CN106241840A - The preparation method of a kind of lithium hexafluoro phosphate and preparation system - Google Patents
The preparation method of a kind of lithium hexafluoro phosphate and preparation system Download PDFInfo
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- CN106241840A CN106241840A CN201610812329.7A CN201610812329A CN106241840A CN 106241840 A CN106241840 A CN 106241840A CN 201610812329 A CN201610812329 A CN 201610812329A CN 106241840 A CN106241840 A CN 106241840A
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- Prior art keywords
- hexafluoro phosphate
- lithium hexafluoro
- gas
- reactor
- freezing
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 96
- 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 title claims abstract description 77
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 76
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 76
- 239000010452 phosphate Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- 238000007710 freezing Methods 0.000 claims abstract description 56
- 230000008014 freezing Effects 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 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
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims description 97
- 238000006243 chemical reaction Methods 0.000 claims description 69
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 claims description 43
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 24
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- 238000003786 synthesis reaction Methods 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 18
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 238000010298 pulverizing process Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 27
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 7
- 239000001110 calcium chloride Substances 0.000 abstract description 7
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 7
- 238000011109 contamination Methods 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 6
- -1 hexafluoro phosphorus Chemical compound 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 229910052756 noble gas Inorganic materials 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000003682 fluorination reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides the preparation method of a kind of lithium hexafluoro phosphate, the preparation method that the present invention provides uses calcium fluoride as fluorine source, uses organic solvent as solvent simultaneously, avoids using Fluohydric acid., make preparation process and product safer in preparation process.Further, obtain the direct freezing and crystallizing of lithium hexafluoro phosphate to be dried and i.e. can get highly purified lithium hexafluoro phosphate, it is not necessary to by any solvent.This method preparation process is not discharged gas, liquid, the chilled recycling use of gas produced when being dried, unique by-product is solid calcium chloride, purified after be extensive general chemical, it is achieved that free of contamination green prepare.
Description
Technical field
The invention belongs to fluorochemical technical field, be specifically related to preparation method and the preparation system of a kind of lithium hexafluoro phosphate
System.
Background technology
The existing technique many employings HF of lithium hexafluoro phosphate for preparing is as fluorine source, and HF belongs to deadly poisonous compound, in production process
There is the health hazard to human body and pollution, simultaneously synthesizing reacted by-product is the hydrochloric acid containing HF, and the cost of process is non-
Chang Gao.Further, the purification of lithium hexafluoro phosphate crude product mainly uses HF technique to carry out, and remaining in the HF in lithium hexafluoro phosphate can affect
The use safety of subsequent product-lithium ion battery.It addition, when dry, many employings vacuum is direct in lithium hexafluoro phosphate preparation process
The mode being dried is carried out, and uneven and over-heating phenomenon of being heated causes lithium hexafluoro phosphate to decompose so that productivity and purity are relatively
Low.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide preparation method and the dress of a kind of lithium hexafluoro phosphate
Putting, the preparation method safety that the present invention provides, the yield of product and purity are high, and by-product does not pollute.
The invention provides the preparation system of a kind of lithium hexafluoro phosphate, including:
Phosphorus pentafluoride gas generator, described phosphorus pentafluoride gas generator includes: reaction chamber, be opened in described reaction
Fluorine source matter inlet on the sidewall of chamber, it is arranged at described reaction chamber top the interruption being connected with described reaction chamber
Charging device and be arranged at the aerofluxus condensing unit on described reaction chamber top；
Gas access efficiently synthesizes reactor with the outlet of described aerofluxus condensing unit is connected, described in efficiently synthesize reaction
Device top offers lithium source substance entrance；
Synthesis liquid entrance exports, with the described synthesis liquid efficiently synthesizing reactor, the freezing and crystallizing device being connected；
Material inlet is that be connected with the discharging opening of described freezing and crystallizing device, rotatable Minton dryer, described very
It is provided with high speed disintegrator in empty drying device.
Preferably, also include being arranged at described aerofluxus condensing unit and the described purification for gas efficiently synthesized between reactor
Device.
Preferably, efficiently synthesize described in the gas access of reactor be opened in described in efficiently synthesize the bottom of reactor.
Present invention also offers a kind of method using above-mentioned preparation system to prepare lithium hexafluoro phosphate, comprise the following steps:
A) calcium fluoride by interruption charging device, is placed in phosphorus pentafluoride gas is sent out by fluorine source matter inlet, phosphorus pentachloride
In the reaction chamber of raw device, mixing is reacted, and product, after described aerofluxus condensing unit carries out freezing, obtains five fluorine
Change phosphorus gas；
B) lithium fluoride joined by lithium source substance entrance be contained with organic solvent efficiently synthesize in reactor, mixing is stirred
Mix, obtain suspension；
Described phosphorus pentafluoride gas efficiently synthesizes the gas access of reactor and is passed through to described suspension described in passing through, and enters
Row stirring reaction；
C) step B) product that obtains enters described freezing and crystallizing by the synthesis liquid entrance of freezing and crystallizing device and fills
Put, carry out step cooling crystallization, obtain lithium hexafluoro phosphate；
D) described lithium hexafluoro phosphate is transported to described Minton dryer by the discharging opening of described freezing and crystallizing device
In, under inert gas conditions with vacuum condition alternating senses, carry out pulverizing and Rotary drying simultaneously, obtain the hexafluoro phosphorus being dried
Acid lithium.
Preferably, step A) in, the temperature of described reaction is 200～400 DEG C, the pressure of described reaction be 0.5～
1.2MPa。
Preferably, step A) in, the temperature of described freezing is-80 DEG C～-40 DEG C.
Preferably, described organic solvent is selected from carbonate based organic solvent, ether organic solvent or acetonitrile.
Preferably, step B) in, the temperature of described stirring reaction is 0～40 DEG C, and the time of described stirring reaction is 6～24
Hour.
Preferably, the method for described step cooling crystallization is:
By the described organic solution containing lithium hexafluoro phosphate through 0～-20 DEG C of freezings 4～after 8 hours, then it is cooled to-30
DEG C～-40 DEG C carry out crystallize 8～16 hours.
Preferably, described dry temperature is 80～120 DEG C, and the pressure of described vacuum condition is-0.08～-0.1MPa.
Compared with prior art, the preparation system that the invention provides a kind of present invention of employing prepares the side of lithium hexafluoro phosphate
Method, comprises the following steps: A) calcium fluoride is placed in five fluorinations by fluorine source matter inlet, phosphorus pentachloride by being interrupted charging device
Mixing is reacted in the reaction chamber of phosphorus gas generator, product after described aerofluxus condensing unit carries out freezing,
Obtain phosphorus pentafluoride gas；B) lithium fluoride joined by lithium source substance entrance be contained with organic solvent efficiently synthesize reactor
In, mix and blend, obtain suspension；Described phosphorus pentafluoride gas pass through described in efficiently synthesize the gas access of reactor be passed through to
In described suspension, it is stirred reaction；C) step B) product that the obtains synthesis liquid entrance by freezing and crystallizing device
Enter described freezing and crystallizing device, carry out step cooling crystallization, obtain lithium hexafluoro phosphate；D) described lithium hexafluoro phosphate is by described
The discharging opening of freezing and crystallizing device is transported in described Minton dryer, replaces feelings at inert gas conditions and vacuum condition
Under condition, carry out pulverizing and Rotary drying simultaneously, obtain the lithium hexafluoro phosphate being dried.The preparation method that the present invention provides uses fluorination
Calcium, as fluorine source, uses organic solvent as solvent simultaneously, avoids using Fluohydric acid., make preparation process and product in preparation process
Thing is safer.Further, obtain the direct freezing and crystallizing of lithium hexafluoro phosphate and be dried and i.e. can get highly purified lithium hexafluoro phosphate, be not required to
Will be by any solvent.Not discharging gas, liquid in this method preparation process, the chilled recovery of gas produced when being dried is circulated
Using, unique by-product is solid calcium chloride, and purified is extensive general chemical afterwards, it is achieved that free of contamination green system
Standby.
Result shows, purity >=99.9% of the lithium hexafluoro phosphate that the preparation method that the present invention provides prepares, yield
>=15%.
Accompanying drawing explanation
The structural representation of the preparation system of the lithium hexafluoro phosphate that Fig. 1 provides for the present invention.
Detailed description of the invention
The invention provides the preparation system of a kind of lithium hexafluoro phosphate, including:
Phosphorus pentafluoride gas generator, described phosphorus pentafluoride gas generator includes: reaction chamber, be opened in described reaction
Fluorine source matter inlet on the sidewall of chamber, it is arranged at described reaction chamber top the interruption being connected with described reaction chamber
Charging device and be arranged at the aerofluxus condensing unit on described reaction chamber top；
Gas access efficiently synthesizes reactor with the outlet of described aerofluxus condensing unit is connected, described in efficiently synthesize reaction
Device top offers lithium source substance entrance；
Synthesis liquid entrance exports, with the described synthesis liquid efficiently synthesizing reactor, the freezing and crystallizing device being connected；
Material inlet is that be connected with the discharging opening of described freezing and crystallizing device, rotatable Minton dryer, described very
It is provided with high speed disintegrator in empty drying device.
In conjunction with Fig. 1, describing the preparation system of the lithium hexafluoro phosphate that the present invention provides in detail, Fig. 1 is that the present invention carries
The structural representation of the preparation system of the lithium hexafluoro phosphate of confession.
The preparation system of the lithium hexafluoro phosphate that the present invention provides includes phosphorus pentafluoride gas generator, described phosphorus pentafluoride gas
Body generator reacts for fluorine source material and phosphorus source material being mixed, and prepares the place of phosphorus pentafluoride.
Concrete, described phosphorus pentafluoride gas generator includes:
Reaction chamber,
The fluorine source matter inlet that is opened on the sidewall of described reaction chamber,
Be arranged at described reaction chamber top the interruption charging device being connected with described reaction chamber,
And it is arranged at the aerofluxus condensing unit on described reaction chamber top；
Described phosphorus pentafluoride gas generator includes reaction chamber, and described reaction raw materials is carried out instead in described reaction chamber
Should.In the present invention, the preparation of described phosphorus pentafluoride gas is to react under high-temperature and high-pressure conditions, therefore, and described reaction
Chamber can bear certain temperature and pressure.
Described phosphorus pentafluoride gas generator also includes the fluorine source matter inlet being opened on the sidewall of described reaction chamber.
Described fluorine source inlet is reaction raw materials calcium fluoride delivery port of the present invention, and described calcium fluoride enters institute by described fluorine source matter inlet
State in reaction chamber.
Described phosphorus pentafluoride gas generator also include being arranged at described reaction chamber top and with described reaction chamber phase
The interruption charging device of connection, reaction raw materials phosphorus pentachloride of the present invention enters described reaction chamber by described interruption charging device
In.
Described phosphorus pentachloride gas generating unit also includes the aerofluxus condensing unit being arranged at described reaction chamber top, institute
State aerofluxus condensing unit for the product for preparing of cooling, such that it is able to obtain phosphorus pentafluoride gas.
The preparation system of lithium hexafluoro phosphate that the present invention provides also includes going out of gas access and described aerofluxus condensing unit
Mouthful be connected efficiently synthesizes reactor, described in efficiently synthesize reactor head and offer lithium source substance entrance.
The described reactor that efficiently synthesizes is phosphorus pentafluoride gas and described lithium fluoride carries out the place reacted.Described efficient conjunction
Become reactor head offer lithium source substance entrance, lithium fluoride by lithium source substance entrance enter to described in efficiently synthesize reaction
Device.
Preferably, described in efficiently synthesize the gas access of reactor be opened in described in efficiently synthesize the bottom of reactor, from
And phosphorus pentafluoride gas can be made to be entered by bottom and efficiently synthesize in reactor, react more abundant with described lithium fluoride.
The present invention some preferred embodiment in, the preparation system of described lithium hexafluoro phosphate also includes being arranged at institute
State aerofluxus condensing unit and the described gas purification apparatus efficiently synthesized between reactor, the outlet of described aerofluxus condensing unit with
The entrance of described gas purification apparatus is connected, and the outlet of described gas purification apparatus enters with the described gas efficiently synthesizing reactor
Mouth is connected.Described gas purification apparatus is used for purification phosphorus pentafluoride gas, thus ensures that the purity of phosphorus pentafluoride gas meets system
The requirement of standby lithium hexafluoro phosphate.
The preparation system of the lithium hexafluoro phosphate that the present invention provides also includes that synthesizing liquid entrance efficiently synthesizes reactor with described
Synthesis liquid outlet be connected freezing and crystallizing device.In the present invention, described freezing and crystallizing device is for closing described in freezing and crystallizing
Become liquid, thus lithium hexafluoro phosphate is separated with described organic solvent, obtain lithium hexafluoro phosphate.Organic molten containing lithium hexafluoro phosphate
Agent, i.e. synthesis liquid pass through described in efficiently synthesize reactor synthesis liquid outlet after, through described and described synthesis liquid outlet be connected
The synthesis liquid entrance of freezing and crystallizing device, enter in described freezing and crystallizing device.
The preparation system of lithium hexafluoro phosphate that the present invention provides also includes going out of material inlet and described freezing and crystallizing device
Material mouth is that be connected, the rotatable Minton dryer for pulverizing and be dried lithium hexafluoro phosphate, in described Minton dryer
It is provided with high speed disintegrator.
In the present invention, described Minton dryer is used for being dried described lithium hexafluoro phosphate, it is preferred that described vacuum drying
Device rotates with the horizontal axis of himself for axle center, such that it is able to realize material uniform heating, it is to avoid hexafluoro phosphorus
Acid lithium causes the decomposition of lithium hexafluoro phosphate owing to being heated uneven or over-heating.
Further, it is additionally provided with high speed disintegrator inside described Minton dryer.Product is carried out vacuum drying with
Time, it is also possible to carry out the operation pulverized, such that it is able to further realize the thermally equivalent of material, improve the yield of product.
Present invention also offers a kind of method using above-mentioned preparation system to prepare lithium hexafluoro phosphate, comprise the following steps:
A) calcium fluoride by interruption charging device, is placed in phosphorus pentafluoride gas is sent out by fluorine source matter inlet, phosphorus pentachloride
In the reaction chamber of raw device, mixing is reacted, and product, after described aerofluxus condensing unit carries out freezing, obtains five fluorine
Change phosphorus gas；
B) lithium fluoride joined by lithium source substance entrance be contained with organic solvent efficiently synthesize in reactor, mixing is stirred
Mix, obtain suspension；
Described phosphorus pentafluoride gas efficiently synthesizes the gas access of reactor and is passed through to described suspension described in passing through, and enters
Row stirring reaction；
C) step B) product that obtains enters described freezing and crystallizing by the synthesis liquid entrance of freezing and crystallizing device and fills
Put, carry out step cooling crystallization, obtain lithium hexafluoro phosphate；
D) described lithium hexafluoro phosphate is transported to described Minton dryer by the discharging opening of described freezing and crystallizing device
In, under inert gas conditions with vacuum condition alternating senses, carry out pulverizing and Rotary drying simultaneously, obtain the hexafluoro phosphorus being dried
Acid lithium.
First calcium fluoride is placed in five fluorinations by fluorine source matter inlet, phosphorus pentachloride by being interrupted charging device by the present invention
In the reaction chamber of phosphorus gas generator, mixing is reacted, and obtains product；
In the present invention, the temperature of described reaction is preferably 200～400 DEG C, more preferably 250～350 DEG C, described reaction
Pressure be preferably 0.5～1.2MPa, preferably 0.8～1.0MPa.
The product obtained carries out freezing through described aerofluxus condensing unit, separates gas, obtains phosphorus pentachloride gas.
Wherein, the temperature of described freezing is preferably-80 DEG C～-40 DEG C, more preferably-70 DEG C～-50 DEG C.In the present invention, described five
Purity ＞ 99.0% of phosphorus chloride gas.
In the present invention, lithium fluoride joined by lithium source substance entrance be contained with organic solvent efficiently synthesize reactor
In, mix and blend, obtain suspension；
In the present invention, described organic solvent, selected from carbonate based organic solvent, ether organic solvent or acetonitrile, is preferably
Dimethyl carbonate, glycol dimethyl ether or acetonitrile.
After obtaining suspension, described phosphorus pentafluoride gas is passed through described in efficiently synthesize the gas access of reactor be passed through to
In described suspension, it is stirred reaction, obtains the organic solution containing lithium hexafluoro phosphate；
Wherein, the temperature of described stirring reaction is preferably 0～40 DEG C, more preferably 10～30 DEG C；Described stirring reaction
Time is preferably 6～24 hours, more preferably 10～20 hours.
Then, the described organic solution containing lithium hexafluoro phosphate enters described by the synthesis liquid entrance of freezing and crystallizing device
Freezing and crystallizing device, carries out step cooling crystallization, obtains lithium hexafluoro phosphate.
In the present invention, the method for described step cooling crystallization is preferably:
By the described organic solution containing lithium hexafluoro phosphate through 0～-20 DEG C of freezings 4～after 8 hours, then it is cooled to-30
DEG C～-40 DEG C carry out crystallize 8～16 hours；
It is furthermore preferred that the described organic solution containing lithium hexafluoro phosphate is passed through-5～-15 DEG C, after freezing 5～7 hours,
It is cooled to-32 DEG C～-38 DEG C again and carries out crystallize 10～14 hours.
Finally, described lithium hexafluoro phosphate is transported to described vacuum drying dress by the discharging opening of described freezing and crystallizing device
In putting, under inert gas conditions with vacuum condition alternating senses, carry out pulverizing and Rotary drying simultaneously, obtain the hexafluoro being dried
Lithium phosphate.
In the present invention, described dry temperature is preferably 80～120 DEG C, more preferably 90～110 DEG C, described vacuum bar
The pressure of part is preferably-0.08～-0.1MPa.Described inert gas conditions is preferably nitrogen atmosphere condition or argon gas atmosphere bar
Part.In the present invention, described inert gas conditions and vacuum condition frequency alternately is 2 times/h～1 time/2h, described rotation
Rotating speed is 15 turns/min～60 turns/min.
The preparation method that the present invention provides uses calcium fluoride as fluorine source, uses organic solvent as solvent, preparation simultaneously
During avoid use Fluohydric acid., make preparation process and product safer.Further, lithium hexafluoro phosphate directly freezing knot is obtained
Brilliant being dried i.e. can get highly purified lithium hexafluoro phosphate, it is not necessary to by any solvent.This method preparation process is not discharged gas
Body, liquid, be dried time produce the chilled recycling use of gas, unique by-product is solid calcium chloride, purified after be
Extensive general chemical, it is achieved that free of contamination green preparation.
Result shows, purity >=99.9% of the lithium hexafluoro phosphate that the preparation method that the present invention provides prepares, yield
>=15%.
In order to be further appreciated by the present invention, below in conjunction with the embodiment preparation method to the lithium hexafluoro phosphate that the present invention provides
Illustrating with preparation system, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Present embodiments provide the preparation system of a kind of lithium hexafluoro phosphate, including:
Phosphorus pentafluoride gas generator, described phosphorus pentafluoride gas generator includes:
Reaction chamber,
The fluorine source matter inlet that is opened on the sidewall of described reaction chamber,
Be arranged at described reaction chamber top the interruption charging device being connected with described reaction chamber,
And it is arranged at the aerofluxus condensing unit on described reaction chamber top；
The gas purification apparatus that entrance is connected with the outlet of described aerofluxus condensing unit；
Gas access efficiently synthesizes reactor with the outlet of described purification devices is connected, described in efficiently synthesize reactor top
Portion offers lithium source substance entrance, described in efficiently synthesize the gas access of reactor be opened in described in efficiently synthesize the end of reactor
Portion；
Synthesis liquid entrance exports, with the described synthesis liquid efficiently synthesizing reactor, the freezing and crystallizing device being connected；
That material inlet is connected with the discharging opening of described freezing and crystallizing device, rotatable for pulverizing and be dried hexafluoro phosphorus
The Minton dryer of acid lithium, is provided with high speed disintegrator in described Minton dryer.
Embodiment 2
1, the preparation system that embodiment 1 provides is used, by calcium fluoride by fluorine source matter inlet, phosphorus pentachloride by being interrupted
Charging device is blended in being placed in the reaction chamber of phosphorus pentafluoride gas generator under the pressure of 0.5MPa, at temperature 300 DEG C
Prepare phosphorus pentafluoride gas, obtain product；
Described product separates gas at described aerofluxus condensing unit is at-80 DEG C and obtains purity and be more than after freezing
The phosphorus pentachloride gas of 99.0%.
2, lithium fluoride joined by lithium source substance entrance be contained with acetonitrile efficiently synthesize in reactor, mix and blend,
Obtain suspension；
Described phosphorus pentafluoride gas efficiently synthesizes the gas access of reactor and is passed through to described suspension described in passing through, and enters
Row stirring reaction, controlling temperature is 20 DEG C, and mixing time is to filter insoluble matter after 6h, and obtain containing lithium hexafluoro phosphate is organic molten
Liquid.
3, the described organic solution containing lithium hexafluoro phosphate enters described cold by the synthesis liquid entrance of freezing and crystallizing device
Freeze crystallization apparatus, substep experience 0 DEG C, be cooled to-40 DEG C again after 8h and carry out crystallize 8h, obtained except knot by discharging opening automatic transport
Containing the high purity lithium hexafluorophosphate that other impurity are little beyond brilliant solvent.
4, described high purity lithium hexafluorophosphate is transported to described vacuum drying by the discharging opening of described freezing and crystallizing device
In device, under noble gas and vacuum-0.1MPa alternately protection, 80 DEG C are dried, described noble gas and vacuum condition alternately
Frequency is 1 time/2h, carries out the lithium hexafluoro phosphate pulverizing and obtaining after rotary heating 24h to be dried simultaneously.
5, determination step 4 obtains the purity of lithium hexafluoro phosphate being dried and calculated yield, result be product purity >=
99.9%, yield 15%.
This method preparation process is not discharged gas, liquid, the chilled recycling use of gas produced when being dried, only
One by-product is solid calcium chloride, and purified is that extensive general chemical is for sale afterwards, it is achieved that free of contamination green system
Standby.
Embodiment 3
1, the preparation system that embodiment 1 provides is used, by calcium fluoride by fluorine source matter inlet, phosphorus pentachloride by being interrupted
Charging device is blended in being placed in the reaction chamber of phosphorus pentafluoride gas generator under the pressure of 1.2MPa, at temperature 200 DEG C
Prepare phosphorus pentafluoride gas, obtain product；
Described product separates gas at described aerofluxus condensing unit is at-80 DEG C and obtains purity and be more than after freezing
The phosphorus pentachloride gas of 99.0%.
2, lithium fluoride joined by lithium source substance entrance be contained with dimethyl carbonate efficiently synthesize in reactor, mixing
Stirring, obtains suspension；
Described phosphorus pentafluoride gas efficiently synthesizes the gas access of reactor and is passed through to described suspension described in passing through, and enters
Row stirring reaction, controlling temperature is 20 DEG C, and mixing time is to filter insoluble matter after 6h, and obtain containing lithium hexafluoro phosphate is organic molten
Liquid.
3, the described organic solution containing lithium hexafluoro phosphate enters described cold by the synthesis liquid entrance of freezing and crystallizing device
Freeze crystallization apparatus, substep experience-10 DEG C, be cooled to-40 DEG C after 8h again and carry out crystallize 8h, removed by discharging opening automatic transport
Containing the high purity lithium hexafluorophosphate that other impurity are little beyond recrystallisation solvent.
4, described high purity lithium hexafluorophosphate is transported to described vacuum drying by the discharging opening of described freezing and crystallizing device
In device, under noble gas and vacuum-0.08MPa alternately protection, 120 DEG C are dried, described noble gas and the friendship of vacuum condition
It is 2 times/h for frequency, carries out the lithium hexafluoro phosphate pulverizing and obtaining after rotary heating 24h to be dried simultaneously.
5, determination step 4 obtains the purity of lithium hexafluoro phosphate being dried and calculated yield, result be product purity >=
99.9%, yield 15%.
This method preparation process is not discharged gas, liquid, the chilled recycling use of gas produced when being dried, only
One by-product is solid calcium chloride, and purified is that extensive general chemical is for sale afterwards, it is achieved that free of contamination green system
Standby.
Embodiment 4
1, the preparation system that embodiment 1 provides is used, by calcium fluoride by fluorine source matter inlet, phosphorus pentachloride by being interrupted
Charging device is blended in being placed in the reaction chamber of phosphorus pentafluoride gas generator under the pressure of 0.9MPa, at temperature 260 DEG C
Prepare phosphorus pentafluoride gas, obtain product；
Described product separates gas at described aerofluxus condensing unit is at-80 DEG C and obtains purity and be more than after freezing
The phosphorus pentachloride gas of 99.0%.
2, lithium fluoride joined by lithium source substance entrance be contained with glycol dimethyl ether efficiently synthesize in reactor, mixed
Close stirring, obtain suspension；
Described phosphorus pentafluoride gas efficiently synthesizes the gas access of reactor and is passed through to described suspension described in passing through, and enters
Row stirring reaction, controlling temperature is 25 DEG C, and mixing time is to filter insoluble matter after 6h, and obtain containing lithium hexafluoro phosphate is organic molten
Liquid.
3, the described organic solution containing lithium hexafluoro phosphate enters described cold by the synthesis liquid entrance of freezing and crystallizing device
Freeze crystallization apparatus, substep experience-10 DEG C, be cooled to-25 DEG C after 8h again and carry out crystallize 8h, removed by discharging opening automatic transport
Containing the high purity lithium hexafluorophosphate that other impurity are little beyond recrystallisation solvent.
4, described high purity lithium hexafluorophosphate is transported to described vacuum drying by the discharging opening of described freezing and crystallizing device
In device, under noble gas and vacuum-0.08MPa alternately protection, 100 DEG C are dried, described noble gas and the friendship of vacuum condition
It is 1 time/h for frequency, carries out the lithium hexafluoro phosphate pulverizing and obtaining after rotary heating 24h to be dried simultaneously.
5, determination step 4 obtains the purity of lithium hexafluoro phosphate being dried and calculated yield, result be product purity >=
99.9%, yield 15%.
This method preparation process is not discharged gas, liquid, the chilled recycling use of gas produced when being dried, only
One by-product is solid calcium chloride, and purified is that extensive general chemical is for sale afterwards, it is achieved that free of contamination green system
Standby.
Embodiment 5
1, the preparation system that embodiment 1 provides is used, by calcium fluoride by fluorine source matter inlet, phosphorus pentachloride by being interrupted
Charging device is blended in being placed in the reaction chamber of phosphorus pentafluoride gas generator under the pressure of 0.9MPa, at temperature 260 DEG C
Prepare phosphorus pentafluoride gas, obtain product；
Described product separates gas at described aerofluxus condensing unit is at-80 DEG C and obtains purity and be more than after freezing
The phosphorus pentachloride gas of 99.0%.
2, lithium fluoride joined by lithium source substance entrance be contained with acetonitrile efficiently synthesize in reactor, mix and blend,
Obtain suspension；
Described phosphorus pentafluoride gas efficiently synthesizes the gas access of reactor and is passed through to described suspension described in passing through, and enters
Row stirring reaction, controlling temperature is 40 DEG C, and mixing time is to filter insoluble matter after 4h, and obtain containing lithium hexafluoro phosphate is organic molten
Liquid.
3, the described organic solution containing lithium hexafluoro phosphate enters described cold by the synthesis liquid entrance of freezing and crystallizing device
Freeze crystallization apparatus, substep experience 0 DEG C, be cooled to-30 DEG C again after 8h and carry out crystallize 8h, obtained except knot by discharging opening automatic transport
Containing the high purity lithium hexafluorophosphate that other impurity are little beyond brilliant solvent.
4, described high purity lithium hexafluorophosphate is transported to described vacuum drying by the discharging opening of described freezing and crystallizing device
In device, under noble gas and vacuum-0.08MPa alternately protection, 120 DEG C are dried, described noble gas and the friendship of vacuum condition
It is 2 times/h for frequency, carries out the lithium hexafluoro phosphate pulverizing and obtaining after rotary heating 16h to be dried simultaneously.
5, determination step 4 obtains the purity of lithium hexafluoro phosphate being dried and calculated yield, result be product purity >=
99.9%, yield 15%.
This method preparation process is not discharged gas, liquid, the chilled recycling use of gas produced when being dried, only
One by-product is solid calcium chloride, and purified is that extensive general chemical is for sale afterwards, it is achieved that free of contamination green system
Standby.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. the preparation system of a lithium hexafluoro phosphate, it is characterised in that including:
Phosphorus pentafluoride gas generator, described phosphorus pentafluoride gas generator includes: reaction chamber, be opened in described reaction chamber
Sidewall on fluorine source matter inlet, be arranged at described reaction chamber top and the interruption that is connected with described reaction chamber feeds intake
Device and be arranged at the aerofluxus condensing unit on described reaction chamber top；
Gas access efficiently synthesizes reactor with the outlet of described aerofluxus condensing unit is connected, described in efficiently synthesize reactor top
Portion offers lithium source substance entrance；
Synthesis liquid entrance exports, with the described synthesis liquid efficiently synthesizing reactor, the freezing and crystallizing device being connected；
Material inlet is that be connected with the discharging opening of described freezing and crystallizing device, rotatable Minton dryer, and described vacuum is done
It is provided with high speed disintegrator in dry device.
Preparation system the most according to claim 1, it is characterised in that also include being arranged at described aerofluxus condensing unit with described
Efficiently synthesize the gas purification apparatus between reactor.
Preparation system the most according to claim 1, it is characterised in that described in efficiently synthesize the gas access of reactor and offer
In the described bottom efficiently synthesizing reactor.
4. using the method that the preparation system described in claims 1 to 3 any one prepares lithium hexafluoro phosphate, its feature exists
In, comprise the following steps:
A) calcium fluoride is placed in phosphorus pentafluoride gas generator by fluorine source matter inlet, phosphorus pentachloride by being interrupted charging device
Reaction chamber in mixing react, product, after described aerofluxus condensing unit carries out freezing, obtains phosphorus pentafluoride
Gas；
B) lithium fluoride joined by lithium source substance entrance be contained with organic solvent efficiently synthesize in reactor, mix and blend,
Obtain suspension；
Described phosphorus pentafluoride gas efficiently synthesizes the gas access of reactor and is passed through to described suspension described in passing through, and stirs
Mix reaction；
C) step B) product that obtains enters described freezing and crystallizing device by the synthesis liquid entrance of freezing and crystallizing device, enters
Row step cooling crystallizes, and obtains lithium hexafluoro phosphate；
D) described lithium hexafluoro phosphate is transported in described Minton dryer by the discharging opening of described freezing and crystallizing device,
Inert gas conditions, with under vacuum condition alternating senses, carries out pulverizing and Rotary drying simultaneously, obtains the lithium hexafluoro phosphate being dried.
Method the most according to claim 4, it is characterised in that step A) in, the temperature of described reaction is 200～400 DEG C,
The pressure of described reaction is 0.5～1.2MPa.
Method the most according to claim 4, it is characterised in that step A) in, the temperature of described freezing is-80 DEG C～-40
℃。
Method the most according to claim 4, it is characterised in that described organic solvent is selected from carbonate based organic solvent, ether
Class organic solvent or acetonitrile.
Method the most according to claim 4, it is characterised in that step B) in, the temperature of described stirring reaction is 0～40
DEG C, the time of described stirring reaction is 6～24 hours.
Method the most according to claim 4, it is characterised in that the method for described step cooling crystallization is:
By the described organic solution containing lithium hexafluoro phosphate through 0～-20 DEG C of freezings 4～after 8 hours, then be cooled to-30 DEG C～-
40 DEG C carry out crystallize 8～16 hours.
Method the most according to claim 4, it is characterised in that described dry temperature is 80～120 DEG C, described vacuum
The pressure of condition is-0.08～-0.1MPa.
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| CN113772645A (en) * | 2021-10-24 | 2021-12-10 | 会昌宏氟高新材料有限责任公司 | Phosphorus pentafluoride synthesis process |
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| CN115196654A (en) * | 2022-08-11 | 2022-10-18 | 胜华新能源科技(东营)有限公司 | Liquid lithium hexafluorophosphate synthesis device and application thereof |
| CN115771906A (en) * | 2022-11-29 | 2023-03-10 | 湖北犇星新能源材料有限公司 | Method for preparing lithium hexafluorophosphate through solid-solid reaction |
| CN116078292A (en) * | 2021-11-08 | 2023-05-09 | 中化蓝天集团有限公司 | Synthesis reactor of lithium hexafluorophosphate, continuous synthesis reaction system and process |
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| IL313534A (en) | 2021-12-22 | 2024-08-01 | Univ Oxford Innovation Ltd | Caf2-based fluorination reagents, methods of preparation and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115771906A (en) * | 2022-11-29 | 2023-03-10 | 湖北犇星新能源材料有限公司 | Method for preparing lithium hexafluorophosphate through solid-solid reaction |
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