CN112047844A - Purification method of perfluorotriethylamine - Google Patents
Purification method of perfluorotriethylamine Download PDFInfo
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- CN112047844A CN112047844A CN202010823362.6A CN202010823362A CN112047844A CN 112047844 A CN112047844 A CN 112047844A CN 202010823362 A CN202010823362 A CN 202010823362A CN 112047844 A CN112047844 A CN 112047844A
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- perfluorotriethylamine
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- closed container
- purifying
- perfluorinated
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- CBEFDCMSEZEGCX-UHFFFAOYSA-N 1,1,2,2,2-pentafluoro-n,n-bis(1,1,2,2,2-pentafluoroethyl)ethanamine Chemical compound FC(F)(F)C(F)(F)N(C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)F CBEFDCMSEZEGCX-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000000746 purification Methods 0.000 title claims abstract description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000005251 gamma ray Effects 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 230000018044 dehydration Effects 0.000 claims abstract description 6
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 6
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- 230000002285 radioactive effect Effects 0.000 claims abstract description 3
- 230000005855 radiation Effects 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical class [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- -1 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for purifying perfluorotriethylamine, and belongs to the technical field of thermal control. The method comprises the steps of filling perfluorinated triethylamine to be purified into a closed container, and irradiating the closed container by using a gamma-ray radioactive source to obtain primarily purified perfluorinated triethylamine; and (3) firstly carrying out alkaline washing on the initially purified perfluorotriethylamine to neutrality, then washing with water, then distilling, and finally carrying out dehydration and decoloration treatment to obtain the purified perfluorotriethylamine. The loss amount of the perfluorinated triethylamine is small while the impurities are fully decomposed by controlling the irradiation dose rate and the irradiation amount at the closed container in the irradiation process. The method can process working media measured by tons, has the capacity of large-scale purification in batches, and is low in cost.
Description
Technical Field
The invention relates to a method for purifying perfluorotriethylamine, and belongs to the technical field of thermal control.
Background
The pump-driven single-phase fluid loop technology is characterized by that the pump can drive working medium to make circular flow to implement collection, transmission and discharge of heatAn active thermal control technique. The working medium most commonly used in the pump-drive single-phase fluid circuit at present is perfluorinated triethylamine working medium. Perfluorotriethylamine is a perfluorinated inert liquid that is suitable for spacecraft applications because of its chemical stability and low pour point. The currently used perfluorotriethylamine is limited by the production process, and contains the main component perfluorotriethylamine ((C)2F5)3N) other components, the purity is generally only about 95%; for the purification of perfluorotriethylamine, a multi-rectification mode is generally adopted, namely, the working medium is heated by utilizing the difference of the boiling points of different components in the working medium, and different components are obtained in different boiling point intervals (namely boiling ranges). However, the method is limited by the defects of small boiling point difference between perfluorotriethylamine and other components, very low yield, low production efficiency and high cost.
Disclosure of Invention
In view of the above, the present invention provides a method for purifying perfluorotriethylamine, in which impurities in perfluorotriethylamine are decomposed under radiation by controlling radiation dose rate and radiation dose, so as to achieve an effect of purifying perfluorotriethylamine, obtain high-purity perfluorotriethylamine, and use the high-purity perfluorotriethylamine as a working medium in a pump-driven single-phase fluid circuit.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for purifying perfluorotriethylamine comprises the following steps:
(1) filling perfluorinated triethylamine to be purified into a closed container, wherein the purity of the perfluorinated triethylamine to be purified is less than or equal to 95%, and the closed container is made of a material which does not react with a perfluorinated triethylamine working medium and is resistant to ray irradiation (does not decompose or change under the ray irradiation);
(2) irradiating the closed container by using a gamma-ray radioactive source, wherein the irradiation dose rate of the closed container is more than or equal to 5Gy/min, and the irradiation dose is more than or equal to 104After the Gy irradiation is finished, obtaining primarily purified perfluorotriethylamine;
(3) firstly, carrying out alkali washing on the initially purified perfluorotriethylamine to neutrality, then washing with water until the acid value is less than 0.03mgKOH/g, then distilling at 62 +/-2 ℃, and finally carrying out dehydration and decoloration treatment to obtain the purified perfluorotriethylamine.
Preferably, the impurities in the perfluorotriethylamine to be purified in the step (1) include CF3N(C2F5)2、CHF2-N(C2F5)2、C2HF4-N(C2F5)2、(C2HF4)2NC2F5、(C2HF4)3N and (C)4F9)3More than one of N.
Preferably, the material of the closed container in the step (1) is polyethylene terephthalate (PET), glass or metal.
Preferably, when the sealed container in the step (1) is not filled with the perfluorinated triethylamine to be purified, the sealed container is subjected to inert gas replacement, so that the influence of oxygen on the irradiation process is reduced.
Preferably, in the step (2), the irradiation dose rate is 5-10 Gy/min, and the irradiation dose is 104～108Gy。
Preferably, saturated ethanol solution of potassium hydroxide is used for the alkaline washing in the step (3).
Preferably, the water washing in step (3) is performed with water having a purity higher than that of deionized water.
Preferably, in the step (3), the distilled perfluorotriethylamine is dehydrated and decolored by adopting a molecular sieve.
Advantageous effects
In the method, under the condition of gamma-ray irradiation, the perfluorotriethylamine and impurities in the perfluorotriethylamine can be decomposed into active components containing carbon-nitrogen bonds, and the components can be hydrolyzed after meeting water. In the irradiation process, the loss amount of the perfluorinated triethylamine is small while impurities are fully decomposed by controlling the irradiation dose rate and the irradiation amount of a closed container filled with the perfluorinated triethylamine to be purified. The method can process working media measured by tons, has the capacity of large-scale purification in batches, and is low in cost.
Drawings
FIG. 1 is a gas chromatographic chart of perfluorotriethylamine to be purified as described in the example.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The following are examples:
the purity of the perfluorotriethylamine to be purified is 95%, and a gas chromatography spectrogram of the perfluorotriethylamine is shown in figure 1, wherein the position of a peak number 1 is CF3N(C2F5)2(ii) a Peak number 2 is (C)2F5)3N (i.e., perfluorotriethylamine); CHF at peak number 32-N(C2F5)2(ii) a C at peak number 42HF4-N(C2F5)2(ii) a Peak number 5 is (C)2HF4)2NC2F5(ii) a At peak number 6 is (C)2HF4)3N; the peak X is incomplete fluoride containing two hydrogen atoms; peak number 7 is (C)4F9)3N。
Example 1
A method for purifying perfluorotriethylamine comprises the following steps:
(1) loading perfluorinated triethylamine to be purified into a closed container, wherein the closed container is made of glass;
(2) placing the closed container at the position of a gamma-ray radiation source with the irradiation dose rate of 5Gy/min for irradiation, wherein the irradiation dose reaches 5 multiplied by 104After Gy, after irradiation is finished, obtaining primarily purified perfluorotriethylamine;
(3) firstly, carrying out alkaline washing on the initially purified perfluorotriethylamine to neutrality by adopting a saturated potassium hydroxide ethanol solution, then washing with distilled water until the acid value is less than 0.03mgKOH/g, then distilling at 62 +/-2 ℃, and finally carrying out dehydration and decoloration treatment by using a molecular sieve (13-X sodium type in specification, 3-5 mm in diameter) to obtain the purified perfluorotriethylamine.
Gas chromatography analysis is carried out on the purified perfluorotriethylamine, and the analysis result shows that the purity of the purified perfluorotriethylamine is more than 99%; the weight of the perfluorinated triethylamine before and after purification is weighed by a weighing method to obtain the loss rate of the perfluorinated triethylamine, wherein the loss rate of the perfluorinated triethylamine is 2-3%.
Example 2
A method for purifying perfluorotriethylamine comprises the following steps:
(1) filling perfluorinated triethylamine to be purified into a closed container, wherein the volume of the closed container is larger than that of the perfluorinated triethylamine to be purified, and performing inert gas replacement on the closed container, wherein the closed container is made of PET (polyethylene terephthalate);
(2) placing the closed container at the position of a gamma-ray radiation source with the irradiation dose rate of 8Gy/min for irradiation, wherein the irradiation dose reaches 5 multiplied by 106After Gy, after irradiation is finished, obtaining primarily purified perfluorotriethylamine;
(3) firstly, carrying out alkaline washing on the initially purified perfluorotriethylamine to neutrality by adopting a saturated potassium hydroxide ethanol solution, then washing with distilled water until the acid value is less than 0.03mgKOH/g, then distilling at 62 +/-2 ℃, and finally carrying out dehydration and decoloration treatment by using a molecular sieve (13-X sodium type in specification, 3-5 mm in diameter) to obtain the purified perfluorotriethylamine.
Gas chromatography analysis is carried out on the purified perfluorotriethylamine, and the analysis result shows that the purity of the purified perfluorotriethylamine is more than 99%; the weight of the perfluorinated triethylamine before and after purification is weighed by a weighing method to obtain the loss rate of the perfluorinated triethylamine, wherein the loss rate of the perfluorinated triethylamine is 2-3%.
Example 3
A method for purifying perfluorotriethylamine comprises the following steps:
(1) filling perfluorinated triethylamine to be purified into an isometric closed container, wherein the volume of the closed container is larger than that of the perfluorinated triethylamine to be purified, and the closed container is made of glass;
(2) placing the closed container at the position of a gamma-ray radiation source with the irradiation dose rate of 10Gy/min for irradiation, wherein the irradiation dose reaches 108After Gy, after irradiation is finished, obtaining primarily purified perfluorotriethylamine;
(3) firstly, carrying out alkaline washing on the initially purified perfluorotriethylamine to neutrality by adopting a saturated potassium hydroxide ethanol solution, then washing with distilled water until the acid value is less than 0.03mgKOH/g, then distilling at 62 +/-2 ℃, and finally carrying out dehydration and decoloration treatment by using a molecular sieve (13-X sodium type in specification, 3-5 mm in diameter) to obtain the purified perfluorotriethylamine.
Gas chromatography analysis is carried out on the purified perfluorotriethylamine, and the analysis result shows that the purity of the purified perfluorotriethylamine is more than 99%; the weight of the perfluorinated triethylamine before and after purification is weighed by a weighing method to obtain the loss rate of the perfluorinated triethylamine, wherein the loss rate of the perfluorinated triethylamine is 2-3%.
In the method, the decomposition and hydrolysis processes of the perfluorinated triethylamine in the irradiation process are shown as the following formula, and the impurity components of the perfluorinated triethylamine are similar to the decomposition and hydrolysis processes of the perfluorinated triethylamine.
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 purifying perfluorotriethylamine is characterized in that: the method comprises the following steps:
(1) filling perfluorinated triethylamine to be purified into a closed container, wherein the purity of the perfluorinated triethylamine to be purified is less than or equal to 95%, and the closed container is made of a material which does not react with the perfluorinated triethylamine and is resistant to radiation;
(2) irradiating the closed container by using a gamma-ray radioactive source, wherein the irradiation dose rate of the closed container is more than or equal to 5Gy/min, and the irradiation dose is more than or equal to 104After the Gy irradiation is finished, obtaining primarily purified perfluorotriethylamine;
(3) firstly, carrying out alkali washing on the initially purified perfluorotriethylamine to neutrality, then washing with water until the acid value is less than 0.03mgKOH/g, then distilling at 62 +/-2 ℃, and finally carrying out dehydration and decoloration treatment to obtain the purified perfluorotriethylamine.
2. The method of claim 1, wherein the purification of perfluorotriethylamine is performed in the presence of a catalystIn the following steps: the impurities in the perfluorinated triethylamine to be purified in the step (1) comprise CF3N(C2F5)2、CHF2-N(C2F5)2、C2HF4-N(C2F5)2、(C2HF4)2NC2F5、(C2HF4)3N and (C)4F9)3More than one of N.
3. The method for purifying perfluorotriethylamine according to claim 1, wherein: the material of the closed container in the step (1) is polyethylene terephthalate, glass or metal.
4. The method for purifying perfluorotriethylamine according to claim 1, wherein: and (2) when the sealed container is not filled with the perfluorinated triethylamine to be purified in the step (1), performing inert gas replacement on the sealed container.
5. The method for purifying perfluorotriethylamine according to claim 1, wherein: in the step (2), the irradiation dose rate is 5-10 Gy/min, and the irradiation dose is 104～108Gy。
6. The method for purifying perfluorotriethylamine according to claim 1, wherein: and (3) adopting a saturated potassium hydroxide ethanol solution during alkaline washing.
7. The method for purifying perfluorotriethylamine according to claim 1, wherein: and (4) adopting water with the purity higher than that of deionized water during water washing in the step (3).
8. The method for purifying perfluorotriethylamine according to claim 1, wherein: and (3) dehydrating and decoloring the distilled perfluorinated triethylamine by adopting a molecular sieve.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010823362.6A CN112047844A (en) | 2020-08-17 | 2020-08-17 | Purification method of perfluorotriethylamine |
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| CN202010823362.6A CN112047844A (en) | 2020-08-17 | 2020-08-17 | Purification method of perfluorotriethylamine |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5799257A (en) * | 1992-10-27 | 1998-08-25 | Lockheed Martin Idaho Technologies Company | Process for gamma ray induced degradation of polychlorinated biphenyls |
| CN103080742A (en) * | 2010-08-27 | 2013-05-01 | 英派尔科技开发有限公司 | Hydrofluorocarbon detection device |
| CN104193056A (en) * | 2014-09-22 | 2014-12-10 | 中国科学技术大学 | Method for efficiently degrading polyfluorinated compound PFOA (perfluoro caprylic acid) in wastewater |
-
2020
- 2020-08-17 CN CN202010823362.6A patent/CN112047844A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5799257A (en) * | 1992-10-27 | 1998-08-25 | Lockheed Martin Idaho Technologies Company | Process for gamma ray induced degradation of polychlorinated biphenyls |
| CN103080742A (en) * | 2010-08-27 | 2013-05-01 | 英派尔科技开发有限公司 | Hydrofluorocarbon detection device |
| CN104193056A (en) * | 2014-09-22 | 2014-12-10 | 中国科学技术大学 | Method for efficiently degrading polyfluorinated compound PFOA (perfluoro caprylic acid) in wastewater |
Non-Patent Citations (2)
| Title |
|---|
| DMITRII D. MOLDAVSKY等: "The purification of perfluorinated compounds for commercial use", 《JOURNAL OF FLUORINE CHEMISTRY》 * |
| 罗世凯等: "氟树脂F2313辐射降解产物研究", 《核化学与放射化学》 * |
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