CN115367774A - Preparation method and application of hexafluorophosphate - Google Patents
Preparation method and application of hexafluorophosphate Download PDFInfo
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- CN115367774A CN115367774A CN202211319974.7A CN202211319974A CN115367774A CN 115367774 A CN115367774 A CN 115367774A CN 202211319974 A CN202211319974 A CN 202211319974A CN 115367774 A CN115367774 A CN 115367774A
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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D13/00—Compounds of sodium or potassium not provided for elsewhere
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- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/005—Lithium hexafluorophosphate
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- C01P2006/82—Compositional purity water content
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Abstract
The invention relates to the field of energy storage batteries, in particular to a preparation method and application of hexafluorophosphate. The preparation method comprises the following steps: (1) Adding the inorganic solvent into the reaction device at low temperature, adding sodium phosphate in batches, and carrying out low-temperature heat preservation reaction; (2) After the reaction is finished, heating up to distill out the inorganic solvent for the first time, and then distilling out water for the second time; (3) Adding organic solvent to dissolve solid product, membrane filtering to remove insoluble substance, and distilling organic solvent for three times. The application provides a novel preparation method of hexafluorophosphate, which can avoid the phenomena of high raw material purity requirement, complex post-treatment method and complex operation existing in the conventional phosphorus pentafluoride synthesis method and hexafluorophosphate compound conversion method.
Description
Technical Field
The invention relates to the field of batteries, in particular to a preparation method and application of hexafluorophosphate.
Background
In order to meet the increasing battery requirements in the field of energy storage batteries, the development of novel batteries is more urgent, and compared with lead-acid batteries, nickel-cadmium batteries and nickel-hydrogen battery secondary batteries, the novel batteries have the advantages of high energy density, small self-discharge rate and long cycle life, and the advantages of the novel batteries can be used as the main development direction of the new energy storage industry.
The novel battery is mainly a lithium ion battery and a sodium ion battery, lithium hexafluorophosphate is always a hot research as the main electrolyte of the lithium ion battery, the sodium ion battery appears as a new battery, and sodium hexafluorophosphate is used as a main additive of the sodium ion battery, so that a larger market space can be provided. Ammonium hexafluorophosphate is one of the more important hexafluorophosphates, and can be used for preparing other hexafluorophosphates and is also an important substance for preventing dental caries.
The research on the preparation method of hexafluorophosphate in the prior art mainly focuses on the synthesis method of phosphorus pentafluoride and fluoride salt, the exchange method of hexafluorophosphate and the salt formation method of hexafluorophosphate. For example, chinese patent application (CN 202210565604) proposes a method of preparing hexafluorophosphoric acid by reacting phosphorus pentoxide with hydrogen fluoride, and then reacting with sodium hydroxide or sodium carbonate to prepare sodium hexafluorophosphate; US patent application (US 5993767A) reports the exchange of pyridinium salts of hexafluorophosphoric acid with lithium compounds of lithium hydroxide, lithium alkoxides and lithium alkyls to give lithium hexafluorophosphate; soc, part4, 4408 (1963) proposed a process for reacting dissolved lithium fluoride with gaseous phosphorus pentafluoride using anhydrous hydrogen fluoride as a solvent; japanese patent application (JP 1997165210) proposes reacting lithium fluoride with phosphorus pentafluoride in an organic non-aqueous solvent to obtain lithium hexafluorophosphate.
Hydrogen fluoride and a phosphorus source are used for preparing the hexafluorophosphoric acid, the phosphorus source is from phosphorus pentoxide, phosphorus trichloride or phosphorus pentachloride, and the requirements of the three on equipment in the charging process are strict; phosphorus pentafluoride gas is difficult to purify and prepare, and phosphorus pentafluoride reacts with fluoride because of the gas-solid two-phase reaction, fluoride needs ultra-fine powder or multiple holes, otherwise, the phenomenon that the surface of fluoride is coated by hexafluorophosphate and the reaction is not complete occurs; the exchange method needs high-purity hexafluorophosphate, and how to obtain the hexafluorophosphate is a problem and is not complete in reaction, so that a product which meets the battery grade is difficult to obtain.
Disclosure of Invention
The problems to be solved are as follows:
the method needs to solve the problems that in the existing preparation method of the hexafluorophosphate, phosphorus pentafluoride is difficult to obtain, the reaction is not thorough, the post-treatment is complex, and the control of the reaction process is complex.
The key content of the invention is as follows:
in order to solve the above problems, the present invention provides a method for preparing hexafluorophosphate, comprising the steps of:
(1) Reacting hydrofluoric acid, phosphoric acid and phosphate to obtain hexafluorophosphate;
(2) Concentrating under reduced pressure, distilling, adding non-aqueous good solvent, dissolving, and filtering;
(3) Concentrating the good solvent under reduced pressure, and adding a non-aqueous poor solvent for crystallization and precipitation;
(4) After filtration, the filter cake is dried under reduced pressure to obtain hexafluorophosphate.
Wherein the anions of the phosphate in the step (1) are dihydrogen phosphate, hydrogen phosphate or phosphate radical, and the cations are sodium ions, lithium ions or ammonium ions.
The non-aqueous good solvent in the step (2) is at least one of cyclic carbonate, chain carboxylate, nitrile, cyclic ether or chain ether.
The nonaqueous poor solvent in the step (3) is at least one of an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent and an aromatic ether solvent.
In the step (1), the reaction temperature of hydrofluoric acid, phosphoric acid and phosphate is-10-80 ℃.
The molar ratio of hydrogen fluoride, phosphoric acid and phosphate in the step (1) is 6 to 60:0 to 3: 1.
The concentration temperature in the step (2) is 25-80 ℃.
The mass ratio of the good nonaqueous solvent to the hexafluorophosphate product in the step (2) is 2 to 20.
The concentration temperature in the step (3) is 25-80 ℃.
The mass ratio of the nonaqueous poor solvent to the hexafluorophosphate product in the step (3) is 2 to 50
The drying temperature in the step (4) is 25-100 ℃.
In a preferred embodiment, the non-aqueous good solvent is dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate chain carbonate, ethylene carbonate, propylene carbonate, vinylene carbonate, fluoroethylene carbonate cyclic carbonate, methyl formate, ethyl acetate, methyl acetate, n-butyl acetate, isopropyl acetate, n-propyl acetate, propyl propionate chain carboxylate; at least one of acetonitrile, propionitrile chain nitrile, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol methyl butyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether chain ether, 1, 4-dioxane, 1, 3-dioxolane, and tetrahydrofuran cyclic ether.
In a preferred embodiment, the mass ratio of the good nonaqueous solvent to the hexafluorophosphate is 2 to 20.
In a preferred embodiment, the non-aqueous poor solvent is at least one of toluene, cyclohexane, dichloromethane, dichloroethane, trichloropropane, dichlorobutane, tetrachloroethylene, tetrachloroethane, chlorobenzene, and xylene.
Preferably, the filtration in step (4) is at least one of reduced pressure filtration, pressure filtration and centrifugal filtration.
Preferably, the crystallization temperature in the crystallization step in the step (3) is from-20 to 40 ℃.
Has the advantages that:
the preparation method of the hexafluorophosphate provided by the application provides a novel preparation method of the hexafluorophosphate, and the method can avoid the problems of high requirement on raw material purity, complex post-treatment method, complex operation and undetermined reaction in the existing phosphorus pentafluoride synthesis method, hexafluorophosphate compound conversion method or hexafluorophosphate salt formation method, can be convenient for researchers to prepare large-batch high-purity hexafluorophosphate, and can obtain more battery-grade hexafluorophosphate.
Detailed Description
The present invention relates to a method for producing a hexafluorophosphate salt, which comprises (1) reacting hydrofluoric acid, phosphoric acid and a phosphate salt to obtain a hexafluorophosphate salt; (2) Concentrating under reduced pressure, distilling, adding non-aqueous good solvent, dissolving, and filtering; (3) Concentrating the good solvent under reduced pressure, and adding a non-aqueous poor solvent for crystallization and precipitation; (4) After filtration, the filter cake is dried under reduced pressure to obtain hexafluorophosphate.
The method comprises the following steps: hydrofluoric acid, phosphoric acid and phosphate reaction
The reaction equation for the trim is as follows:
step (1): reacting hydrofluoric acid, phosphoric acid and phosphate to obtain hexafluorophosphate.
The phosphate used in the present invention has a cation selected from lithium, sodium or ammonium and an anion selected from dihydrogen phosphate, hydrogen phosphate and phosphate. Specific examples include the following:
1) Sodium salt
Sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate;
2) Lithium salt
Lithium phosphate, lithium dihydrogen phosphate, dilithium hydrogen phosphate;
3) Ammonium salts
Ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium polyphosphate.
The phosphate used in the reaction of the present invention may be a commercially available product as it is, may be used after purification, or may be used after production from another compound. The purity is not particularly limited, and a phosphate having a purity of 99% or more is preferable.
The phosphoric acid used in the reaction of the present invention is not particularly limited, but electronic grade phosphoric acid is preferable in order to obtain metal ions of hexafluorophosphate in accordance with the requirements of battery electrolyte, and the mass concentration of phosphoric acid is selected to be 50% or more, preferably 85% or more.
The concentration of the hydrofluoric acid is not particularly required, anhydrous hydrogen fluoride can be selected, and a 20-80% hydrofluoric acid aqueous solution can be selected; in order to reduce the energy consumption of the post-concentration water removal and ensure the smooth stirring of the reaction system, the mass ratio of the water to the hexafluorophosphate in the system is 1 to 1.5 when the reaction is finished.
In a preferable embodiment, the molar ratio of the hydrogen fluoride, phosphoric acid and phosphate is 6 to 60:0 to 3: 1. From the viewpoint of raw material cost, when the reaction condition is equation one, the molar ratio of hydrogen fluoride, phosphoric acid and phosphate is 18 to 36:2 to 3:1, preferably 18 to 24, 2 to 2.5, and further preferably 18 to 22: 2 to 2.25, wherein when the reaction condition is the equation II, the molar ratio of hydrogen fluoride, phosphoric acid and phosphate is 12 to 24:1 to 2:1, preferably 12 to 18: 1 to 1.5, and further preferably 12 to 15: 1 to 1.2, wherein when the reaction condition is the formula III, the molar ratio of hydrogen fluoride to phosphate is 6 to 12:1, preferably 6 to 10: 1, and further preferably 6 to 7.5: 1, when the reaction condition is equation four, the phosphate used is tripolyphosphate, and the molar ratio of hydrogen fluoride to phosphate is 30 to 60:2 to 3:1, preferably 30 to 45, 2 to 2.5, and more preferably 30 to 36, wherein when the molar ratio of hydrogen fluoride to phosphoric acid to phosphate is adjusted within the range described above, a high-purity hexafluorophosphate can be produced in a high yield without going through a complicated purification step.
In the reaction procedure of the invention, the feeding mode of hydrofluoric acid, phosphoric acid and phosphate is not particularly limited, in order to avoid the reaction runaway and product decomposition caused by high temperature due to large amount of heat release in the material mixing process, the phosphate is preferably slowly added into the cooled mixed liquid of hydrofluoric acid and phosphoric acid or the cooled hydrofluoric acid, the upper limit of the reaction temperature is controlled to be 80 ℃, the reaction temperature is controlled to be too slow due to too low temperature, the lower limit of the reaction temperature is-10 ℃, preferably to 0 ℃ to 50 ℃, further preferably to 25 ℃ to 40 ℃, and the reaction time is 2 to 12 hours, preferably to 4 to 8 hours. The reaction can be carried out at normal pressure, and in order to avoid hydrogen fluoride overflow, the reaction can also be carried out in a closed reactor.
Step (2): concentrating under reduced pressure, distilling, dissolving in non-aqueous solvent, and filtering
In the reaction step of the present invention, when the first step is completed, concentration under reduced pressure is required to remove excess hydrogen fluoride, hexafluorophosphoric acid and water. In order to avoid the decomposition of hexafluorophosphate caused by overhigh temperature, the upper limit of the temperature is controlled to be 80 ℃, the efficiency is deteriorated due to overlow temperature, the lower limit of the temperature is 25 ℃, preferably 40-60 ℃, the vacuum degree has no special requirement, and the vacuum degree is below 5000Pa, preferably below 1000 Pa. When the decompression concentration is started, redundant hydrogen fluoride in the system firstly overflows, the hexafluorophosphoric acid is decomposed into hydrogen fluoride and phosphorus pentafluoride along with the rise of temperature, then the hydrogen fluoride and the phosphorus pentafluoride overflow the system along with the vacuum, and finally water in the system overflows the system along with the vacuum.
The hexafluorophosphate gradually precipitates as the water content in the system decreases, and after completion of the concentration, the water content in the system is controlled to be within 1%, preferably within 0.5%, and more preferably within 0.2%.
The non-aqueous good solvent selected in the dissolving step of the present invention is a non-aqueous organic solvent, and in order to effectively remove solvent residues, a solvent having a boiling point of 300 ℃ or less, more preferably a solvent having an atmospheric boiling point of 200 ℃ or less, and still more preferably a solvent having an atmospheric boiling point of 160 ℃ or less is selected.
As a preferred embodiment, the non-aqueous organic solvent is a polar organic solvent; more preferably, the polar aprotic organic solvent includes at least one of a chain carbonate, a cyclic carbonate, a chain carboxylate, a chain ether, a cyclic ether, or a chain nitrile solvent.
As a preferable scheme, the polar aprotic organic solvent is dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate chain carbonate; ethylene carbonate, propylene carbonate, vinylene carbonate, fluoroethylene carbonate cyclic carbonate; methyl formate, ethyl acetate, methyl acetate, n-butyl acetate, isopropyl acetate, n-propyl acetate, propyl propionate chain carboxylate; acetonitrile, propionitrile chain nitrile; ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol methyl butyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether chain ether; at least one of 1, 4-dioxane, 1, 3-dioxolane, tetrahydrofuran cyclic ether; more preferably at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl acetate, n-butyl acetate, acetonitrile, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.
The mass ratio of the nonaqueous organic solvent used in the present invention to the hexafluorophosphate is not particularly limited, but is preferably 20 times or less, more preferably 15 times or less, and still more preferably 10 times or less. The mass ratio of the nonaqueous organic solvent used in the reaction to the hexafluorophosphate is preferably 2 times or more, and more preferably 3 times or more. Within the above range, the dissolution efficiency is excellent and the hexafluorophosphate salt is not precipitated.
The filtering temperature of the non-aqueous good solvent is not particularly limited in the present invention, and in order to prevent the product from being dissolved slowly or precipitated due to too low temperature, the lower limit of the temperature is 10 ℃, preferably 25 ℃, the solvent is volatilized due to too high temperature filtering, and the upper limit of the temperature is set to 80 ℃, preferably 60 ℃.
As a preferable mode, the filtration mode includes any one of reduced pressure filtration, pressure filtration and centrifugal filtration; in a further embodiment, the filtration can also be carried out by standing and pouring out the supernatant. Further, these methods may be combined or the same method may be repeated. The filtering medium may be any one of a filter membrane, a filter paper, a filter cloth, a filter element, and a sintered mesh, and the pore size of the filtering medium is 5 μm or less, preferably 1 μm or less, and more preferably 0.1 μm or less.
And (3): concentration and crystallization process
The method for concentrating the filtered hexafluorophosphate solution is not particularly limited, and may be atmospheric distillation concentration or vacuum distillation concentration, but when the concentration temperature is too high, unexpected side reactions may occur, and vacuum concentration tends to have higher concentration efficiency, and is preferably vacuum distillation concentration at 80 ℃ or lower, and more preferably vacuum concentration at 60 ℃ or lower. The lower limit of the degree of vacuum is not limited, and in consideration of the degree to which the actual degree of vacuum is easily achieved, the lower limit is preferably 5000Pa or less, and more preferably 1000Pa or less; the upper limit of the degree of vacuum is not limited, but is preferably 1Pa or more, more preferably 10Pa or more, and still more preferably 20Pa or more, in consideration of the limit of the degree of vacuum measurement and the degree of vacuum system equipment that can be practically achieved. The concentration of the good solvent takes away the residual water, so that the water content in the system is further reduced to be less than 100 ppm.
The yield of the product is reduced due to a large amount of the concentrated residual good solvent, and the upper limit of the concentration residual amount of the reaction solvent is selected as follows: the amount of the hexafluorophosphate added is preferably 5 times or less, more preferably 3 times or less, and still more preferably 2 times or less by weight. On the other hand, when the residual amount is too small, the slurry becomes viscous, and stirring becomes difficult. Therefore, the lower limit of the concentration-remaining amount of the reaction solvent is preferably 0.5 times or more, more preferably 1 time or more, the weight of the hexafluorophosphate charged.
Adding a non-aqueous poor solvent in the crystallization process, wherein the non-aqueous poor solvent is at least one of an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent and an aromatic ether solvent; the aromatic hydrocarbon solvent also comprises halogenated aromatic hydrocarbon, and the aliphatic hydrocarbon solvent also comprises halogenated aromatic hydrocarbon.
In a preferred embodiment, the aliphatic hydrocarbon is at least one of n-hexane, n-heptane, petroleum ether, cyclohexane, methylcyclohexane, methylene chloride, dichloroethane, tetrachloroethane, trichloropropane, tetrachloroethylene, and 1, 4-dichlorobutane.
In a preferred embodiment, the aromatic hydrocarbon is at least one of toluene, benzene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, and trichlorobenzene.
In a preferred embodiment, the aromatic ether is at least one of anisole, phenetole, and diphenyl ether.
In view of removal of the solvent during drying, the solvent is preferably 300 ℃ or lower, more preferably 160 ℃ or lower, and among the above solvents, at least one of toluene, cyclohexane, dichloromethane, dichloroethane, trichloropropane, dichlorobutane, tetrachloroethylene, tetrachloroethane, chlorobenzene, and xylene is preferable.
The weight ratio of the poor solvent used in the present invention to the hexafluorophosphate is not particularly limited, but is preferably 50 times or less, more preferably 25 times or less, and still more preferably 10 times or less. The weight ratio of the poor solvent used in the crystallization step to the hexafluorophosphate is preferably 2 times or more, and more preferably 3 times or more. Within the range, the method can ensure higher yield of the crystals and better purification effect of the crystals, and obtain the hexafluorophosphate with better quality and performance.
The temperature at the time of crystallization by adding the poor solvent in the present invention is not particularly limited, but is preferably 100 ℃ or lower, more preferably 80 ℃ or lower, and still more preferably 60 ℃ or lower. The temperature at the time of crystallization by adding the poor solvent is preferably 0 ℃ or higher, more preferably 10 ℃ or higher, and still more preferably 20 ℃ or higher. When the temperature for crystallization by adding the poor solvent is within the above range, the hexafluorophosphate is not precipitated in a large amount because of the excessively low crystallization temperature.
The charging time in the crystallization step by adding a poor solvent is not limited, but is preferably 6 hours or less, more preferably 4 hours or less, and further preferably 2 hours or less. In the present invention, the charging time in the poor solvent-added crystallization step is preferably 1min or more, more preferably 10min or more, and still more preferably 30min or more. By setting the charging time in the reaction step of the present invention within the above range, a relatively high efficiency can be obtained while a relatively good crystal purification effect is obtained.
And (4): filtering and drying to obtain the product
The solid-liquid separation method in the present invention is not particularly limited, and any of reduced pressure filtration, pressure filtration and centrifugal filtration can be preferably used.
The temperature at the time of solid-liquid separation in the crystallization step with the addition of a poor solvent is not particularly limited in the present invention, but is preferably 40 ℃ or lower, more preferably 25 ℃ or lower, and still more preferably 20 ℃ or lower in order to increase the crystal yield. On the other hand, too low a temperature causes deterioration of crystallization effect and deterioration of quality of hexafluorophosphate, and therefore, it is preferably-20 ℃ or higher, more preferably-10 ℃ or higher, and still more preferably 0 ℃ or higher.
The hexafluorophosphate obtained through the above steps is preferably removed by drying under reduced pressure because the organic solvent used in the above steps remains. If the temperature is too high, the hexafluorophosphate may be thermally decomposed, and if the temperature is too low, the hexafluorophosphate may not be sufficiently removed. The temperature for removal is preferably 100 ℃ or lower, more preferably 80 ℃ or lower, and still more preferably 60 ℃ or lower. Further, it is preferably 0 ℃ or higher, more preferably 10 ℃ or higher, and still more preferably 25 ℃ or higher. The longer the drying time, the better the removal effect, but at the same time, the production efficiency is lowered, and the drying time is preferably 30min or more, more preferably 1h or more, and further preferably 2h or more. The time for drying and removing is preferably 24 hours or less, more preferably 18 hours or less, and further preferably 12 hours or less.
The technical solution of the present invention is further explained by the following embodiments.
Example 1
Example 1 provides a method for the preparation of sodium hexafluorophosphate comprising the steps of: (1) 34.0g of 70% hydrofluoric acid aqueous solution is added into a reaction device at low temperature of minus 5 ℃ and low temperature, 12.0g of sodium dihydrogen phosphate is slowly added in batches, and after the addition, the reaction is carried out for 8 hours at the temperature of 2 ℃; (2) After the reaction, 45 ℃ reduced pressure concentration to about 17.0g, adding 50.0g diethyl carbonate to dissolve solid product, filtering through a polytetrafluoroethylene membrane with the aperture of 0.22 μm to remove insoluble substances and mechanical impurities, (3) filtrate at 50 ℃ reduced pressure concentration to about 40.0g, dripping 51.0g dichloromethane, cooling to 10 ℃, filtering, and drying filter cake at 25 ℃ under reduced pressure for 8 hours to obtain 15.0g sodium hexafluorophosphate, wherein the yield is 89.3%, the purity is 99.9%, the water content is 30ppm, the acid value is 15ppm (calculated by HF), the chloride ion is less than 1.0ppm, the sulfate radical is less than 5.0ppm, the potassium is less than 2.0ppm, the iron is less than 2.0ppm, the calcium is less than 2.0ppm, and the rest metal ion is less than 1.0ppm.
Example 2
Embodiment 2 provides a method for preparing sodium hexafluorophosphate, comprising the following steps: (1) 28.0g of 64 percent hydrofluoric acid aqueous solution is added into a reaction device at low temperature of 0 ℃ and slowly added with 12.0g of sodium dihydrogen phosphate in batches, and after the addition is finished, the reaction is carried out for 6 hours at 40 ℃; (2) After the reaction is finished, concentrating under reduced pressure at 45 ℃ to about 16.9g, adding ethylene glycol dimethyl ether 68.0g to dissolve a solid product, filtering through a polytetrafluoroethylene membrane with the membrane aperture of 0.22 mu m to remove insoluble substances and mechanical impurities, (3) concentrating the filtrate under reduced pressure at 25-30 ℃ to about 34.0g, dropwise adding 68.0g of 1, 2-dichloroethane, cooling to 5 ℃, filtering, drying the filter cake under reduced pressure at 45 ℃ for 6 hours to obtain 14.6g of sodium hexafluorophosphate, wherein the yield is 86.9%, the purity is 99.9%, the water content is 20ppm, the acid value is 14ppm (calculated by HF), the chloride ion is less than 1.0ppm, the sulfate radical is less than 5.0ppm, the potassium is less than 2.0ppm, the iron is less than 2.0ppm, the calcium is less than 2.0ppm, and the rest metal ions are less than 1.0ppm.
Example 3
Embodiment 3 provides a method for preparing sodium hexafluorophosphate, comprising the following steps: (1) 22.1g of 57 percent hydrofluoric acid aqueous solution is added into a reaction device at the temperature of 5 ℃ at low temperature and slowly added with 12.0g of sodium dihydrogen phosphate in batches, and after the addition is finished, the reaction is carried out for 4 hours at the temperature of 80 ℃; (2) After the reaction, 45 ℃ vacuum concentration to about 17.3g, adding diethylene glycol dimethyl ether 40.0g dissolved solid product, filtering through a polytetrafluoroethylene membrane with the membrane aperture of 0.22 μm to remove insoluble matters and mechanical impurities, (3) vacuum concentration of the filtrate at 80 ℃ to about 35.0g, dripping 85.0g of toluene, cooling to 0 ℃, filtering, and drying the filter cake at 80 ℃ under reduced pressure for 4 hours to obtain 15.4g of sodium hexafluorophosphate, the yield is 91.7%, the purity is 99.9%, the moisture content is 15ppm, the acid value is 17ppm (calculated by HF), the chloride ion is less than 1.0ppm, the sulfate radical is less than 5.0ppm, the potassium is less than 2.0ppm, the iron is less than 2.0ppm, the calcium is less than 2.0ppm, and the rest metal ions are less than 1.0ppm.
Example 4
Embodiment 4 provides a method for preparing sodium hexafluorophosphate, comprising the following steps: (1) 45.4g of 57.7% hydrofluoric acid aqueous solution is added into a reaction device at the temperature of 5 ℃ for low-temperature cooling, 14.4g of 85% phosphoric acid is added, 14.2g of disodium hydrogen phosphate is slowly added in batches, and after the addition, the reaction is carried out at the temperature of 45 ℃ for 6 hours; (2) After the reaction is finished, concentrating under reduced pressure to about 35.0g at 25-65 ℃, adding 136.0g of ethyl acetate to dissolve a solid product, filtering by a polytetrafluoroethylene membrane with the membrane pore size of 0.22 mu m to remove insoluble substances and mechanical impurities, (3) concentrating the filtrate under reduced pressure to about 67.0g at 50 ℃, dropwise adding 170.0g of dimethylbenzene, cooling to 10 ℃, filtering, and drying the filter cake under reduced pressure at 60 ℃ for 5 hours to obtain 29.6g of sodium hexafluorophosphate, wherein the yield is 88.1%, the purity is 99.9%, the moisture content is 16ppm, the acid value is 15ppm (calculated by HF), the chloride ion is less than 1.0ppm, the sulfate radical is less than 5.0ppm, the potassium is less than 2.0ppm, the iron is less than 2.0ppm, the calcium is less than 2.0ppm, and the rest metal ions are less than 1.0ppm.
Example 5
Example 5 provides a method for preparing sodium hexafluorophosphate, comprising the steps of: (1) 82.8g 65.2% hydrofluoric acid aqueous solution is added into a reaction device at the temperature of 5 ℃ for low-temperature cooling, 28.8g 85% phosphoric acid is added, 16.4g of sodium phosphate is slowly added in batches, and after the addition is finished, the reaction is carried out at the temperature of 45 ℃ for 6 hours; (2) After the reaction, the temperature is raised to 45 ℃, the mixture is decompressed and concentrated to about 52.2g, 204.0g of butyl acetate is added to dissolve solid products, undissolved substances and mechanical impurities are removed by filtering through a polytetrafluoroethylene membrane with the membrane aperture of 0.22 mu m, the filtrate (3) is decompressed and concentrated to about 102.5g at 80 ℃, 255.0g of 1,2, 3-trichloropropane is dripped in the filtrate, the mixture is cooled to 10 ℃, filtered, and the filter cake is decompressed and dried at 60 ℃ for 5h to obtain 45.8g of sodium hexafluorophosphate, the yield is 90.9 percent, the purity is 99.9 percent, the water content is 19ppm, the acid value is 18ppm (calculated by HF), the chloride ion is less than 1ppm, the sulfate radical is less than 5ppm, the potassium is less than 2.0ppm, the iron is less than 2.0ppm, the calcium is less than 2.0ppm, and the rest metal ions are less than 1.0ppm.
Example 6
Example 6 provides a method for preparing sodium hexafluorophosphate, comprising the steps of: (1) 152.1g of 65.8% hydrofluoric acid aqueous solution is added into a reaction device at low temperature and low temperature of 5 ℃, 25.4g of 85% phosphoric acid is added, 27.6g of sodium tripolyphosphate is slowly added in batches, and after the addition, the reaction is carried out for 6 hours at the temperature of 45 ℃; (2) After the reaction is finished, heating to 45 ℃, concentrating under reduced pressure to about 86g, adding 255.0g of acetonitrile to dissolve a solid product, filtering by a polytetrafluoroethylene membrane with the membrane aperture of 0.22 mu m to remove insoluble substances and mechanical impurities, (3) concentrating the filtrate at 30 ℃ under reduced pressure to about 180g, dripping 332g of chlorobenzene, cooling to 10 ℃, filtering, drying the filter cake at 60 ℃ under reduced pressure for 5 hours to obtain 75.0g of sodium hexafluorophosphate, wherein the yield is 89.3%, the purity is 99.9%, the water content is 19ppm, the acid value is 18ppm (calculated by HF), the chloride ion is less than 1.0ppm, the sulfate radical is less than 5.0ppm, the potassium is less than 2.0ppm, the iron is less than 2.0ppm, the calcium is less than 2.0ppm, and the rest metal ions are less than 1.0ppm.
Example 7
Embodiment 7 provides a method for preparing lithium hexafluorophosphate, comprising the following steps: (1) 21.0g of 62.3% hydrofluoric acid aqueous solution is added into a reaction device at the temperature of 5 ℃ for low temperature cooling, 10.3g of lithium dihydrogen phosphate is slowly added in batches, and after the addition is finished, the reaction is carried out for 7 hours at the temperature of 15 ℃; (2) After the reaction, the temperature is raised to 45 ℃ and the mixture is concentrated to about 15.9g under reduced pressure, then 45.6 g of methyl ethyl carbonate is added to dissolve solid products, insoluble substances and mechanical impurities are removed by filtration through a polytetrafluoroethylene membrane with the membrane aperture of 0.22 mu m, and (3) the filtrate is concentrated to about 38.1 g under reduced pressure at 50 ℃, 76.0 g of 1, 2-tetrachloroethane is dripped, the mixture is cooled to 15 ℃, filtered, and the filter cake is dried under reduced pressure at 60 ℃ for 6 hours to obtain 13.4g of lithium hexafluorophosphate, wherein the yield is 89%, the purity is 99.9%, the water content is 21ppm, the acid value is 13ppm (calculated by HF), the chloride ion is less than 1.0ppm, the sulfate radical is less than 5.0ppm, the sodium is less than 2.0ppm, the potassium is less than 2.0ppm, the iron is less than 2.0ppm, the calcium is less than 2.0ppm, and the rest of metal ions is less than 1.0ppm.
Example 8
Embodiment 8 provides a method for preparing lithium hexafluorophosphate, comprising the steps of: (1) 42.2g of 62.1 percent hydrofluoric acid aqueous solution is added into a reaction device at the temperature of 5 ℃ for low temperature cooling, 14.4g of 85 percent phosphoric acid is added, 11.0g of dilithium hydrogen phosphate is slowly added in batches, and after the addition, the reaction is carried out for 4 hours at the temperature of 50 ℃; (2) After the reaction, the temperature is raised to 45 ℃ and the pressure is reduced and the concentration is reduced to about 31.8 g, then 91.2 g of diethyl carbonate is added to dissolve solid products, undissolved substances and mechanical impurities are removed by filtration through a polytetrafluoroethylene membrane with the membrane aperture of 0.22 mu m, 3) the filtrate is reduced and concentrated to about 76.1 g at 50 ℃, 152.0 g of 1, 4-dichlorobutane is dripped, the filtrate is cooled to 15 ℃, filtered, and the filter cake is dried at 60 ℃ for 6 hours under reduced pressure to obtain 27.1g of lithium hexafluorophosphate, the yield is 89.1 percent, the purity is 99.9 percent, the water content is 12ppm, the acid value is 11ppm (calculated by HF), the chloride ion is less than 1.0ppm, the sulfate radical is less than 5.0ppm, the sodium content is less than 2ppm, the potassium content is less than 2.0ppm, the iron content is less than 2.0ppm, the calcium content is less than 2.0ppm, and the rest metal ions are less than 1.0ppm.
Example 9
Example 9 provides a method for preparing lithium hexafluorophosphate, comprising the steps of: (1) 77.9g of 69.5% hydrofluoric acid aqueous solution is cooled at 5 ℃ and added into the reaction device, 28.9g of 85% phosphoric acid is added, 11.6g of lithium phosphate is slowly added in batches, and after the addition is finished, the reaction is carried out for 5 hours at 40 ℃; (2) After the reaction is finished, heating to 25-65 ℃, concentrating under reduced pressure to about 46.8g, adding 137g of dimethyl carbonate to dissolve a solid product, filtering by a polytetrafluoroethylene membrane with the membrane pore diameter of 0.22 mu m to remove insoluble substances and mechanical impurities, (3) concentrating the filtrate under reduced pressure to about 114g at 50 ℃, dropwise adding 228 g of 1, 2-tetrachloroethylene, cooling to 15 ℃, filtering, drying the filter cake under reduced pressure at 60 ℃ for 6 hours to obtain 40.1g of lithium hexafluorophosphate, wherein the yield is 87.8%, the purity is 99.9%, the water content is 10ppm, the acid value is 16ppm (calculated by HF), the chloride ion is less than 1.0ppm, the sulfate radical is less than 5.0ppm, the sodium is less than 2.0ppm, the potassium is less than 2.0ppm, the iron is less than 2.0ppm, the calcium is less than 2.0ppm, and the rest metal ions are less than 1.0ppm.
Example 10
Example 10 provides a method for producing ammonium hexafluorophosphate comprising the steps of: (1) 22.1g of 58.8 percent hydrofluoric acid aqueous solution is added into a reaction device at the temperature of 5 ℃ at low temperature and slowly added with 11.5g of ammonium dihydrogen phosphate in batches, and after the addition is finished, the reaction is carried out for 8 hours at the temperature of 5 ℃; (2) After the reaction is finished, heating to 25-65 ℃, decompressing and concentrating to about 16.6 g, adding 49.0g of methyl ethyl carbonate to dissolve a solid product, filtering by a polytetrafluoroethylene membrane with the membrane aperture of 0.22 mu m to remove insoluble substances and mechanical impurities, (3) decompressing and concentrating filtrate at 50 ℃ to about 36.1g, dripping 82 g of dichloromethane, cooling to 5 ℃, filtering, decompressing and drying filter cake at 60 ℃ for 5 hours to obtain 14.8g of ammonium hexafluorophosphate, wherein the yield is 90.8%, the purity is 99.9%, the moisture is 21ppm, the acid value is 25ppm (calculated by HF), the chloride ion is less than 1.0ppm, the sulfate radical is less than 5.0ppm, the sodium is less than 2.0ppm, the potassium is less than 2.0ppm, the iron is less than 2.0ppm, the calcium is less than 2.0ppm, and the rest metal ions are less than 1.0ppm.
Example 11
Example 11 provides a method for producing ammonium hexafluorophosphate comprising the steps of: (1) 46.2g of 60.6% hydrofluoric acid aqueous solution is added into a reaction device at low temperature and low temperature of 5 ℃, 14.4g of 85% phosphoric acid is added, 13.2g of diammonium hydrogen phosphate is slowly added in batches, and after the addition, the reaction is carried out for 4 hours at 70 ℃; (2) After the reaction, the temperature is raised to 45 ℃, the mixture is decompressed and concentrated to about 33.4 g, then 98 g of diethyl carbonate is added to dissolve solid products, insoluble substances and mechanical impurities are removed by filtering through a polytetrafluoroethylene membrane with the membrane aperture of 0.22 mu m, the filtrate (3) is decompressed and concentrated to about 72.0 g at 30 ℃, 163 g of toluene is dripped, the mixture is cooled to 10 ℃, and the filtration is carried out, the filter cake is decompressed and dried for 5 hours at 60 ℃ to obtain 29.1g of ammonium hexafluorophosphate, the yield is 89.3%, the purity is 99.9%, the moisture is 19ppm, the acid value is 17ppm (calculated by HF), the chloride ion is less than 1.0ppm, the sulfate radical is less than 5.0ppm, the sodium is less than 2.0ppm, the iron is less than 2.0ppm, the calcium is less than 2.0ppm, and the rest metal ions are less than 1.0ppm.
Example 12
Example 12 provides a method for producing ammonium hexafluorophosphate, comprising the steps of: (1) 81.3g of 66.4 percent hydrofluoric acid aqueous solution is added into a reaction device at the temperature of 5 ℃ at low temperature and low temperature, 28.9g of 85 percent phosphoric acid is added, 14.9g of ammonium phosphate is slowly added in batches, and after the addition is finished, the reaction is carried out at the temperature of 40 ℃ for 5 hours; (2) After the reaction is finished, the temperature is raised to 45 ℃, the mixture is decompressed and concentrated to about 50.4 g, 149g of dimethyl carbonate is added to dissolve a solid product, insoluble substances and mechanical impurities are removed through filtration of a polytetrafluoroethylene membrane with the membrane aperture of 0.22 mu m, (3) the filtrate is decompressed and concentrated to about 108g at 60 ℃, 24pg 1, 2-dichloroethane is dripped, the mixture is cooled to 10 ℃, and filtration is carried out, and the filter cake is decompressed and dried for 5 hours at 60 ℃ to obtain 42g of ammonium hexafluorophosphate, wherein the yield is 85.9%, the purity is 99.9%, the moisture is 17ppm, the acid value is 11ppm (calculated by HF), the chloride ion is less than 1.0ppm, the sulfate radical is less than 5.0ppm, the sodium is less than 2.0ppm, the potassium is less than 2.0ppm, the iron is less than 2.0ppm, the calcium is less than 2.0ppm, and the rest metal ions are less than 1.0ppm.
According to the embodiments, the preparation method of hexafluorophosphate provided by the invention provides a novel preparation method of hexafluorophosphate, which can avoid the phenomena of high requirement on raw material purity, complex post-treatment method and complex operation existing in the existing phosphorus pentafluoride synthesis method and hexafluorophosphate compound conversion method, and can facilitate enterprises to prepare large-batch high-purity hexafluorophosphate.
Claims (6)
1. A method for preparing hexafluorophosphate is characterized in that: the method comprises the following steps: (1) Reacting hydrofluoric acid, phosphoric acid and phosphate to obtain hexafluorophosphate; (2) Concentrating under reduced pressure, distilling, adding non-aqueous good solvent, dissolving, and filtering; (3) Concentrating the good solvent under reduced pressure, and adding a non-aqueous poor solvent for crystallization and precipitation; (4) After filtering, decompressing and drying a filter cake to obtain hexafluorophosphate;
wherein the anion of the phosphate is dihydrogen phosphate, hydrogen phosphate or phosphate radical, and the cation is sodium ion, lithium ion or ammonium ion;
the nonaqueous good solvent in the step (2) is at least one of cyclic carbonate, chain carboxylate, nitrile, cyclic ether or chain ether;
the nonaqueous poor solvent in the step (3) is at least one of an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent and an aromatic ether solvent;
in the step (1), the reaction temperature of hydrofluoric acid, phosphoric acid and phosphate is-10-80 ℃;
the step (1) is hydrogen fluoride: phosphoric acid: the molar ratio of the phosphate is 6 to 60:0 to 3: 1;
the temperature of the reduced pressure concentration distillation in the step (2) is 25-80 ℃;
the mass ratio of the good nonaqueous solvent in the step (2) to the hexafluorophosphate product is 2 to 20;
the temperature of the good solvent subjected to reduced pressure concentration in the step (3) is 25-80 ℃;
the mass ratio of the nonaqueous poor solvent to the hexafluorophosphate product in the step (3) is 2 to 50;
the temperature of reduced pressure drying in the step (4) is 25-100 ℃;
the mass ratio of the good nonaqueous solvent to the hexafluorophosphate is 2 to 20.
2. The method for producing hexafluorophosphate according to claim 1, wherein: the non-aqueous good solvent is dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate chain carbonate, ethylene carbonate, propylene carbonate, vinylene carbonate, fluoroethylene carbonate cyclic carbonate, methyl formate, ethyl acetate, methyl acetate, n-butyl acetate, isopropyl acetate, n-propyl acetate and propyl propionate chain carboxylate; at least one of acetonitrile, propionitrile chain nitrile, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol methyl butyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether chain ether, 1, 4-dioxane, 1, 3-dioxolane, and tetrahydrofuran cyclic ether.
3. The method for producing hexafluorophosphate according to claim 2, wherein: the non-aqueous poor solvent is at least one of toluene, cyclohexane, dichloromethane, dichloroethane, trichloropropane, dichlorobutane, tetrachloroethylene, tetrachloroethane, chlorobenzene and xylene.
4. The method for producing hexafluorophosphate according to claim 3, wherein: the filtration mode in the step (4) is at least one of reduced pressure filtration, pressure filtration and centrifugal filtration.
5. The method for producing hexafluorophosphate according to claim 4, wherein: the crystallization temperature in the crystallization step (3) is-20 to 40 ℃.
6. Use of the process for the preparation of hexafluorophosphate of any one of claims 1 to 5, wherein: the preparation method of the hexafluorophosphate is applied to a preparation process of the hexafluorophosphate and a preparation process of a hexafluorophosphate solution.
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| CN101605723A (en) * | 2007-02-08 | 2009-12-16 | 斯泰拉化工公司 | The manufacture method of hexafluorophosphate |
| CN102659090A (en) * | 2012-04-20 | 2012-09-12 | 四川大学 | Preparation method of lithium hexafluorophate |
| CN104310327A (en) * | 2007-02-08 | 2015-01-28 | 斯泰拉化工公司 | Method of manufacturing phosphorous pentafluoride and hexafluorophosphate |
| CN108217622A (en) * | 2017-12-21 | 2018-06-29 | 珠海市赛纬电子材料股份有限公司 | A kind of preparation method of sodium hexafluoro phosphate |
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| CN101605723A (en) * | 2007-02-08 | 2009-12-16 | 斯泰拉化工公司 | The manufacture method of hexafluorophosphate |
| CN104310327A (en) * | 2007-02-08 | 2015-01-28 | 斯泰拉化工公司 | Method of manufacturing phosphorous pentafluoride and hexafluorophosphate |
| CN102659090A (en) * | 2012-04-20 | 2012-09-12 | 四川大学 | Preparation method of lithium hexafluorophate |
| CN108217622A (en) * | 2017-12-21 | 2018-06-29 | 珠海市赛纬电子材料股份有限公司 | A kind of preparation method of sodium hexafluoro phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115849410A (en) * | 2022-12-14 | 2023-03-28 | 九江天赐高新材料有限公司 | Preparation method of alkali metal hexafluorophosphate |
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