CN102275895A - Method of synthesizing lithium hexafluorophosphate - Google Patents
Method of synthesizing lithium hexafluorophosphate Download PDFInfo
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- CN102275895A CN102275895A CN2011101850315A CN201110185031A CN102275895A CN 102275895 A CN102275895 A CN 102275895A CN 2011101850315 A CN2011101850315 A CN 2011101850315A CN 201110185031 A CN201110185031 A CN 201110185031A CN 102275895 A CN102275895 A CN 102275895A
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- hexafluoro phosphate
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Abstract
The invention relates to a method of synthesizing lithium hexafluorophosphate, which comprises the following steps of: A. adding lithium fluoride and anhydrous hydrogen fluoride to a reactor under the protection of inert gases, and preparing into a hydrofluoric acid solution of the lithium fluoride; B. adding dichloro hexafluorophosphoric acid into the hydrofluoric acid solution of the lithium fluoride, and stirring to form a suspension liquid; C. reacting the dichloro hexafluorophosphoric acid with the lithium fluoride to form a hydrofluoric acid solution of the lithium hexafluorophosphate, wherein the reaction temperature is 16-60 DEG C, and the reaction time is 4-6 hours; D. after the reaction is ended, removing unreacted hydrogen chloride gas; and obtaining hexafluorophosphoric acid crystals through the separation of the hydrofluoric acid solution of the lithium hexafluorophosphate. The process for synthesizing the lithium hexafluorophosphate by reacting the dichloro hexafluorophosphoric acid and the lithium fluoride at a higher temperature has the advantages of effectively increasing the reaction efficiency of the dichloro hexafluorophosphoric acid and the lithium fluoride, shortening the reaction time, increasing the output ratio of the product in unit volume, simplifying the crystallization and purification process flows of the lithium hexafluorophosphate and reducing the production cost.
Description
Technical field
The present invention relates to a kind of synthetic method of lithium hexafluoro phosphate, belong to technical field of inorganic.
Background technology
Lithium hexafluoro phosphate (LiPF
6) as lithium ion battery electrolyte materials, be the main raw material of making lithium ion battery.Lithium ion battery is present universally acknowledged desirable green energy resource, and its volume is little, electrical capacity is big, has been widely used in the main power supply of portable electronics such as notebook computer, mobile phone, electric bicycle, power tool.In recent years, lithium ion battery also is applied to the energy of new-energy automobiles such as electromobile, hybrid vehicle, and application prospect is boundless.
The method of at present synthetic lithium hexafluoro phosphate generally adopts the hydrogen fluoride solution reaction of phosphorus pentafluoride or phosphofluoric acid and lithium fluoride to synthesize lithium hexafluoro phosphate.The application for a patent for invention name is called " with the synthetic lithium hexafluoro phosphate of rheological phase reaction method ", publication number is: CN101962181A, open day be: 2011.2.2, disclosing a kind of is the method for the synthetic lithium hexafluoro phosphate of raw material with dichloro phosphofluoric acid and lithium fluoride, comprise dichloro phosphofluoric acid and lithium chloride are added in the reactor, add anhydrous hydrogen fluoride again and make rheological body; Under function composite by electromagnetic stirring, carry out rheological phase reaction then and obtain lithium hexafluoro phosphate crystallite and hydrofluoric solidliquid mixture; After fractionation by distillation liquid-fluorination hydrogen and purify with soaked in absolute ethyl alcohol and to obtain the phosphofluoric acid crystalline lithium.This method equipment is simple, reaction temperature and, safe, finished product lithium hexafluoro phosphate purity is greater than 99.9%, the few and recyclable utilization of hydrogen fluoride consumption, production cost is low.
But still there are shortcomings and deficiencies in the method for the disclosed synthetic lithium hexafluoro phosphate of this application for a patent for invention: the one, and the temperature of reaction of dichloro phosphofluoric acid and lithium chloride is lower, causes long reaction time, reacts abundant inadequately; The 2nd, the hydrogen fluoride solution concentration of lithium fluoride is lower, cause the reaction efficiency of dichloro phosphofluoric acid and lithium chloride low, and lithium hexafluoro phosphate finished product output capacity is low; The 3rd, crystallization from the hydrofluoric acid solution of lithium hexafluoro phosphate, the method complexity of purification lithium hexafluoro phosphate, cost are higher.
Summary of the invention
In order to overcome the shortcoming that prior art exists, the invention provides a kind of dichloro phosphofluoric acid and lithium fluoride of utilizing and be raw material, the method of the synthetic lithium hexafluoro phosphate of reaction under comparatively high temps, effectively improved the reaction efficiency of dichloro phosphofluoric acid and lithium fluoride, shortened the reaction times, significantly improve an output capacity of lithium hexafluoro phosphate finished product, and simplified the crystallization and the method for purification flow process of lithium hexafluoro phosphate, reduced production cost.
The present invention realizes that the technical scheme that technical purpose adopts is:
A kind of method of synthetic lithium hexafluoro phosphate may further comprise the steps: A. adds lithium fluoride and anhydrous hydrogen fluoride in protection of inert gas downhill reaction device, is configured to the hydrofluoric acid solution of lithium fluoride, and its mass concentration is 20%～40%;
B. in the hydrofluoric acid solution of lithium fluoride, add the dichloro phosphofluoric acid, stir and form suspension liquid;
C. dichloro phosphofluoric acid and lithium fluoride react, and temperature of reaction is 16～60 ℃, react 4～6 hours, form the hydrofluoric acid solution of lithium hexafluoro phosphate;
D. after reaction finishes, get rid of unreacted hydrogen chloride gas, and obtain the phosphofluoric acid crystal from the hydrofluoric acid solution separation of lithium hexafluoro phosphate.
A kind of method of synthetic lithium hexafluoro phosphate, described step D may further comprise the steps:
D1. after reaction finished, the hydrofluoric acid solution of cooling lithium hexafluoro phosphate was separated out the lithium hexafluoro phosphate crystallization;
D2. with crystalline phosphofluoric acid crystalline lithium filtration drying, obtain the lithium hexafluoro phosphate finished product.
A kind of method of synthetic lithium hexafluoro phosphate, among the described step D1, the hydrofluoric acid solution cooling step of lithium hexafluoro phosphate comprises that earlier the hydrofluoric acid solution with lithium hexafluoro phosphate naturally cools to room temperature, again gradient cooling to 0 ℃.
A kind of method of synthetic lithium hexafluoro phosphate, described reactor are tank reactor, and the reaction pressure in the described tank reactor is 1～2MPa.
A kind of method of synthetic lithium hexafluoro phosphate, the mol ratio of dichloro phosphofluoric acid and lithium fluoride are 1: 1.
A kind of method of synthetic lithium hexafluoro phosphate after the described step D, also comprises step e: the hydrofluoric acid solution behind the separation lithium hexafluoro phosphate, obtain anhydrous hydrogen fluoride, and be recycled and reused in the steps A.
In the method for utilizing dichloro phosphofluoric acid and the synthetic lithium hexafluoro phosphate of lithium fluoride of prior art, temperature of reaction is generally 0～15 ℃, and the invention provides a kind of method of synthesizing lithium hexafluoro phosphate under 16～60 ℃ high temperature.16～60 ℃ temperature of reaction is still in safety range, and higher temperature of reaction has effectively improved the concentration and the reaction efficiency of reaction solution, thereby significantly improved the production efficiency of conversion unit unit volume, simplified technical process, improved the quality and the one-pass finished output capacity of product, the output capacity that once goes out product of synthetic method provided by the invention is increased to 85%.Pyroreaction has also been saved simultaneously to keeping the required energy that low temperature consumed of reaction, and significantly shortened the reaction times, the reaction times of method provided by the invention shortened to 4～6 hours by original 5～10 hours, had effectively improved production efficiency, had saved production cost.
In the method for synthetic lithium hexafluoro phosphate provided by the invention, the hydrofluoric acid solution concentration of the lithium fluoride of configuration is 20%～40%, belongs to highly concentrated solution, and the concentration of reaction back finished product lithium hexafluoro phosphate mixing solutions is increased, improved reaction efficiency, and an output capacity of lithium hexafluoro phosphate finished product.
Dichloro phosphofluoric acid and lithium fluoride pyroreaction generate the hydrofluoric acid solution of pyritous lithium hexafluoro phosphate, pass through naturally cooling, the lithium hexafluoro phosphate crystal structure is separated out, steps such as fractionation by distillation, alcohol immersion have been avoided, simplified method of purification, reduced production cost, and be the nature decrease temperature crystalline, the product crystallization is even, the product purity height.In addition, the recyclable utilization of isolating hydrogen fluoride mother liquor can further improve utilization ratio of raw materials.The reactor that building-up reactions provided by the invention is used is autoclave, and dichloro phosphofluoric acid and lithium fluoride react under sealed state, has avoided the secondary pollution of external environment, has ensured quality product.And reaction all is to carry out in same reactor, and conversion unit is simplified greatly, has reduced equipment cost and production cost significantly.
Embodiment
Below by embodiment, further illustrate outstanding feature of the present invention and marked improvement, only be the present invention is described and never limit the scope of the invention.
Embodiment 1
At a pressure is in the 1MPa magnetic agitation reactor; add 52g lithium fluoride and 122g anhydrous hydrogen fluoride under nitrogen protection, induction stirring makes it to form the hydrofluoric acid solution of lithium fluoride, adds 438g dichloro phosphofluoric acid then; stir and form suspension liquid, temperature of reaction kettle is 25 ℃.Then with the temperature of reactor be increased to 60 ℃ gradually, reacted 4 hours; The system that makes naturally cooled to room temperature after reaction finished, and was cooled to 0 ℃ then, and kept 2 hours, guaranteed that crystallization separates out fully; Get rid of the hydrogen chloride gas have neither part nor lot in reaction then, and filtration drying obtains the lithium hexafluoro phosphate finished product, mother liquor is in order to reuse; Finally obtaining the phosphofluoric acid finished product is 258.8g, and disposable output capacity reaches 84.8%.
Embodiment 2
At a pressure is in the 2MPa magnetic agitation reactor; under nitrogen protection, add 26g lithium fluoride and 20g anhydrous hydrogen fluoride and 42g mother liquor (mother liquor that embodiment 1 obtains); induction stirring makes it to form the hydrofluoric acid solution of lithium fluoride; add 219g dichloro phosphofluoric acid then; at room temperature stir and form suspension liquid, temperature of reaction kettle is 16 ℃.Then with the temperature of reactor be increased to 60 ℃ gradually, reacted 6 hours; The system that makes naturally cooled to room temperature after reaction finished, and was cooled to 0 ℃ then, and kept 2 hours, guaranteed that crystallization separates out fully; Get rid of the hydrogen chloride gas have neither part nor lot in reaction then, and filtration drying obtains the lithium hexafluoro phosphate finished product, mother liquor is in order to reuse.Finally obtaining the phosphofluoric acid finished product is 129g, and disposable output capacity reaches 85%.
The detected result of technical target of the product sees Table 1.
The detected result of table 1. lithium hexafluoro phosphate technical target of the product
Claims (6)
1. the method for a synthetic lithium hexafluoro phosphate is characterized in that may further comprise the steps:
A. add lithium fluoride and anhydrous hydrogen fluoride in protection of inert gas downhill reaction device, be configured to the hydrofluoric acid solution of lithium fluoride, its mass concentration is 20%～40%;
B. in the hydrofluoric acid solution of lithium fluoride, add the dichloro phosphofluoric acid, stir and form suspension liquid;
C. dichloro phosphofluoric acid and lithium fluoride react, and temperature of reaction is 16～60 ℃, 4～6 hours reaction times, the hydrofluoric acid solution of formation lithium hexafluoro phosphate;
D. after reaction finishes, get rid of unreacted hydrogen chloride gas, and obtain the phosphofluoric acid crystal from the hydrofluoric acid solution separation of lithium hexafluoro phosphate.
2. synthetic method according to claim 1 is characterized in that described step D may further comprise the steps:
D1. after reaction finished, the hydrofluoric acid solution of cooling lithium hexafluoro phosphate was separated out the lithium hexafluoro phosphate crystallization;
D2. with crystalline phosphofluoric acid crystalline lithium filtration drying, obtain the lithium hexafluoro phosphate finished product.
3. synthetic method according to claim 2 is characterized in that: among the described step D1, the hydrofluoric acid solution cooling step of lithium hexafluoro phosphate comprises that earlier the hydrofluoric acid solution with lithium hexafluoro phosphate naturally cools to room temperature, again gradient cooling to 0 ℃.
4. synthetic method according to claim 1 is characterized in that: described reactor is a tank reactor, and the reaction pressure in the described tank reactor is 1～2MPa.
5. synthetic method according to claim 1 is characterized in that: the mol ratio of dichloro phosphofluoric acid and lithium fluoride is 1: 1.
6. synthetic method according to claim 1 is characterized in that: after the described step D, also comprise step e: the hydrofluoric acid solution behind the separation lithium hexafluoro phosphate, obtain anhydrous hydrogen fluoride, and be recycled and reused in the steps A.
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| CN 201110185031 CN102275895B (en) | 2011-06-30 | 2011-06-30 | Method of synthesizing lithium hexafluorophosphate |
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| CN 201110185031 CN102275895B (en) | 2011-06-30 | 2011-06-30 | Method of synthesizing lithium hexafluorophosphate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106882819A (en) * | 2017-03-29 | 2017-06-23 | 东营石大胜华新能源有限公司 | A kind of lithium hexafluoro phosphate prepares purification process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19805356C1 (en) * | 1998-02-12 | 1999-06-17 | Metallgesellschaft Ag | Lithium hexafluorophosphate is produced by reacting phosphorus pentachloride with an acidified lithium fluoride-diethylether suspension |
| CN1850592A (en) * | 2006-05-30 | 2006-10-25 | 天津化工研究设计院 | Method for preparing potassium hexafluoro phosphate |
| CN101962181A (en) * | 2010-11-17 | 2011-02-02 | 湖北省宏源药业有限公司 | Preparation of lithium hexafluorophosphate by rheological phase reaction method |
-
2011
- 2011-06-30 CN CN 201110185031 patent/CN102275895B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19805356C1 (en) * | 1998-02-12 | 1999-06-17 | Metallgesellschaft Ag | Lithium hexafluorophosphate is produced by reacting phosphorus pentachloride with an acidified lithium fluoride-diethylether suspension |
| CN1850592A (en) * | 2006-05-30 | 2006-10-25 | 天津化工研究设计院 | Method for preparing potassium hexafluoro phosphate |
| CN101962181A (en) * | 2010-11-17 | 2011-02-02 | 湖北省宏源药业有限公司 | Preparation of lithium hexafluorophosphate by rheological phase reaction method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106882819A (en) * | 2017-03-29 | 2017-06-23 | 东营石大胜华新能源有限公司 | A kind of lithium hexafluoro phosphate prepares purification process |
| CN106882819B (en) * | 2017-03-29 | 2018-12-25 | 东营石大胜华新能源有限公司 | A kind of lithium hexafluoro phosphate prepares purification process |
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Address after: 438600 Fengshan City, Huanggang province Luotian County, north of the town of water Yi Road, No. 428 Patentee after: HUBEI HONGYUAN PHARMACEUTICAL TECHNOLOGY CO., LTD. Address before: 438600 Fengshan City, Huanggang province Luotian County, north of the town of water Yi Road, No. 428 Patentee before: Hubei Hongyuan Pharmaceutical Co., Ltd. |
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