CN102180456B - Method for purifying lithium hexafluorophosphate and special device thereof - Google Patents
Method for purifying lithium hexafluorophosphate and special device thereof Download PDFInfo
- Publication number
- CN102180456B CN102180456B CN2011100545495A CN201110054549A CN102180456B CN 102180456 B CN102180456 B CN 102180456B CN 2011100545495 A CN2011100545495 A CN 2011100545495A CN 201110054549 A CN201110054549 A CN 201110054549A CN 102180456 B CN102180456 B CN 102180456B
- Authority
- CN
- China
- Prior art keywords
- gas
- reaktionsofen
- vibration
- circulation loop
- hexafluoro phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- -1 lithium hexafluorophosphate Chemical compound 0.000 title abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 24
- 239000011737 fluorine Substances 0.000 claims abstract description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000007599 discharging Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 103
- 229910052744 lithium Inorganic materials 0.000 claims description 47
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 46
- 229910019142 PO4 Inorganic materials 0.000 claims description 46
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 46
- 239000010452 phosphate Substances 0.000 claims description 46
- 238000001179 sorption measurement Methods 0.000 claims description 36
- 239000011261 inert gas Substances 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000010924 continuous production Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 37
- 229910013870 LiPF 6 Inorganic materials 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 14
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 11
- 229910013872 LiPF Inorganic materials 0.000 description 10
- 101150058243 Lipf gene Proteins 0.000 description 10
- 230000003534 oscillatory effect Effects 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910012258 LiPO Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001815 facial effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 208000036142 Viral infection Diseases 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
Abstract
The invention discloses a method for purifying lithium hexafluorophosphate, which comprises the following steps of: with the protection of dry inactive gas, adding coarse lithium hexafluorophosphate in a feed hopper of a vibration reacting furnace in a glove box, starting the vibration reacting furnace and simultaneously injecting the mixed gas of the dry inactive gas and fluorine gas in a gas circulating circuit, and controlling the adding speed and adding amount of the coarse lithium hexafluorophosphate through controlling rotation frequency and feeding time of the spiral feeder of the vibration reacting furnace; and starting a compressor to circulate the mixed gas of the dry inactive gas and the fluorine gas, evacuating the system through an Al2O3 absorption column, evacuating the gas circulating circuit through a molecular sieve absorption column, re-injecting dry inactive gas in the gas circulating circuit at last, and discharging. The invention has the advantages of high reliability, simple purifying process, and realizable continuous production.
Description
Technical field
The present invention relates to a kind of purification process and isolated plant thereof of lithium hexafluoro phosphate.
Background technology
Lithium hexafluoro phosphate is that outward appearance is white in color Powdered or small grains, is soluble in DEC (diethyl carbonate), the EC organic solvents such as (NSC 11801s), and chemicalstability is better; Do not react with most of organic and inorganicss, but be virose chemical reagent, meet water decomposition and become acid; When injected organism tissue there is corrosive nature, can not directly contacts, must be stored in the airtight container; Must prevent to decompose at the dry atmosphere of the absolute humidity＜10ppm work of finishing drilling during use.
In in the past more than 10 year, lithium hexafluoro phosphate is the topmost electrolyte lithium salt that uses in the commercialization lithium ion battery always.Lithium hexafluoro phosphate mainly contains following advantage as the lithium ion battery electrolyte lithium salts: it can especially on the carbon negative pole, form suitable solid electrolyte phase boundary facial mask (1) on electrode; (2) it can realize effective passivation to plus plate current-collecting body, to stop its dissolving; (3) it has broad electrochemical stability window; (4) it has suitable solubleness and higher specific conductivity in various non-aqueous solvents; (5) it has environment friendly relatively preferably.Though forefathers have carried out extensive studies to the electrolyte lithium salt of various structure types, lithium hexafluoro phosphate remains and can't challenge as the status of the leading electrolyte lithium salt in the lithium-ion electric pool technology.It can form suitable solid electrolyte phase boundary facial mask and the Al collector is realized that effective passivation is its major cause of still dominating commercialization lithium ion battery electrolyte lithium salts market at present on the carbon negative pole.
As the lithium hexafluoro phosphate of lithium ion battery electrolyte lithium salts, its most important mass parameter mainly is to contain less water and free acid (in HF) in the requirement product except that product gas purity.Generally speaking, it has following quality index at least:
(1) purity is greater than 99.9%;
(2) H
2O content is less than 20ppm;
(3) HF content is less than 80ppm.
LiPF
6Usually the halogenide with phosphorus is raw material with LiF or LiCl, and the employing anhydrous hydrogen fluoride is produced as solvent.Adopting the Crystallization Separation of this handicraft product to be easier to, be easy to realize industriallization, is more sophisticated at present LiPF
6Production process route.All disclosed like CN1339401A and CN1850592A, adopting anhydrous hydrogen fluoride, phosphorus pentahalides, lithium halide is the production technique of feedstock production lithium hexafluoro phosphate.Then having disclosed among the CN1317445, is raw material with phosphorus pentafluoride and LiF, is the production technique that solvent prepares lithium hexafluoro phosphate with hydrogen fluoride.
But because LiPF
6Use anhydrous hydrogen fluoride to make solvent, LiPF in the production
6Be prone to generate LiPF with HF
6* the HF mixture causes LiPF
6Usually all contain a certain amount of hydrogen fluoride in the thick product.In addition, owing to produce LiPF
6Raw material in usually all contain the oxide compound of trace, at LiPF
6Production process in can and hydrogen fluoride reaction generate water, and also contain the water of trace usually in the anhydrous hydrogen fluoride solvent.Therefore, adopt anhydrous hydrogen fluoride to produce LiPF
6Production technique in, the final LiPF that obtains
6Contain a certain amount of water in the thick product and hydrogen fluoride is inevitable.Therefore, how to remove LiPF
6Water and hydrogen fluoride in the thick product make it meet the requirement of lithium ion battery industry, are LiPF
6One of step of most critical in the production.But LiPF
6Very easily hydrolysis, and thermostability is relatively poor, and this makes LiPF
6The purifying difficulty that becomes very.
LiPF
6Main thermovacuum desiccating method of the most frequently used purification process and dissolving-recrystallization method.The dissolving-recrystallization method is exactly with LiPF
6Be dissolved at a certain temperature in ether, methylcarbonate or the diethyl carbonate, the centrifugal insolubles of removing reduces temperature then, makes LiPF
6Can be from organic solvent recrystallization come out the LiPF that filtration is obtained
6Crystal obtains final product, as just disclosing this purification process among the CN1884046 through after the vacuum-drying.But the operation of this method is comparatively complicated, can't continuous production, and make LiPF
6When obtaining purifying, the recrystallization product can be carried certain organic solvent secretly, influences product purity, and uses a large amount of organic solvents to cause production cost to increase in the purifying, therefore is difficult to be applied to LiPF
6Large-scale production.In addition, disclose a kind of use acid gas removal LiPF among the CN1462722
6The method of middle moisture, this method can't remove LiPF on the one hand
6Hydrogen fluoride in the thick product, and introduce acid gas impurities.Than aforesaid method, the thermovacuum desiccating method is just to LiPF
6Thick product is heating purifying under vacuum state directly, is a kind of LiPF of being suitable for
6The purifying mode of large-scale production can be avoided the LiPF that exists in the dissolving-recrystallization method
6Secondary pollution problem.The subject matter that the thermovacuum desiccating method exists is how to avoid LiPF in the heat-processed
6Decomposition and LiPF
6Each particle of thick product can both fully be exposed in the vacuum, makes its final LiPF that obtains
6There is not the hydrofluoric problem that is mingled with in the product, thereby makes LiPF
6Hydrofluoric content is less than 80ppm in the product.
Summary of the invention
The object of the present invention is to provide a kind of subject matter that exists when adopting the thermovacuum desiccating method to remove HF in the thick product of lithium hexafluoro phosphate, the purification process and the isolated plant thereof of the continuous good lithium hexafluoro phosphate of a kind of efficient, safety, production is provided with water.
Technical solution of the present invention is:
A kind of purification process of lithium hexafluoro phosphate is characterized in that: will vibrate at first that Reaktionsofen vacuumizes and use drying nitrogen to clean repeatedly, and in advance to Al
2O
3Adsorption column and molecular sieve adsorption post carry out activation, and make condensing surface and molecular sieve adsorption post be cooled to-180～-140 ℃, assemble gas circulation loop, Al
2O
3Adsorption column is connected with gas circulation loop with the molecular sieve adsorption post, in gas circulation loop, adds the dry inert gas less than 0.1MPa simultaneously in advance; In glove box under dry inert gas protection; In vibration Reaktionsofen hopper, add the thick product of lithium hexafluoro phosphate; The Vibration on Start-up Reaktionsofen; In gas circulation loop, inject the mixed gas of dry inert gas and fluorine gas simultaneously, the rotational frequency of the feeding screw through control vibration Reaktionsofen and adding speed and the amount that feed time is controlled the thick product of lithium hexafluoro phosphate; Start compressor, make the mixed gas circulation of dry inert gas and fluorine gas, then pass through Al
2O
3Adsorption column vacuumizes system, through the molecular sieve adsorption post gas circulation loop is vacuumized again, in gas circulation loop, refills dry inert gas, discharging at last;
Said gas circulation loop is made up of vibration Reaktionsofen → compressor → NaF adsorption column → vibration Reaktionsofen successively.
Said rare gas element is nitrogen or argon gas, and its purity is higher than 99.9%, and moisture content is less than 20ppm.
The mass content of dry inert gas is 95-97% in the mixed gas of dry inert gas and fluorine gas, and the mass content of fluorine gas is 3-5%.
Vacuum system adopts molecular pump, and in the purge process, after vacuumizing through the molecular sieve adsorption post, the pressure in the vibration Reaktionsofen should be less than 10
-5Pa.
When mixed gas fed the vibration Reaktionsofen, the pressure in the vibration Reaktionsofen device was less than 0.15MPa; The temperature of vibration Reaktionsofen is between 80-100 ℃ in the purge process.
A kind of isolated plant of purification process of lithium hexafluoro phosphate is characterized in that: comprise successively by the vibration gas circulation loop that Reaktionsofen → compressor → the NaF adsorption column → the vibration Reaktionsofen is formed, Al
2O
3Adsorption column is connected with gas circulation loop with the molecular sieve adsorption post; Said vibration Reaktionsofen comprises support; Dress oscillatory type reaction tubes is provided with the pallet of adorning material on the support in the oscillatory type reaction tubes, and oscillatory type reaction tubes two ends are respectively equipped with the communication port that communicates with the pipeline of gas circulation loop; The front portion of oscillatory type reaction tubes is provided with the opening for feed that communicates with the feeding screw outlet; The rear portion of oscillatory type reaction tubes is provided with the discharge port that joins with discharging hopper, and feeding screw space loading hopper joins, and discharging hopper and auger stripper join.
The rotational frequency of feeding screw is 1～20 rev/min among the present invention; Can effectively control the feeding rate of the thick product of lithium hexafluoro phosphate through the rotational frequency of adjusting screw feeder; Can confirm the amount of charging according to feed time, simple, the effective and easy handling of present method.
The rare gas element that adds in advance in the gas circulation loop among the present invention is argon gas or nitrogen, and the adding in advance of rare gas element can guarantee effective circulation of gas in the whole gas circulation loop.
Among the present invention in fluorine gas and the rare gas element mixed gas rare gas element be 95-97%; The content of fluorine gas is 3-5%; The existence of fluorine gas in fluorine gas and the rare gas element mixed gas can be emitted boiling point extremely low (145 ℃), volatile oxyfluoride OF through the reaction of moisture in following formula and the thick product of lithium hexafluoro phosphate
2, reach the purpose that removes.
H
2O+2F
2→2HF+OF
2
The use of vibration Reaktionsofen through the vibration of the thick product tray of lithium hexafluoro phosphate is housed, can guarantee that the thick product of lithium hexafluoro phosphate fully contacts with the rare gas element mixed gas with fluorine gas among the present invention, and moisture thoroughly removes in the thick product of assurance lithium hexafluoro phosphate.The major cause that causes lithium hexafluoro phosphate to be easy to decompose is exactly to contain more water in its product; When the thick product moisture content less of lithium hexafluoro phosphate when (as less than 50ppm); Tangible decomposition can not take place in the thick product of lithium hexafluoro phosphate below 100 ℃, and this is the important foundation that can carry out the dry purifying of thermovacuum to lithium hexafluoro phosphate.In addition, the existence of fluorine gas in fluorine gas and the rare gas element mixed gas among the present invention can be through the LiPO in following formula and the thick product of lithium hexafluoro phosphate
xF
yReaction reaches the purpose of it being carried out purifying,
LiPO
xF
y+F
2→LiPF
6+OF
2。
Vesicular structure NaF among the present invention in the NaF adsorption column can pass through following formula, the hydrogen fluoride in the thick product of lithium hexafluoro phosphate that gets in the gas circulation loop and the fluorine gas hydrogen fluoride with water reaction generation removed,
NaF+HF→NaHF
2。
Vacuum system adopts turbomolecular pump among the present invention, can guarantee that the pressure in the vibration Reaktionsofen is less than 10 to the thick product of lithium hexafluoro phosphate being carried out thermovacuum when dry
-5Pa, Al
2O
3Can protection effectively be provided to turbomolecular pump with the existence of molecular sieve adsorption post, avoid turbomolecular pump to be corroded by fluoro-gas.
The temperature of vibration Reaktionsofen is between 80-100 ℃ in the dry purge process of thermovacuum among the present invention, and pressure is less than 10-5Pa.Vibration through in the vibration Reaktionsofen the thick product tray of lithium hexafluoro phosphate being housed can guarantee that the thick product of lithium hexafluoro phosphate fully is exposed in the thermovacuum atmosphere, reaches the purpose that hydrogen fluoride thoroughly removes.
The present invention is a kind of efficient, safety, the production purification process of good lithium hexafluoro phosphate continuously, and isolated plant is rational in infrastructure, and is easy to use.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is described further.
Fig. 1 is the isolated plant block diagram of one embodiment of the invention.
Fig. 2 is the structural representation of vibration Reaktionsofen.
Embodiment
Embodiment 1:
A kind of purification process of lithium hexafluoro phosphate will vibrate at first that Reaktionsofen vacuumizes and use drying nitrogen to clean repeatedly, and in advance to Al
2O
3Adsorption column and molecular sieve adsorption post carry out activation, and make condensing surface and molecular sieve adsorption post be cooled to-180～-140 ℃, assemble gas circulation loop, Al
2O
3Adsorption column is connected with gas circulation loop with the molecular sieve adsorption post, in gas circulation loop, adds the dry inert gas of 0.06MPa simultaneously in advance; In glove box under dry inert gas protection; In vibration Reaktionsofen hopper, add the thick product of lithium hexafluoro phosphate; This material contains free acid HF600ppm and water 100ppm; The Vibration on Start-up Reaktionsofen injects the mixed gas of dry inert gas and fluorine gas simultaneously in gas circulation loop, the rotational frequency (rotational frequency of feeding screw is 10 rev/mins) of the feeding screw through control vibration Reaktionsofen and adding speed and the amount that feed time is controlled the thick product of lithium hexafluoro phosphate; Start compressor, make the mixed gas circulation of dry inert gas and fluorine gas, the pressure position 0.09MPa to the gas circulation loop, maintenance gas circulation 2 hours is then passed through Al
2O
3Adsorption column vacuumizes system, through the molecular sieve adsorption post gas circulation loop is vacuumized, to vibrating the interior pressure of Reaktionsofen less than 10 again
-5During Pa, stop to vacuumize and keep 6 hours, and in gas circulation loop, refill dry inert gas at last, the purifying to the thick product of lithium hexafluoro phosphate is promptly accomplished in discharging.Purity through product sampling analysis lithium hexafluoro phosphate is 99.93%, and free acid HF content is 76ppm, and the content of water is 12ppm.
Said gas circulation loop is made up of vibration Reaktionsofen → compressor → NaF adsorption column → vibration Reaktionsofen successively.
Said rare gas element is nitrogen or argon gas, and its purity is higher than 99.9%, and moisture content is less than 20ppm.
The mass content of dry inert gas is 95-97% in the mixed gas of dry inert gas and fluorine gas, and the mass content of fluorine gas is 3-5%.
Vacuum system adopts molecular pump.
When mixed gas fed the vibration Reaktionsofen, the pressure in the vibration Reaktionsofen device was less than 0.15MPa; The temperature of vibration Reaktionsofen is between 80-100 ℃ in the purge process.
A kind of isolated plant of purification process of lithium hexafluoro phosphate comprises successively by the vibration gas circulation loop that Reaktionsofen → compressor → the NaF adsorption column → the vibration Reaktionsofen is formed, Al
2O
3Adsorption column is connected with gas circulation loop with the molecular sieve adsorption post; Said vibration Reaktionsofen comprises support 12; Dress oscillatory type reaction tubes 3 is provided with the pallet of adorning material on the support in the oscillatory type reaction tubes, and oscillatory type reaction tubes two ends are respectively equipped with the communication port that communicates with the pipeline of gas circulation loop; The front portion of oscillatory type reaction tubes is provided with the opening for feed that communicates with feeding screw 2 outlets; The rear portion of oscillatory type reaction tubes is provided with the discharge port that joins with discharging hopper 9, and feeding screw and loading hopper 1 join, and discharging hopper and auger stripper 10 join.
Also have dismountable electric furnace 4, phonomoter 5, eccentric wheel 6 (realizing vibration) among the figure, support reaction tubes spring 7, sinuflo tube 8, receive hopper 11, adjustment bolt 13.
Embodiment 2:
In glove box, in helical stir Reaktionsofen feed hopper, add 1 kilogram of thick product of lithium hexafluoro phosphate in advance, this material contains free acid HF620ppm and water 130ppm.Gas circulation loop is vacuumized, then in gas circulation loop, feed the high-purity argon gas of 0.06MPa, repeat said process 3 times.Make the molecular sieve adsorption post be cooled to-180 to-140 ℃, start compressor afterwards, gas in the gas circulation loop is circulated.The feeding screw of Vibration on Start-up Reaktionsofen; On the pallet of vibration Reaktionsofen, push the thick product of lithium hexafluoro phosphate; In gas circulation loop, slowly feed the mixed gas of fluorine gas and argon gas simultaneously, the pressure to gas circulation loop is 0.1MPa, stops in gas circulation loop, to feed the mixed gas of fluorine gas and argon gas; And kept gas circulation 3 hours; Then stop gas circulation and will vibrate Reaktionsofen through adsorption column vacuumizing, will vibrate Reaktionsofen simultaneously and be heated to 90 ℃, vacuum pressure is less than 10 in the vibration Reaktionsofen
-5Behind the Pa, stop to vacuumize and keep 8 hours, and in gas circulation loop, refill dry inert gas at last, discharging can be accomplished the purifying to the thick product of lithium hexafluoro phosphate.Purity through product sampling analysis lithium hexafluoro phosphate is 99.90%, and free acid HF content is 72ppm, and the content of water is 8ppm.All the other are with embodiment 1.
Claims (4)
1. the purification process of a lithium hexafluoro phosphate is characterized in that: will vibrate at first that Reaktionsofen vacuumizes and use drying nitrogen to clean repeatedly, and in advance to Al
2O
3Adsorption column and molecular sieve adsorption post carry out activation, and make condensing surface and molecular sieve adsorption post be cooled to-180 ~-140 ℃, assemble gas circulation loop, Al
2O
3Adsorption column is connected with gas circulation loop with the molecular sieve adsorption post, in gas circulation loop, adds the dry inert gas less than 0.1 MPa simultaneously in advance; In glove box under dry inert gas protection; In vibration Reaktionsofen hopper, add the thick product of lithium hexafluoro phosphate; The Vibration on Start-up Reaktionsofen; In gas circulation loop, inject the mixed gas of dry inert gas and fluorine gas simultaneously, the rotational frequency of the feeding screw through control vibration Reaktionsofen and adding speed and the amount that feed time is controlled the thick product of lithium hexafluoro phosphate; Start compressor, make the mixed gas circulation of dry inert gas and fluorine gas, then pass through Al
2O
3Adsorption column vacuumizes system, through the molecular sieve adsorption post gas circulation loop is vacuumized again, in gas circulation loop, refills dry inert gas, discharging at last;
Said gas circulation loop is made up of vibration Reaktionsofen → compressor → NaF adsorption column → vibration Reaktionsofen successively.
2. the purification process of lithium hexafluoro phosphate according to claim 1, it is characterized in that: said rare gas element is nitrogen or argon gas, and its purity is higher than 99.9%, and moisture content is less than 20ppm.
3. the purification process of lithium hexafluoro phosphate according to claim 1 and 2, it is characterized in that: the mass content of dry inert gas is 95-97% in the mixed gas of dry inert gas and fluorine gas, the mass content of fluorine gas is 3-5%.
4. the purification process of lithium hexafluoro phosphate according to claim 1 and 2 is characterized in that: vacuum system adopts molecular pump, and in the purge process, after vacuumizing through the molecular sieve adsorption post, the pressure in the vibration Reaktionsofen should be less than 10
-5Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100545495A CN102180456B (en) | 2011-03-08 | 2011-03-08 | Method for purifying lithium hexafluorophosphate and special device thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100545495A CN102180456B (en) | 2011-03-08 | 2011-03-08 | Method for purifying lithium hexafluorophosphate and special device thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102180456A CN102180456A (en) | 2011-09-14 |
| CN102180456B true CN102180456B (en) | 2012-11-28 |
Family
ID=44566783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100545495A Active CN102180456B (en) | 2011-03-08 | 2011-03-08 | Method for purifying lithium hexafluorophosphate and special device thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102180456B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496713B (en) * | 2011-12-19 | 2013-08-28 | 中国海洋石油总公司 | Method for reducing free acid content in lithium hexafluorophosphate |
| CN103553009B (en) * | 2013-10-11 | 2016-03-09 | 浙江巨化凯蓝新材料有限公司 | A kind of Chemical deep purification method of lithium hexafluoro phosphate |
| CN109865313A (en) * | 2017-12-04 | 2019-06-11 | 北京市合众创能光电技术有限公司 | A kind of method of trace water in removal ionic liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850593A (en) * | 2006-05-30 | 2006-10-25 | 天津化工研究设计院 | Method for purifying lithium hexafluoro phosphate |
| CN201981007U (en) * | 2011-03-08 | 2011-09-21 | 江苏九九久科技股份有限公司 | Device special for purifying lithium hexafluorophosphate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3483107B2 (en) * | 1997-11-12 | 2004-01-06 | セントラル硝子株式会社 | Purification method of lithium hexafluorophosphate |
-
2011
- 2011-03-08 CN CN2011100545495A patent/CN102180456B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850593A (en) * | 2006-05-30 | 2006-10-25 | 天津化工研究设计院 | Method for purifying lithium hexafluoro phosphate |
| CN201981007U (en) * | 2011-03-08 | 2011-09-21 | 江苏九九久科技股份有限公司 | Device special for purifying lithium hexafluorophosphate |
Non-Patent Citations (2)
| Title |
|---|
| JP特开平11-147705A 1999.06.02 |
| 庄全超 等.六氟磷酸锂生产工艺研究.《电池工业》.2005,第10卷(第3期),第169-172页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102180456A (en) | 2011-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107720717B (en) | Preparation method of lithium difluorophosphate | |
| CN113135554A (en) | Preparation method of lithium bis (fluorosulfonyl) imide | |
| CN109415209B (en) | Process for producing bis (fluorosulfonyl) imide alkali metal salt | |
| CN109941978A (en) | The method for preparing double fluorine sulfimide ammoniums and double fluorine sulfimide alkali metal salts | |
| WO2010146710A1 (en) | Method for producing tetrafluoroborate | |
| JP5845955B2 (en) | Method for producing lithium hexafluorophosphate concentrate | |
| EP2857408B1 (en) | Method for producing tetrafluoro(oxalate)phosphate solution | |
| CN102826563A (en) | Preparation method of high-purity lithium tetrafluoroborate | |
| JP5862094B2 (en) | Method for producing lithium hexafluorophosphate concentrate | |
| CN105859760A (en) | A synthetic method of electronic grade lithium difluoro(oxalato)borate | |
| CN104310421A (en) | Preparation method of high-purity lithium tetrafluoroborate | |
| CN103483368B (en) | A kind of preparation method of difluorine oxalic acid boracic acid lithium | |
| CN112707418A (en) | Preparation method of lithium hexafluorophosphate | |
| CN102180456B (en) | Method for purifying lithium hexafluorophosphate and special device thereof | |
| KR20180069736A (en) | Manufacturing method for lithium hydroxide from lithium phosphate | |
| CN114560456A (en) | Preparation method of lithium difluorophosphate | |
| JP5165364B2 (en) | Method for producing hexafluorophosphate | |
| CN113549095A (en) | Preparation process of lithium bis (oxalato) borate | |
| CN115385352B (en) | Preparation method of lithium tetrafluoroborate | |
| CN115924881A (en) | Method for producing hexafluorophosphate with yellow phosphorus as raw material | |
| CN106829908A (en) | A kind of preparation method of difluorophosphate and the non-aqueous electrolyte for lithium ion cell containing difluorophosphate | |
| Bankole et al. | Silicon exchange effects of glassware on the recovery of LiPF6: Alternative route to preparation of Li2SiF6 | |
| CN201981007U (en) | Device special for purifying lithium hexafluorophosphate | |
| CN112678795B (en) | Preparation method of lithium difluorophosphate | |
| JP5252908B2 (en) | Method for producing tetrafluoroborate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: 226407 Rudong Economic Development Zone, Nantong, the Yellow Sea, No., No. three road, No. 12 Patentee after: Jiangsu BICON Pharmaceutical Co., Ltd. Address before: 226401 Jiangsu city of Nantong province Rudong County town of Jianshe Road Matang No. 40 Patentee before: Jiangsu Jiujiujiu Technology Co., Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20180103 Address after: 226407 Rudong Economic Development Zone, Nantong, the Yellow Sea, No., No. three road, No. 12 Patentee after: Jiangsu nine Jiangsu jiujiujiu Technology Co. Ltd. Address before: 226407 Rudong Economic Development Zone, Nantong, the Yellow Sea, No., No. three road, No. 12 Patentee before: Jiangsu BICON Pharmaceutical Co., Ltd. |
|
| TR01 | Transfer of patent right |