for preparing trifluoromethanesulfonic acid |
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