CN115947375A - Preparation method of manganese trifluoride - Google Patents
Preparation method of manganese trifluoride Download PDFInfo
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- CN115947375A CN115947375A CN202310006352.7A CN202310006352A CN115947375A CN 115947375 A CN115947375 A CN 115947375A CN 202310006352 A CN202310006352 A CN 202310006352A CN 115947375 A CN115947375 A CN 115947375A
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- manganese
- trifluoride
- difluoride
- fluorine gas
- perfluoropolyether oil
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- 229910021571 Manganese(III) fluoride Inorganic materials 0.000 title claims abstract description 59
- SRVINXWCFNHIQZ-UHFFFAOYSA-K manganese(iii) fluoride Chemical compound [F-].[F-].[F-].[Mn+3] SRVINXWCFNHIQZ-UHFFFAOYSA-K 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims abstract description 47
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 38
- 239000011737 fluorine Substances 0.000 claims abstract description 38
- 239000003921 oil Substances 0.000 claims abstract description 35
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 8
- 239000002612 dispersion medium Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000003513 alkali Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 15
- 239000012467 final product Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000003756 stirring Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012025 fluorinating agent Substances 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of manganese trifluoride. The preparation method comprises the following steps: the perfluoropolyether oil is used as a dispersion medium, and manganese difluoride and fluorine gas are reacted to generate manganese trifluoride. The method ensures that manganese difluoride uniformly dispersed in perfluoropolyether oil reacts with fluorine gas to generate manganese trifluoride, thereby reducing the consumption of the fluorine gas in the fluorination reaction process, improving the content of the manganese trifluoride in a final product, and ensuring that the content of the manganese trifluoride in a produced manganese trifluoride product can reach 99% and the content of the manganese difluoride is not more than 2%.
Description
Technical Field
The invention relates to the technical field of preparation of manganese trifluoride, in particular to a preparation method of manganese trifluoride.
Background
Manganese trifluoride is a chemical substance with the chemical formula of MnF 3 For use as fluorinating agents. Manganese, manganese carbide or manganese chloride directly react with fluorine to obtain MnF 2 And MnF 3 A mixture of (a). It is a solid, and although its decomposition pressure is less than 10.1325kPa (0.1 atm) at 600 ℃, fluorine is released upon heating. It is a strong fluorinating agent which reacts with sulfur, boron, silicon, carbon, phosphorus trichloride and carbon tetrachloride when heated. It is used to fluorinate gaseous hydrocarbons.
In industrial production, manganese dichloride or manganese difluoride and fluorine gas are directly reacted at high temperature to prepare manganese trifluoride. In addition, manganese trifluoride can also be obtained by fluorinating manganese metal with chlorine trifluoride. Among them, the direct fluorination method of manganese difluoride is commonly used, i.e. fluorine gas is directly introduced into a reaction kettle filled with manganese difluoride at high temperature, and the fluorine gas and the manganese difluoride react to generate manganese trifluoride. In practice, because manganese difluoride is a solid stack, the internal manganese difluoride is not easily reacted, so that even if much fluorine gas is consumed, a small amount of manganese difluoride is still typically present in the final product. That is, the conventional direct manganese difluoride fluorination method has a large fluorine gas consumption and a low manganese trifluoride content in the final product.
Disclosure of Invention
The invention aims to overcome the technical defects, provides a preparation method of manganese trifluoride, and solves the technical problems of high fluorine gas consumption and low product yield in the prior art when manganese trifluoride is produced by a direct fluorination method of manganese difluoride.
The invention provides a preparation method of manganese trifluoride, which comprises the following steps: the perfluoropolyether oil is used as a dispersion medium, and manganese difluoride and fluorine gas are reacted to generate manganese trifluoride.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, manganese difluoride uniformly dispersed in perfluoropolyether oil reacts with fluorine gas to generate manganese trifluoride, so that the consumption of the fluorine gas is reduced in the fluorination reaction process, the content of the manganese trifluoride in a final product is increased, the content of the manganese trifluoride in the produced manganese trifluoride product can reach 99%, and the content of the manganese difluoride is not more than 2%.
Drawings
FIG. 1 is a photograph of a manganese trifluoride product prepared in example 1;
FIG. 2 is a report of the measurement of the manganese trifluoride product prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of manganese trifluoride, which comprises the following steps: the perfluoropolyether oil is used as a dispersion medium, and manganese difluoride and fluorine gas are reacted to generate manganese trifluoride.
The conventional high-temperature gas-solid reaction method for preparing manganese difluoride has the following defects: due to the stacking of solid manganese difluoride, in order to completely fluorinate the manganese difluoride, the manganese difluoride needs to be spread as thin as possible, so that the single-kettle capacity is very low, the conversion rate of the manganese difluoride is difficult to reach more than 95%, and the consumption of fluorine gas is obviously excessive. In the invention, after the manganese difluoride and the perfluoropolyether oil are properly mixed in the reaction kettle, the oil density of the perfluoropolyether oil is very high (2-3 g/cubic centimeter), the oil density of the perfluoropolyether oil is close to that of the manganese difluoride, and the viscosity of the perfluoropolyether oil is relatively high, so that the manganese difluoride can be uniformly dispersed in the perfluoropolyether oil and cannot be deposited at the bottom of the reaction kettle. When the fluorine gas is introduced to react at a proper temperature, the manganese difluoride and the fluorine gas can be in full contact reaction, the conversion rate of the manganese difluoride is improved, the fluorination reaction in the manganese difluoride is complete, the content of the manganese trifluoride in a manganese trifluoride product produced by the method can reach 99%, and the content of the manganese difluoride is not more than 2%. In addition, the used perfluoropolyether oil can be repeatedly used after centrifugal separation, thereby ensuring the economical efficiency and practicability of the invention.
In the present embodiment, the molecular weight of the perfluoropolyether oil is 2000 to 10000. If the molecular weight of the perfluoropolyether oil is too low, the dispersity of manganese difluoride is not good, the boiling point of the low-molecular-weight perfluoropolyether oil is not high enough, obvious loss of the perfluoropolyether oil can occur in the subsequent heating fluorine gas introduction reaction process, and the cost is increased; if the molecular weight of the perfluoropolyether oil is too high, the viscosity of the perfluoropolyether oil is too high, and manganese difluoride is not well dispersed in the perfluoropolyether oil, so that the fluorine passing effect is influenced. Within the molecular weight range, the manganese dioxide has the optimal dispersion effect, the production efficiency is improved, and the loss of the perfluoropolyether oil is reduced. Preferably, the perfluoropolyether oil has a molecular weight of 2000 to 5000, more preferably 5000.
In the present embodiment, the mass ratio of manganese difluoride to perfluoropolyether oil is (0.05 to 1.5): 1. If the addition amount of manganese difluoride is too small, the single kettle productivity is too low, the economy is not high, and the efficiency is low; if the manganese difluoride is added too much, it is difficult to ensure that the manganese dioxide is uniformly dispersed in the perfluoropolyether oil, which affects the effect of fluorine gas. Within the above mass ratio range, the economic effect and the product yield can be better considered. Preferably, the mass ratio of manganese difluoride to perfluoropolyether oil is 1.
In the present embodiment, the mass ratio of manganese difluoride to fluorine gas is 1: (0.25-0.5). Within the mass ratio range, the reaction can be fully performed, and the waste caused by excessive consumption of fluorine gas can be avoided. Preferably, the mass ratio of manganese difluoride to fluorine gas is 1: (0.25-0.35).
In the present embodiment, the reaction temperature is 190 to 220 ℃, preferably 200 ℃.
In this embodiment, the reaction is carried out under stirring.
In this embodiment, the method for producing manganese trifluoride includes the steps of: and uniformly mixing manganese difluoride and perfluoropolyether oil, introducing fluorine gas to perform fluorination reaction after the temperature is raised to the reaction temperature, and obtaining manganese trifluoride.
In this embodiment, during the reaction, the tail gas is absorbed by the alkali solution. Further, the alkali is potassium hydroxide, sodium hydroxide or the like.
Example 1
A method of preparing manganese trifluoride, said method comprising the steps of:
step 1, adding 1000 g of perfluoropolyether oil with the molecular weight of 5000 into a two-liter stainless steel reaction kettle.
And 2, adding 1000 g of manganese difluoride into the reaction kettle. The reaction kettle is provided with a heating device, a drying device is arranged at the tail gas discharge position of the reaction kettle, and tail gas is introduced into the potassium hydroxide aqueous solution for absorption.
And 3, starting a stirring and heating device, heating to 200 ℃, starting to introduce fluorine gas, and controlling the temperature in the kettle to be about 200 ℃ during the whole reaction process. Sampling is carried out in the reaction process, products are detected in a laboratory until the content of manganese trifluoride is more than 98%, and the reaction is confirmed to be finished.
After the reaction, 298g of fluorine gas was consumed altogether, and 1202.76g of manganese trifluoride mixed product was prepared altogether, wherein the manganese trifluoride content was 99.17%.
Example 2
A method of preparing manganese trifluoride, said method comprising the steps of:
step 1, adding 1000 g of perfluoropolyether oil with molecular weight of 2000 into a two-liter stainless steel reaction kettle.
And 2, adding 50 g of manganese difluoride into the reaction kettle. The reaction kettle is provided with a heating device, a drying device is arranged at the tail gas discharge position of the reaction kettle, and tail gas is introduced into the potassium hydroxide aqueous solution for absorption.
And 3, starting a stirring and heating device, heating to 190 ℃, starting to introduce fluorine gas, and controlling the temperature in the kettle to be about 190 ℃ during the whole reaction process. Sampling is carried out in the reaction process, products are detected in a laboratory until the content of manganese trifluoride is more than 98%, and the reaction is confirmed to be finished.
After the reaction, 14g of fluorine gas was consumed, and 60.15g of manganese trifluoride mixed product was prepared, wherein the manganese trifluoride content was 99.30%.
Example 3
A method of preparing manganese trifluoride, said method comprising the steps of:
step 1, adding 1000 g of perfluoropolyether oil with the molecular weight of 10000 into a two-liter stainless steel reaction kettle.
And 2, adding 1500 g of manganese difluoride into the reaction kettle. The reaction kettle is provided with a heating device, a drying device is arranged at the tail gas discharge position of the reaction kettle, and tail gas is introduced into the potassium hydroxide water solution for absorption.
And 3, starting a stirring and heating device, heating to 220 ℃, and introducing fluorine gas, wherein the temperature in the kettle is controlled to be about 220 ℃ during the whole reaction process. Sampling is carried out in the reaction process, products are detected in a laboratory until the content of the manganese trifluoride is more than 98%, and the reaction is confirmed to be finished.
After the reaction, 482g of fluorine gas was consumed and 1802.17g of a manganese trifluoride mixed product was prepared, wherein the manganese trifluoride content was 98.53%.
Comparative example 1
A method of preparing manganese trifluoride, said method comprising the steps of:
step 1, adding 1000 g of manganese difluoride into a two-liter reaction kettle. The reaction kettle is provided with a heating device, a drying device is arranged at the tail gas discharge position of the reaction kettle, and tail gas is introduced into the potassium hydroxide aqueous solution for absorption.
And 2, starting a stirring and heating device, heating to 200 ℃, and introducing fluorine gas, wherein the temperature in the kettle is controlled to be about 200 ℃ during the whole reaction process. Sampling is carried out in the reaction process, and the content of manganese trifluoride in the product is detected in a laboratory. When the fluorine gas is in a significant excess, the content of manganese trifluoride reaches 90%, and the experiment is ended.
After the reaction is finished, 990g of fluorine gas is consumed, and 1186.95g of manganese trifluoride mixed product is prepared, wherein the content of manganese trifluoride is 91.44%.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The preparation method of manganese trifluoride is characterized by comprising the following steps: the perfluoropolyether oil is used as a dispersion medium, and manganese difluoride and fluorine gas react to generate manganese trifluoride.
2. The method of producing manganese trifluoride according to claim 1, wherein the molecular weight of said perfluoropolyether oil is 2000 to 10000.
3. The method of producing manganese trifluoride according to claim 1, wherein said perfluoropolyether oil has a molecular weight of 2000 to 5000.
4. The method of producing manganese trifluoride according to claim 1, wherein the mass ratio of manganese difluoride to perfluoropolyether oil is (0.05 to 1.5): 1.
5. The method for producing manganese trifluoride according to claim 1, wherein the mass ratio of manganese difluoride to perfluoropolyether oil is 1.
6. The method of producing manganese trifluoride according to claim 1, wherein the mass ratio of manganese difluoride to fluorine gas is 1: (0.25-0.5).
7. The method of claim 1, wherein the mass ratio of manganese difluoride and fluorine gas is 1: (0.25-0.35).
8. The method of producing manganese trifluoride according to claim 1, wherein the reaction temperature is 190 to 220 ℃.
9. The method of preparing manganese trifluoride according to claim 1, comprising the steps of: and uniformly mixing manganese difluoride and perfluoropolyether oil, introducing fluorine gas to perform fluorination reaction after the temperature is raised to the reaction temperature, and obtaining manganese trifluoride.
10. The method for preparing manganese trifluoride according to claim 1, wherein the off-gas is absorbed with an alkali solution during the reaction.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4438088A (en) * | 1982-03-11 | 1984-03-20 | The Dow Chemical Company | Preparation of antimony trifluorodichloride and fluorination of fluorinatable hydrocarbons and halocarbons therewith |
| JP2006104048A (en) * | 2004-09-10 | 2006-04-20 | Showa Denko Kk | Method for producing manganese fluoride |
| CN101014541A (en) * | 2004-09-10 | 2007-08-08 | 昭和电工株式会社 | Process for producing manganese fluoride |
| CN102351636A (en) * | 2011-08-26 | 2012-02-15 | 湖北卓熙氟化科技有限公司 | Novel technology for preparing pentafluoroethyl iodide by one-step method |
| CN114751458A (en) * | 2022-04-20 | 2022-07-15 | 天津大学 | Manganese trifluoride material with edge-free fused body structure and preparation method thereof |
-
2023
- 2023-01-04 CN CN202310006352.7A patent/CN115947375A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4438088A (en) * | 1982-03-11 | 1984-03-20 | The Dow Chemical Company | Preparation of antimony trifluorodichloride and fluorination of fluorinatable hydrocarbons and halocarbons therewith |
| JP2006104048A (en) * | 2004-09-10 | 2006-04-20 | Showa Denko Kk | Method for producing manganese fluoride |
| CN101014541A (en) * | 2004-09-10 | 2007-08-08 | 昭和电工株式会社 | Process for producing manganese fluoride |
| CN102351636A (en) * | 2011-08-26 | 2012-02-15 | 湖北卓熙氟化科技有限公司 | Novel technology for preparing pentafluoroethyl iodide by one-step method |
| CN114751458A (en) * | 2022-04-20 | 2022-07-15 | 天津大学 | Manganese trifluoride material with edge-free fused body structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Z. MAZEJ: "Room temperature syntheses of MnF3, MnF4 and hexafluoromanganete(IV) salts of alkali cations", JOURNAL OF FLUORINE CHEMISTRY, vol. 114, no. 1, 28 March 2002 (2002-03-28), pages 75 - 80, XP004344321, DOI: 10.1016/S0022-1139(01)00566-8 * |
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