CN1212264C - Method and equipment for synthesizing hexafluorophosphate - Google Patents
Method and equipment for synthesizing hexafluorophosphate Download PDFInfo
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- CN1212264C CN1212264C CN 03113898 CN03113898A CN1212264C CN 1212264 C CN1212264 C CN 1212264C CN 03113898 CN03113898 CN 03113898 CN 03113898 A CN03113898 A CN 03113898A CN 1212264 C CN1212264 C CN 1212264C
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Abstract
The present invention relates to a method for synthesizing hexafluorophosphate, which orderly comprises the process steps of anhydrous hydrogen fluoride, hexafluorophosphate synthesis, low temperature crystallization, crystallization filtration and washing filtration, airflow drying and vacuum strengthening drying. Synthesis equipment comprises an electrolyzing and dewatering device of anhydrous hydrogen fluoride and a synthesis reaction device of lithium hexafluorophosphate. Before synthesis reaction, the moisture content of a solvent is reduced to be within an admissible range, impurities which are generated because of the moisture are eliminated, and the free acid content is reduced. As the solid and liquid separation of low temperature is used, the product purity is improved, and purification post treatment which wastes time, is cockamamie and can further bring in pollution possibility is avoided. As airflow carried by inert gas is used for drying, the present invention has the advantages of high efficiency, energy source saving and cost reduction. The method is simple and feasible, and the synthesized lithium hexafluorophosphate product has high purity, low moisture content and low free acid content and can be directly used as the electrolyte of a secondary lithium ion battery. An abbreviation inner lining of a synthesis reaction device is used, and the metallic ion content in the product is reduced.
Description
Technical field the present invention relates to the preparation of halogen-containing condensed phosphoric acid salt, relates in particular to a kind of synthetic method and equipment thereof of hexafluorophosphate.
The background technology hexafluorophosphate is lithium hexafluoro phosphate particularly, because of its unique physical chemistry and chemical property, has become and has made one of important ionogen that secondary lithium battery uses.Existing lithium hexafluoro phosphate preparation method is many, as ion-exchange-resin process, gas-solid reaction method, substitution method, non-aqueous solvent method and Chinese patent CN1210810A, CN1263047A and the CN1339401A production of disclosed lithium hexafluoro phosphate or preparation method etc. respectively.In the aforesaid method; ion-exchange-resin process cost height; because costing an arm and a leg of ion exchange resin and attendant equipment; and common meeting lingering section small molecule monomer or small molecules polymer in the used exchange resin; can cause the change of electrical property equally; the gas-solid reaction method can only be in solid surface reaction because of reaction; transformation efficiency is low; and substitution method is introduced too much impurity easily, aftertreatment difficulty, the synthetic method that adopts phosphorus pentachloride and lithium fluoride to react in anhydrous hydrogen fluoride; because of there being hydrogenchloride to generate; be difficult to separate with unreacted hydrogen fluoride, general adopt utilizes the reaction of phosphorus pentafluoride and lithium fluoride to synthesize lithium hexafluoro phosphate in non-aqueous solvent hydrogen fluoride more, yet; because lithium hexafluoro phosphate is to the unstable of moisture; even a spot of moisture also can react with the resultant lithium hexafluoro phosphate, produce fluorine oxygen phosphoric acid salt; cause difficulty for separation subsequently; even adopt the method for recrystallization also to be difficult to its separation, other method also cuts both ways, and is necessary to do further research and improves.
Summary of the invention is to remedy the defective that prior art exists, and the present invention proposes a kind of synthetic method and equipment thereof of hexafluorophosphate.The technical scheme that adopts is as follows:
The synthetic method of this hexafluorophosphate is characterized in that following operation is arranged successively:
(1) pre-treatment anhydrous hydrogen fluoride: being provided with temperature controlling range at custom-designed shell is in 20～100 ℃ the electrolysis dewatering unit of insulation jacket, insert anhydrous hydrogen fluoride, again according to the weight ratio of setting, insert metal halide as the conduction toughener, weight ratio is a metal halide: anhydrous hydrogen fluoride=1～50: 100, preferably 5～10: 100.5～12 volts of volts DSs, 50～100 amperes of galvanic currents, electrolysis treatment 2～60 hours, to hydrogen fluoride water content＜30ppm, standby;
(2) synthetic hexafluorophosphate: with the drying solid fluorochemical (moisture＜50ppm) insert in the synthetic reaction device of set amount, insert pretreated anhydrous hydrogen fluoride behind the sealed reactor again as solvent, weight ratio is the drying solid fluorochemical: anhydrous hydrogen fluoride=1: 1～50, preferably 1: 5～10, fully stir and make the drying solid fluoride dissolution, import the gaseous state phosphorus pentafluoride then, mol ratio is the gaseous state phosphorus pentafluoride: drying solid fluorochemical=1～2: 1, preferably 1.2～1.5: 1, continue to stir and finish until building-up reactions, control synthetic reaction device temperature is 0～20 ℃;
(3) low temperature solid-liquid separation comprises low temperature recrystallization, crystallization filtration and washing and filtering:
The low temperature recrystallization is inserted refrigeration agent in synthetic reaction device, cooling temperature-20～10 ℃, preferably-20～0 ℃, 0.5～10 hour cooling time, preferably 2～4 hours;
Crystallization is filtered, and synthetic reaction device is inverted is filtered;
Washing and filtering, the solvent that adopts reaction system to use, i.e. anhydrous hydrogen fluoride washing, washing and filtering 3 times makes the hexafluorophosphate crystalline particle at last;
The crystalline particle size is 0.1～2.0 millimeter, and is colourless.
(4) drying comprises air stream drying and vacuum forced drying:
Air stream drying, rare gas element from input dew point-180～-60, inverted synthetic reaction device bottom ℃, rare gas element passes the hexafluorophosphate crystallized product, unreacted gas reactant and solvent carrier band are gone out synthetic reaction device, rare gas element temperature-20～160 ℃, 1～10 hour time of drying;
The carrier band of discharging from synthetic reaction device has the rare gas element of solvent, entering circulation device after reclaiming solvent through cold-trap, inserts synthetic reaction device more again.
Vacuum forced drying, to synthetic reaction device heating and vacuumize, vacuum forced drying is carried out in the hexafluorophosphate crystallization, 0～100 ℃ of temperature, preferably 20～60 ℃, pressure-0.10～0.00 MPa, preferably-0.09～-0.10 MPa, 6～24 hours time of drying, make the hexafluorophosphate finished product at last.
The waste gas that vacuum system is discharged enters atmosphere through behind the emission-control equipment.
The further feature of the synthetic method of this hexafluorophosphate is:
Above-mentioned metal halide can be a lithium fluoride, also can be Sodium Fluoride, can also be Potassium monofluoride or Neutral ammonium fluoride.
Above-mentioned solid fluoride is an alkaline metal fluoride cpd, can be lithium fluoride, also can be Sodium Fluoride, can also be Potassium monofluoride or fluoride amine.
Above-mentioned rare gas element is air, nitrogen, carbonic acid gas and argon gas, nitrogen preferably, and expense is low.
The measurement result of the lithium hexafluoro phosphate finished product that employing the inventive method makes is:
Purity (weighting method)＞99.5%;
Moisture (karl Fischer method)＜20ppm;
Free acid (acid base titration)＜70ppm.
Other hexafluorophosphates such as Potassium Hexafluorophosphate, the sodium hexafluoro phosphate etc. that adopt the inventive method to make have gratifying measurement result equally.
Implement the inventive method and custom-designed equipment, comprise the electrolysis dewatering unit and the lithium hexafluoro phosphate synthetic reaction device of anhydrous hydrogen fluoride.
The electrolysis dewatering unit that the present invention adopts, comprise negative electrode, graphite anode, porous plate barrier film, shell and be located at the Waste gas outlet of cathode and anode chamber respectively, it is characterized in that negative electrode, porous plate barrier film adopt specific carbon steel to make, shell is provided with insulation jacket, and temperature controlling range is 20～100 ℃.The electrolysis power that connects between the cathode and anode can be voltage, the electric current silicon controlled rectifier direct supply of independent regulation respectively.
The present invention adopts and to assemble, crystallization, filtration, dryly be the multi-functional synthetic reaction device of one, synthesizes, crystallization, filtration and drying finish successively.Synthetic reaction device is inserted and is reacted the finished product conveying end and form with solvent relief outlet, reaction solid by reaction chamber, agitator, screen plate, outside sandwich, reactant gases input aperture, rare gas element input, it is characterized in that the liner of reaction chamber adopts macromolecular material to make.The liner of coupled pipeline, valve, matching used wet tank and inertial gas tank also all adopts macromolecular material to make.Macromolecular material can be tetrafluoroethylene, polyethylene, polystyrene, polyvinyl chloride, also can be polysulfones, can also be polypropylene, polymethyl acrylate.The macromolecular lining material thickness is 0.5～10 millimeter.Screen plate is a titanium matter MULTILAYER COMPOSITE microwell plate, is used for the separation of solid-liquid after the crystallization.Reaction gas inlet links to each other with reaction raw materials gas storage tank, be used for feeding the reactant gases phosphorus pentafluoride in reaction process, the rare gas element input is connected with inertial gas tank, wet tank respectively through Y-tube with the solvent relief outlet, rare gas element in the gas reservoir is used for drying process carrier band solvent, and the solvent in the wet tank can recycle.
The present invention's beneficial effect against existing technologies is, the present invention adopts and inject anhydrous hydrogen fluoride in the electrolysis dewatering unit, and add a certain amount of metal halide as the conduction toughener, utilize electrolytic method to remove the electrochemical method of the contained moisture of hydrogen fluoride, the pre-treatment anhydrous hydrogen fluoride can be before building-up reactions, with the water content of solvent be reduced to permission scope (＜50ppm) in, eliminate the impurity that produces because of moisture, also reduced the content of free acid.Adopt the low temperature solid-liquid separation, improved product purity, avoided time-consuming, loaded down with trivial details and may further bring the purifying aftertreatment of possibility of pollution into.And the air stream drying of employing rare gas element carrier band has improved efficient, has saved the energy, has reduced cost.Test shows, the inventive method is simple and feasible, synthetic lithium hexafluoro phosphate product purity height (＞99.5%), moisture and free acid content low (be respectively＜20ppm,＜70ppm), can directly be used as the ionogen of secondary lithium battery, have advantages such as favorable charge-discharge characteristic, self-discharge is little, high temperature performance is good, can satisfy lithium ion battery fully electrolytical requirement.With synthetic other hexafluorophosphates of the inventive method,, gratifying effect is arranged equally as Potassium Hexafluorophosphate, sodium hexafluoro phosphate etc.Adopt custom-designed electrolysis dewatering unit and multi-functional synthetic reaction device, synthetic, crystallization, filtration and drying process are finished successively, and be easy and simple to handle, the reliability height.Adopt the reactor linings of macromolecular material, solved and in building-up process, adopted metallic reactors may introduce the problem of metal ion, can reduce the content of metal ion neutralization product.
Description of drawings the present invention has the following drawings:
Fig. 1 is the electrolysis dewatering unit structural representation of anhydrous hydrogen fluoride of the present invention;
Fig. 2 is a lithium hexafluoro phosphate synthetic reaction device structural representation of the present invention.
The synthetic method of a kind of lithium hexafluoro phosphate of embodiment and equipment thereof
Below the contrast accompanying drawing and in conjunction with embodiment the invention will be further described.
(1) synthetic method of hexafluorophosphate
Embodiment 1:
(1) pre-treatment anhydrous hydrogen fluoride: being provided with temperature controlling range at custom-designed shell is in 50 ℃ the electrolysis dewatering unit of insulation jacket, insert anhydrous hydrogen fluoride, again according to the weight ratio of setting, insert metal halide as the conduction toughener, weight ratio is a metal halide: anhydrous hydrogen fluoride=8: 100,12 volts of volts DSs, 50～100 amperes of galvanic currents, electrolysis treatment 24 hours, to hydrogen fluoride water content＜30ppm, standby;
(2) synthetic hexafluorophosphate: with 500 gram drying solid lithium fluoride (moisture＜50ppm) insert in the synthetic reaction device, insert pretreated anhydrous hydrogen fluoride 2500 grams behind the sealed reactor again as solvent, weight ratio is the drying solid fluorochemical: anhydrous hydrogen fluoride=1: 5, fully stir and make the drying solid fluoride dissolution, import the gaseous state phosphorus pentafluoride then, continue to stir and finish until building-up reactions, control synthetic reaction device temperature is 0～20 ℃;
(3) low temperature solid-liquid separation:
The low temperature recrystallization is inserted refrigeration agent in synthetic reaction device, cooling temperature-20～0 ℃, fully cools off synthetic reaction device at 2～4 hours cooling times;
Crystallization is filtered, and synthetic reaction device is inverted is filtered;
Washing and filtering, the solvent that adopts reaction system to use, i.e. anhydrous hydrogen fluoride washing, washing and filtering 3 times; Make grain size at last and be 0.1～2.0 millimeter colourless hexafluorophosphate crystallization;
(4) drying:
Air stream drying is from the nitrogen of 60 ℃ of inverted synthetic reaction device bottom input dew points-120 ℃, temperature, 2 hours time of drying;
Vacuum forced drying to synthetic reaction device heating and vacuumize, carries out vacuum forced drying with the hexafluorophosphate crystallization, 60 ℃ of temperature, and pressure-0.09 MPa, makes the hexafluorophosphate finished product at last at 24 hours time of drying.
Open synthetic reaction device, take out product, weigh 2.36 kilograms, yield 80.7%, purity 99.7%, moisture 15ppm, free acid (in hydrogen fluoride) 58ppm, insolubles (in methylcarbonate)＜0.3%, metal K, Na, Ca, Mg ionic content＜5ppm, other ion＜2ppm.
Embodiment 2:
(1) pre-treatment anhydrous hydrogen fluoride: identical with embodiment 1 (1);
(2) synthetic hexafluorophosphate: with 500 gram drying solid lithium fluoride (moisture＜50ppm) add in the synthetic reaction device, add pretreated anhydrous hydrogen fluoride 5000 grams behind the sealed reactor again as solvent, weight ratio is the drying solid fluorochemical: anhydrous hydrogen fluoride=1: 10, below identical with embodiment 1 (2);
(3) low temperature solid-liquid separation: identical with embodiment 1 (3);
(4) drying: identical with embodiment 1 (4).
Open synthetic reaction device, take out product, weigh 2.48 kilograms, yield 84.8%, purity 99.7%, moisture 17ppm, free acid (in hydrogen fluoride) 50ppm, insolubles (in methylcarbonate)＜0.3%, metal K, Na, Ca, Mg ionic content＜5ppm, other ion＜2ppm.
Embodiment 3:
(1) pre-treatment anhydrous hydrogen fluoride: identical with embodiment 1,2 (1);
(2) synthetic hexafluorophosphate: with 500 gram drying solid Sodium Fluorides (moisture＜20ppm) add in the synthetic reaction device, below identical with embodiment 2 (2);
(3) low temperature solid-liquid separation: identical with embodiment 1,2 (3);
(4) drying: identical with embodiment 1,2 (4).
Open synthetic reaction device, take out product, weigh 1.50 kilograms, yield 75.0%, purity 99.5%, moisture 17ppm, free acid (in hydrogen fluoride) 58ppm, insolubles (in methylcarbonate)＜0.3%, metal K, Ca, Mg ionic content＜5ppm, other ion＜2ppm.
(2) specific equipment of hexafluorophosphate synthetic method
Embodiment 4:
The electrolysis dewatering unit comprises negative electrode 1, graphite anode 2, porous plate barrier film 3, shell 4 and is located at the useless hydrogen discharge mouth 5 of cathode and anode chamber, useless fluorine gas discharge outlet 6 respectively, negative electrode 1, porous plate barrier film 3 adopt the Q235 carbon steel to make, shell 4 is provided with insulation jacket 7, and temperature controlling range is 20～100 ℃.The electrolysis power that connects between the cathode and anode 1,2 is the silicon controlled rectifier direct supply, and voltage, electric current be independent regulation respectively, 5～12 volts of voltages, 50～100 amperes in electric current.
The useless hydrogen that the electrolysis dehydration produces, useless fluorine gas also enter atmosphere from useless hydrogen discharge mouth 5, useless fluorine gas discharge outlet 6 respectively after the assay was approved through matching used twin gas treating system processing.
Embodiment 5:
Synthetic reaction device is inserted and is reacted finished product conveying end 13 and form with solvent relief outlet 12, reaction solid by reaction chamber 8, agitator 9, screen plate 10, outside sandwich (not drawing among Fig. 2), reactant gases input aperture 11, rare gas element input, and the liner of reaction chamber 8 (also not drawing among Fig. 2) adopts the macromolecular material tetrafluoroethylene to make.The liner of coupled pipeline, valve, matching used wet tank and inertial gas tank also all adopts the macromolecular material tetrafluoroethylene to make.The macromolecular lining material thickness is 8 millimeters.Screen plate 10 is titanium matter MULTILAYER COMPOSITE microwell plates, is used for the separation of solid-liquid after the crystallization.Reaction gas inlet 11 links to each other with reaction raw materials gas storage tank, be used for feeding the reactant gases phosphorus pentafluoride in reaction process, the rare gas element input is connected with inertial gas tank, wet tank respectively through Y-tube with solvent relief outlet 12, rare gas element in the gas reservoir is used for drying process carrier band solvent, and the solvent in the wet tank can recycle.
Claims (10)
1, a kind of synthetic method of hexafluorophosphate is characterized in that following operation is arranged successively:
(1) pre-treatment anhydrous hydrogen fluoride: adopt the Q235 carbon steel to make at negative electrode, porous plate barrier film, and it is in 20～100 ℃ the electrolysis dewatering unit of insulation jacket that shell is provided with temperature controlling range, insert anhydrous hydrogen fluoride, again according to the weight ratio of setting, insert metal halide as the conduction toughener, weight ratio is a metal halide: anhydrous hydrogen fluoride=1～50: 100,5～12 volts of volts DSs, 50～100 amperes of galvanic currents, electrolysis treatment 2～60 hours, to hydrogen fluoride water content＜30ppm, standby;
(2) synthetic hexafluorophosphate: the drying solid fluorochemical of moisture＜50ppm is inserted the liner that adopts macromolecular material making reaction chamber, screen plate is in the synthetic reaction device of titanium matter MULTILAYER COMPOSITE microwell plate, insert pretreated anhydrous hydrogen fluoride behind the sealed reactor again as solvent, weight ratio is the drying solid fluorochemical: anhydrous hydrogen fluoride=1: 1～50, fully stir and make the drying solid fluoride dissolution, import the gaseous state phosphorus pentafluoride then, mol ratio is the gaseous state phosphorus pentafluoride: drying solid fluorochemical=1～2: 1, continue to stir and finish until building-up reactions, control synthetic reaction device temperature is 0～20 ℃;
(3) low temperature solid-liquid separation comprises low temperature recrystallization, crystallization filtration and washing and filtering:
The low temperature recrystallization is inserted refrigeration agent in synthetic reaction device, cooling temperature is-20～10 ℃, and be 0.5～10 hour cooling time;
Crystallization is filtered, and synthetic reaction device is inverted is filtered;
Washing and filtering, the solvent that adopts reaction system to use, i.e. anhydrous hydrogen fluoride washing, washing and filtering 3 times makes the hexafluorophosphate crystalline particle at last;
(4) drying comprises air stream drying and vacuum forced drying:
Air stream drying, rare gas element from input dew point-180～-60, inverted synthetic reaction device bottom ℃, rare gas element passes the hexafluorophosphate crystallized product, unreacted gas reactant and solvent carrier band are gone out synthetic reaction device, rare gas element temperature-20～160 ℃, 1～10 hour time of drying;
Vacuum forced drying to synthetic reaction device heating and vacuumize, carries out vacuum forced drying with the hexafluorophosphate crystallization, 0～100 ℃ of temperature, and pressure-0.10～0.00 MPa, makes the hexafluorophosphate finished product at last at 6～24 hours time of drying.
2, the synthetic method of hexafluorophosphate as claimed in claim 1 is characterized in that above-mentioned metal halide is lithium fluoride, Sodium Fluoride, Potassium monofluoride or Neutral ammonium fluoride.
3, the synthetic method of hexafluorophosphate as claimed in claim 1 is characterized in that above-mentioned solid fluoride is an alkaline metal fluoride cpd, and this alkaline metal fluoride cpd is lithium fluoride, Sodium Fluoride, Potassium monofluoride or Neutral ammonium fluoride.
4, the synthetic method of hexafluorophosphate as claimed in claim 1 is characterized in that above-mentioned rare gas element is air, nitrogen, carbonic acid gas or argon gas.
5, a kind of method as claimed in claim 1 is synthesized the electrolysis dewatering unit that hexafluorophosphate is used, comprise negative electrode, graphite anode, porous plate barrier film, shell and be located at the Waste gas outlet of cathode and anode chamber respectively, it is characterized in that negative electrode, porous plate barrier film adopt the Q235 carbon steel to make, shell is provided with insulation jacket, and temperature controlling range is 20～100 ℃.
6, electrolysis dewatering unit as claimed in claim 5 is characterized in that the electrolysis power that connects between the cathode and anode, is voltage, the electric current silicon controlled rectifier direct supply of independent regulation respectively.
7, a kind of method as claimed in claim 1 is synthesized the synthetic reaction device that hexafluorophosphate is used, insert and react the finished product conveying end and form with solvent relief outlet, reaction solid by reaction chamber, agitator, screen plate, outside sandwich, reactant gases input aperture, rare gas element input, the liner that it is characterized in that reaction chamber adopts macromolecular material to make, and screen plate is a titanium matter MULTILAYER COMPOSITE microwell plate.
8, synthetic reaction device as claimed in claim 7 is characterized in that the liner of coupled pipeline, valve, matching used wet tank and inertial gas tank, all adopts macromolecular material to make.
9,, it is characterized in that macromolecular material is tetrafluoroethylene, polyethylene, polystyrene, polyvinyl chloride, polysulfones, polypropylene or polymethyl acrylate as claim 7 or 8 described synthetic reaction devices.
10,, it is characterized in that the macromolecular lining material thickness is 0.5～10 millimeter as claim 7 or 8 described synthetic reaction devices.
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| CN 03113898 CN1212264C (en) | 2003-03-08 | 2003-03-08 | Method and equipment for synthesizing hexafluorophosphate |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393609C (en) * | 2006-05-30 | 2008-06-11 | 天津化工研究设计院 | Method for refining solvent of lithium hexafluorophosphate |
| CN102170023A (en) * | 2011-03-18 | 2011-08-31 | 中国海洋石油总公司 | Preparation method of lithium hexafluorophosphate electrolyte solution |
| CN102153064A (en) * | 2011-03-29 | 2011-08-17 | 张家港市亚源高新技术材料有限公司 | Synthesis method of a lithium hexafluorophosphate non-aqueous solvent method |
| US20160158696A1 (en) * | 2013-06-27 | 2016-06-09 | Kanto Denka Kogyo Co., Ltd. | Treatment process of phosphorous pentafluoride |
| CN103508432B (en) * | 2013-07-17 | 2016-01-13 | 多氟多化工股份有限公司 | Lithium hexafluorophosphate synthesis device |
| CN104211029B (en) * | 2014-07-22 | 2016-09-07 | 浙江东氟塑料科技有限公司 | A kind of preparation method of lithium hexafluoro phosphate |
| CN108147386B (en) * | 2017-12-25 | 2020-06-09 | 衢州北斗星化学新材料有限公司 | Preparation method of dynamic crystalline lithium hexafluorophosphate |
| CN108946769A (en) * | 2018-07-20 | 2018-12-07 | 森田新能源材料（张家港）有限公司 | Sodium hexafluoro phosphate preparation method |
| CN113772694A (en) * | 2021-09-29 | 2021-12-10 | 湖北省宏源药业科技股份有限公司 | Preparation method of high-purity sodium hexafluorophosphate |
| CN114713169A (en) * | 2022-04-12 | 2022-07-08 | 陈湘杰 | Electrolyte generator and electrolyte purification method |
| CN114751431B (en) * | 2022-04-25 | 2023-03-14 | 山东大学 | Preparation method of sodium salt for sodium battery |
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