CN111116347A - Perfluoropolyether carboxylic acids with low HF content and process for their preparation - Google Patents
Perfluoropolyether carboxylic acids with low HF content and process for their preparation Download PDFInfo
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- CN111116347A CN111116347A CN201911399540.0A CN201911399540A CN111116347A CN 111116347 A CN111116347 A CN 111116347A CN 201911399540 A CN201911399540 A CN 201911399540A CN 111116347 A CN111116347 A CN 111116347A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/04—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1425—Regeneration of liquid absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/125—Saturated compounds having only one carboxyl group and containing ether groups, groups, groups, or groups
- C07C59/135—Saturated compounds having only one carboxyl group and containing ether groups, groups, groups, or groups containing halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/324—Polymers modified by chemical after-treatment with inorganic compounds containing oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/10—Inorganic absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2047—Hydrofluoric acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of fluorine chemical industry, and particularly relates to a preparation method of perfluoropolyether carboxylic acid with low HF content, which comprises the following steps: dropwise adding saturated sodium fluoride aqueous solution into a reaction tank containing perfluoropolyether acyl fluoride at the speed of 1-10ml/min, and allowing the product after the reaction to flow into an absorption tower loaded with a NaF recycling agent to absorb HF, thereby obtaining the perfluorocarboxylic acid with the HF content of less than 0.1%. The method has the advantages that the perfluoropolyether acyl fluoride reacts with the saturated sodium fluoride aqueous solution to generate the perfluoropolyether carboxylic acid and the hydrogen fluoride, the hydrogen fluoride and the sodium fluoride generate sodium bifluoride which is dissolved in water to be smaller, the sodium bifluoride can be obtained again through filtering, drying and heating (160 ℃), and the sodium fluoride can be reused.
Description
Technical Field
The invention belongs to the field of fluorine chemical industry, and particularly relates to a preparation method of perfluoropolyether carboxylic acid with low HF content.
Background
Low molecular weight perfluoropolyether carboxylic acids and carboxylates are important fluorocarbon surfactants useful as dispersing agents for the dispersion polymerization of fluorinated monomers in an aqueous polymerization medium to produce various fluororesins. Because of the environmental problems generated by the traditional fluorine-containing surfactant perfluorooctanoic acid and salt, the perfluoropolyether carboxylic acid and carboxylate are regarded as an important novel green and environment-friendly fluorocarbon surfactant because the perfluoropolyether carboxylic acid and the carboxylate are easier to degrade, and have wide application values in the fields of fluorine-containing polymer preparation, water and oil resistance, oil exploitation and the like.
The reaction of perfluoroacyl fluoride with water is commonly used to produce perfluoropolyether carboxylic acids, but during the production process large amounts of hydrofluoric acid are produced, which are readily soluble in the perfluoropolyether carboxylic acids and affect the quality of the perfluoropolyether carboxylic acids.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of perfluorocarboxylic acid with low HF content.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing perfluoropolyether carboxylic acid with low HF content comprises the following steps: dropwise adding saturated sodium fluoride aqueous solution into a reaction tank containing perfluoropolyether acyl fluoride at the speed of 1-10ml/min, and allowing the product after the reaction to flow into an absorption tower loaded with a NaF recycling agent to absorb HF, thereby obtaining the perfluorocarboxylic acid with the HF content of less than 0.1%.
And a heating device is arranged outside the absorption tower, and after the reaction is finished, the absorption tower is heated to 160 ℃ for NaF recovery.
A baffle plate is arranged in the reaction tank; a filter screen is arranged on the clapboard; the top of the reaction tank is provided with an air outlet connected with a recovery tank containing NaOH.
The upper end of the absorption tower is provided with an outlet connected with a recovery tank loaded with NaOH.
The invention also provides the perfluoropolyether carboxylic acid prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
in the application, the saturated sodium fluoride aqueous solution is used for replacing the traditional water and the full-side polyether acyl fluoride to react to generate the perfluoropolyether carboxylic acid, and because the water which is one of the raw materials for reacting with the generated perfluoroacyl fluoride is added in a saturated sodium fluoride mode, most of HF generated by the reaction can not enter the water but enters the NaOH absorption tank to be absorbed, so that the working efficiency is improved. Introducing perfluorocarboxylic acid containing a small amount of HF into an absorption tower containing NaF, reacting NaF with HF to generate NaHF2 according to a reaction formula, and absorbing the NaHF 2; heating of the NaHF2 can generate NaF as well as HF, so that the NaF in the absorber can be regenerated by heating to 160 ℃ using this principle. This arrangement can greatly reduce HF in the reaction product.
Description of the drawings:
FIG. 1 is a schematic diagram of an apparatus for preparing perfluoropolyether carboxylic acids with low HF content.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the following preferred embodiments.
Example 1: 100 g of perfluoropolyether acyl fluoride CF3CF2CF2OCF (CF3) -COF is added into a reaction tank at the temperature of 0-10 ℃, the temperature is kept, 115g of NaF saturated aqueous solution is added at the speed of 1-10ml/min without stirring, after the reaction is finished, a partition plate in the reaction tank is opened, a reaction product flows into an absorption tower loaded with NaF recovery agent through a filter screen arranged on the partition plate, a small amount of NaHF2 is left on the filter screen, a large amount of generated HF gas enters a NaOH recovery tank through a gas outlet at the upper part of the reaction tank to finish the recovery of a large amount of HF gas, a product CF3CF2CF2OCF (CF3) -COOH containing a small amount of HF enters the absorption tower, the HF and the NaF react to generate NaHF2, the CF3CF2CF2OCF (CF3) -COOH after absorbing the HF enters a storage tank of perfluoropolyether carboxylic acid, and the content of HF in the final CF3CF2CF2OCF (CF3) -COOH is less than 0.1%.
After the device is used for a period of time, the absorption tower is heated to 160 ℃, NaHF2 is decomposed after the heating, the regeneration of NaF is realized, and the upper end of the absorption tower is provided with an outlet which is connected with a recovery tank containing NaOH to absorb the decomposed HF.
FIG. 1 shows an apparatus for producing the low HF content perfluorocarboxylic acid, comprising a perfluorocarboxylic acid producing apparatus 1, an absorption column 2 containing a NaF-recovering agent, and a perfluorocarboxylic acid storage tank 3, which are connected in series; the perfluorocarboxylic acid generating device comprises a reaction tank, a partition plate 4 arranged in the reaction tank and a filter screen 5 arranged above the partition plate; the top of the reaction tank is provided with a dropping funnel and an air outlet; the dropping funnel is used for adding saturated NaF aqueous solution, and the air outlet is connected with a NaOH recovery tank 7; the bottom of the reaction tank is provided with a product outlet which is used for being connected with an inlet of the absorption tower 2; NaF solid is filled in the absorption tower; and an outlet at the bottom of the absorption tower is communicated with a 3-tank of perfluorocarboxylic acid. A heating jacket 6 is arranged outside the absorption tower; the top of the absorption tower is provided with an HF recovery port connected with a NaOH recovery tank.
The method has the advantages that the perfluoropolyether acyl fluoride reacts with the saturated sodium fluoride aqueous solution to generate the perfluoropolyether carboxylic acid and the hydrogen fluoride, the hydrogen fluoride and the sodium fluoride generate sodium bifluoride which is dissolved in water to be smaller, the sodium bifluoride can be obtained again through filtering, drying and heating (160 ℃), and the sodium fluoride can be reused. Because the water which is one of the raw materials for reacting with generated perfluoroacyl fluoride is added in the form of saturated sodium fluoride, HF generated by the reaction is not dissolved in the water, but most of the HF enters an NaOH absorption tank to be absorbed, the working efficiency is improved, a small amount of HF reacts with NaF to generate NaHF2, and the NaHF2 is precipitated in a solid form due to the absence of excessive water; after the reaction is finished, the partition plate is opened, the NaHF2 is remained on the filter screen, and the reaction product, namely the perfluorocarboxylic acid enters an HF absorption device. The method adopting the device can greatly reduce the HF content in the product and effectively improve the quality of the product.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (5)
1. A method for preparing perfluoropolyether carboxylic acid with low HF content is characterized by comprising the following steps: dropwise adding saturated sodium fluoride aqueous solution into a reaction tank containing perfluoropolyether acyl fluoride at the speed of 1-10ml/min, and allowing the product after the reaction to flow into an absorption tower loaded with a NaF recycling agent to absorb HF, thereby obtaining the perfluorocarboxylic acid with the HF content of less than 0.1%.
2. The process according to claim 1, wherein a heating unit is provided outside the absorption column, and after the reaction, the absorption column is heated to 160 ℃ to recover NaF.
3. The process for producing a perfluoropolyether carboxylic acid having a low HF content according to claim 1, wherein a partition plate is provided in the reaction tank; a filter screen is arranged on the clapboard; the top of the reaction tank is provided with an air outlet connected with a recovery tank containing NaOH.
4. The process according to claim 3, wherein the absorption tower has an outlet at its upper end connected to a recovery tank containing NaOH.
5. A perfluoropolyether carboxylic acid obtained by the production process described in any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911399540.0A CN111116347A (en) | 2019-12-30 | 2019-12-30 | Perfluoropolyether carboxylic acids with low HF content and process for their preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911399540.0A CN111116347A (en) | 2019-12-30 | 2019-12-30 | Perfluoropolyether carboxylic acids with low HF content and process for their preparation |
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| Publication Number | Publication Date |
|---|---|
| CN111116347A true CN111116347A (en) | 2020-05-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911399540.0A Pending CN111116347A (en) | 2019-12-30 | 2019-12-30 | Perfluoropolyether carboxylic acids with low HF content and process for their preparation |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5196579A (en) * | 1990-12-24 | 1993-03-23 | Hoechst Ag | Process for the recovery of perfluoroethercarboxylic acids |
| CN1466562A (en) * | 2000-09-27 | 2004-01-07 | ������������ʽ���� | Process for producing acyl fluoride and carboxylic acid salt |
| CN1466563A (en) * | 2000-09-27 | 2004-01-07 | ������������ʽ���� | Process for producing fluorinated ester compound |
| CN105646177A (en) * | 2015-12-31 | 2016-06-08 | 天津市长芦化工新材料有限公司 | Method for preparing perfluoropolyether carboxylic acid |
-
2019
- 2019-12-30 CN CN201911399540.0A patent/CN111116347A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5196579A (en) * | 1990-12-24 | 1993-03-23 | Hoechst Ag | Process for the recovery of perfluoroethercarboxylic acids |
| CN1466562A (en) * | 2000-09-27 | 2004-01-07 | ������������ʽ���� | Process for producing acyl fluoride and carboxylic acid salt |
| CN1466563A (en) * | 2000-09-27 | 2004-01-07 | ������������ʽ���� | Process for producing fluorinated ester compound |
| CN105646177A (en) * | 2015-12-31 | 2016-06-08 | 天津市长芦化工新材料有限公司 | Method for preparing perfluoropolyether carboxylic acid |
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Application publication date: 20200508 |
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