CN109678898A - A kind of preparation method of difluorine oxalic acid boracic acid lithium - Google Patents
A kind of preparation method of difluorine oxalic acid boracic acid lithium Download PDFInfo
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- CN109678898A CN109678898A CN201910113353.5A CN201910113353A CN109678898A CN 109678898 A CN109678898 A CN 109678898A CN 201910113353 A CN201910113353 A CN 201910113353A CN 109678898 A CN109678898 A CN 109678898A
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- oxalic acid
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- difluorine oxalic
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 195
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 63
- 235000006408 oxalic acid Nutrition 0.000 title claims abstract description 51
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title claims abstract description 50
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229960002645 boric acid Drugs 0.000 title claims abstract description 50
- 235000010338 boric acid Nutrition 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims abstract description 33
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 239000000376 reactant Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 11
- 238000009423 ventilation Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 230000003519 ventilatory effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- -1 lithium tetrafluoroborate Chemical compound 0.000 description 8
- 229910015900 BF3 Inorganic materials 0.000 description 7
- OUGOOSHGPCBMLD-UHFFFAOYSA-N [B].FOC(C(=O)OF)=O Chemical compound [B].FOC(C(=O)OF)=O OUGOOSHGPCBMLD-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910013098 LiBF2 Inorganic materials 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- MUETXHPIRUFIOK-UHFFFAOYSA-N B([O-])([O-])[O-].[K+].C(C(=O)O)(=O)O.[K+].[K+] Chemical compound B([O-])([O-])[O-].[K+].C(C(=O)O)(=O)O.[K+].[K+] MUETXHPIRUFIOK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RTZKMGZSJBRJFI-UHFFFAOYSA-N boric acid;lithium Chemical compound [Li].OB(O)O RTZKMGZSJBRJFI-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 description 1
- WDGRWFSBSJISCI-UHFFFAOYSA-N tripotassium difluoro oxalate borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-].FOC(=O)C(=O)OF WDGRWFSBSJISCI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The present invention provides a kind of preparation method of difluorine oxalic acid boracic acid lithium, include the following steps: that 1) it is 35-45 DEG C that LiBF4 is dissolved to the temperature for adjusting solution in organic solvent；2) anhydrous oxalic acid is added in Xiang Suoshu solution, the temperature for controlling solution is 35-45 DEG C；3) it is slowly introducing boron trichloride gas in Xiang Suoshu solution, is reacted, obtains reactant；4) reactant is filtered, separates solid impurity, obtain difluorine oxalic acid boracic acid lithium solution；5) it crystallizes the difluorine oxalic acid boracic acid lithium solution to obtain difluorine oxalic acid boracic acid lithium crystal, is dried to obtain finished product.Preparation method industrialized production of the present invention is simple, and without wastage of material, raw material comprehensive utilization ratio is high；By-product is few, and product purity is high, does not need to purify again and can reach LITHIUM BATTERY；There is no the generation of waste water in production process, preparation method is very environmentally friendly.
Description
Technical field
The invention belongs to chemical products preparation technical field more particularly to a kind of preparation methods of difluorine oxalic acid boracic acid lithium.
Background technique
Difluorine oxalic acid boracic acid lithium, novel lithium battery electrolyte lithium salt, chemical formula LiBF2(CO2)2.English name:
LiDFOB, CAS:409071-16-5.It is mainly used as lithium-ion battery electrolytes additive, can be used in lithium battery electrolytes making
For film for additive, there is good thermal stability and electrochemical stability, to adjust the high current of lithium ion secondary battery
With high rate charge-discharge ability, have become the important composition material of lithium-ion battery electrolytes.
At present for the preparation of difluorine oxalic acid boracic acid lithium, such as: boron-containing compound and potassium oxalate carry out reaction synthesis difluoro
Then oxalic acid potassium borate will carry out neutralization reaction with LiOH after the acidified processing of difluoro oxalate potassium borate, obtain difluoro oxalate
Lithium borate crude product；Or it is prepared by a certain percentage using lithium oxalate and boron trifluoride ether.Above method some is new because introducing
Metal impurities, the problems such as more white precipitate can be generated after some preparations and cause purification difficult.
Summary of the invention
In view of the above-mentioned drawbacks in the prior art, the main purpose of the present invention is to provide a kind of difluorine oxalic acid boracic acid lithiums
Preparation method reacts easily operated, reaction product purity is high, no exclusive impurity of lithium-ion battery electrolytes.
In order to achieve the above object, the present invention adopts the following technical scheme: a kind of preparation method of difluorine oxalic acid boracic acid lithium,
Include the following steps:
1) temperature in organic solvent by LiBF4 dissolution, adjusting solution is 35-45 DEG C；
2) anhydrous oxalic acid is added in Xiang Suoshu solution, the temperature for controlling solution is 35-45 DEG C；
3) it is slowly introducing boron trichloride gas in Xiang Suoshu solution, is reacted, obtains reactant；
4) reactant is filtered, separates solid impurity, obtain difluorine oxalic acid boracic acid lithium solution；
5) it crystallizes the difluorine oxalic acid boracic acid lithium solution to obtain difluorine oxalic acid boracic acid lithium crystal, is dried to obtain finished product.
As a further preference, in step 1), the organic solvent is dimethyl carbonate.
As a further preference, in step 1), the concentration of LiBF4 is 20-25%(Wt% in the solution).
As a further preference, in step 2, the additional amount of the anhydrous oxalic acid is the molar ratio with LiBF4
For 0.98:1.
As a further preference, in step 3), for the gas that is passed through to solvent bottom, when ventilatory response, is kept stirring shape
State, the speed of agitator are 20-40r/min.
As a further preference, in step 3), the speed for being passed through gas is 50L-100L/min, and ventilation total amount is pressed
The molar ratio of itself and LiBF4 is 1:1, stirring the reaction was continued 1-2h after the completion of ventilation.
As a further preference, in step 4), the filtering uses material for the accurate filter of PP, PTFE, described
Accurate filter aperture is 0.1~1um.
As a further preference, in step 4), the accurate filter aperture is 0. 1um.
The beneficial effects of the present invention are:
Raw material LiBF4 batch conversion ratio of the present invention is more than 90%, and remainder enters the life of next batch with solvent
It produces, is recycled, the more theoretical usage amount of anhydrous oxalic acid is slightly lower, therefore reaction completely, therefore does not have wastage of material；Use trichlorine
Change boron as auxiliary agent to participate in reacting, ultimately generates boron trifluoride (BF3) and hydrogen chloride (HCL) gas evolution reaction solution, so that
Reaction process does not introduce other impurity substances, and product purity is high, does not need to purify again and can reach LITHIUM BATTERY, industrial application
Simply；The organic solvent of production and application can be recycled, and not be related to water, therefore not have the generation of waste water in production process, former
Expect that anhydrous oxalic acid and LiBF4 are high-purity grade of raw material, passes through rarely solid after accurate filter filtering after the reaction was completed
Waste, therefore preparation method of the invention is very environmentally friendly.
Detailed description of the invention
Fig. 1 is the process flow chart of the preparation method of difluorine oxalic acid boracic acid lithium of the embodiment of the present invention.
Specific embodiment
The embodiment of the present invention solves existing difluoro oxalate boron by providing a kind of preparation method of difluorine oxalic acid boracic acid lithium
The defect of sour lithium preparation method hardly possible.
To solve the above-mentioned problems, the main thought of the embodiment of the present invention is:
The preparation method of difluorine oxalic acid boracic acid lithium of the embodiment of the present invention, includes the following steps:
1) temperature in organic solvent by LiBF4 dissolution, adjusting solution is 35-45 DEG C；
2) anhydrous oxalic acid is added in Xiang Suoshu solution, the temperature for controlling solution is 35-45 DEG C；
3) it is slowly introducing boron trichloride gas in Xiang Suoshu solution, is reacted, obtains reactant；
4) reactant is filtered, separates solid impurity, obtain difluorine oxalic acid boracic acid lithium solution；
5) it crystallizes the difluorine oxalic acid boracic acid lithium solution to obtain difluorine oxalic acid boracic acid lithium crystal, is dried to obtain finished product.
In order to better understand the above technical scheme, being done below by specific embodiment to technical scheme detailed
Explanation, it should be understood that the specific features in the embodiment of the present application and embodiment be to technical scheme specifically
It is bright, rather than the restriction to technical scheme, in the absence of conflict, the skill in the embodiment of the present application and embodiment
Art feature can be combined with each other.It should be understood that term "and/or" used herein above includes listed by one of them or more
Any and all combinations of associated item out.
Above-mentioned each raw material or agent formulations can be bought by commercially available channel or be prepared by existing method.
Above-mentioned steps 1) in, the temperature for adjusting the solution is 35-45 DEG C；It is insufficient to cross low reaction, it is excessively high to be easy
It induces and generates di-oxalate lithium borate (LiB (C2O4)2) side reaction.
Above-mentioned steps 2) in, the process that anhydrous oxalic acid is added can generate heat of solution, 2-3 DEG C can be risen under the concentration operating condition,
The temperature of the solution is adjusted to 35-45 DEG C of optimal reaction temperature.
Above-mentioned steps 2) in solvent be dimethyl carbonate (DMC), experiment show the nonaqueous solvents to the yield of product
It influences little.
The concentration of LiBF4 is 20-25%(Wt% in above-mentioned solution).Lithium tetrafluoroborate solution is adjusted to suitably instead
Concentration is answered, solution temperature is excessively high when being unlikely to excessive concentration and causing to react, and is also unlikely to the too low product for leading to reaction of concentration
Difluorine oxalic acid boracic acid lithium single batch yield is too low.In addition, the additional amount of anhydrous oxalic acid is by the molar ratio of itself and LiBF4
0.98:1 is added, and reacts anhydrous oxalic acid sufficiently, the micro- excess of LiBF4, and final excessive LiBF4 is with solvent
It is recycled into next batch and participates in reaction.
Above-mentioned steps 3) in, boron trichloride gas is passed through solvent bottom, and ventilatory response Process liquor will be stirred continuously, stirring
Speed 20-40r/min with ordered mixing and preferably controls reaction process.When above-mentioned stirring, ultrasonic power or auxiliary can be used
Help mixing plant, such as magnetic stirring apparatus.
Above-mentioned steps 3) in, the speed for being passed through gas is 50L-100L/min, controls optimum response speed, has ventilated
At rear stirring the reaction was continued 1-2h.
Total amount of ventilating is 1:1 by the molar ratio of itself and LiBF4, and slightly excessive compared with anhydrous oxalic acid, excessive portion finally escapes
Solvent enters vent gas treatment out.
Above-mentioned steps 4) in reactant filtered into away the impurity such as insoluble matter by accurate filter, obtain difluoro oxalate boron
Sour lithium solution.
Above-mentioned steps 5) in, difluorine oxalic acid boracic acid lithium solution condensing crystallizing is obtained into difluorine oxalic acid boracic acid lithium crystal.
Above-mentioned filtering uses material for the accurate filter of PP, PTFE, and the accurate filter aperture is 0.1~1um, excellent
It is selected as 0. 1um, filters out the impurity in target product, the smaller filter effect of number is better.
Use metal chloride reaction can also be made to carry out to target product as catalyst under experimental conditions, and produces
Metal fluoride precipitating, but metal impurities can be introduced target product by result, and the present invention screens boron trifluoride as auxiliary agent, very well
Avoid the introducing of metal impurities, and generate gas phase BF3Reaction solution, the B in nonaqueous solvents are escaped with HCL3+With metal from
Son is reduced compared to polarity, it is suppressed that the generation of side reaction di-oxalate lithium borate.Experiment is repeated several times and shows raw material LiBF4
Batch conversion ratio is more than 90%, and non-reacted parts are recycled with solvent, and controllable anhydrous oxalic acid reacts completely, therefore does not have raw material
Waste；The organic solvent of production and application can be recycled, and not have the generation of waste water, therefore preparation side of the invention in production process
Method is very environmentally friendly.
It is for a more detailed description to the application by the following examples.These embodiments are only to the best embodiment party of the application
The description of formula does not have any limitation to scope of the present application.
Embodiment 1
Fig. 1 is the process flow chart of the preparation method of difluorine oxalic acid boracic acid lithium of the embodiment of the present invention；The present embodiment difluoro oxalate boron
The preparation method of sour lithium, includes the following steps:
Configuration lithium tetrafluoroborate solution: it takes 500Kg dimethyl carbonate liquid to be added in reactor, is slowly added to 120Kg tetrafluoro boron
Sour lithium stirs 40min after the completion, and adjusts solution temperature to 40 DEG C.
Anhydrous oxalic acid is added: taking 112.6Kg anhydrous oxalic acid to be slowly added in lithium tetrafluoroborate solution, stirs after the completion
30min, and solution temperature is adjusted to 40 DEG C.
98.7Kg boron triflouride gas is passed through in previous solu by the speed of 100L/min, is during which kept stirring, is ventilated
Process needs about 1.5-2.5 hours altogether, continues to be stirred solution 2 hours after the completion of ventilation, be reacted.
Difluorine oxalic acid boracic acid lithium solution is obtained after the reaction was completed, and difluorine oxalic acid boracic acid lithium solution passes through accurate filter mistake
Filter, the accurate filter aperture are 0.5um, take filtrate to enter crystallizer stirring evaporative crystallization, after the completion by difluoro oxalate boron
Sour lithium product sampling analysis, drying effect reach requirement.Total 165.4Kg, (180.2 Kg of theory) yield 91.8%.
Difluorine oxalic acid boracic acid lithium product purity analysis result see the table below 1:
Table 1
| Serial number | Project | Unit | Specification | Remarks |
| 1 | LiBF2(CO2)2 | wt.% | 99.12 | |
| 2 | LiBF4 | wt.% | 0.11 | |
| 3 | DMC | wt.% | 0.77 | |
| 4 | Free acid (as HF) | wt.ppm | 98 | |
| 5 | Moisture | wt.ppm | 6 | |
| 6 | Metal ion | wt.ppm | / |
Embodiment 2
The preparation method of the present embodiment difluorine oxalic acid boracic acid lithium, includes the following steps:
Configuration lithium tetrafluoroborate solution: it takes 100Kg dimethyl carbonate liquid to be added in reactor, is slowly added to 26Kg tetrafluoro boric acid
Lithium stirs 30min after the completion, and adjusts solution temperature to 35 DEG C.
Anhydrous oxalic acid is added: taking 24.4Kg anhydrous oxalic acid to be slowly added in lithium tetrafluoroborate solution, stirs after the completion
30min, and solution temperature is adjusted to 35 DEG C.
21.4Kg boron triflouride gas is passed through in previous solu by the speed of 50L/min, during which keeps stirring, ventilated
Journey needs about 1-2 hours altogether, continues to be stirred solution 1 hour after the completion of ventilation, be reacted.
Difluorine oxalic acid boracic acid lithium solution is obtained after the reaction was completed, and difluorine oxalic acid boracic acid lithium solution passes through accurate filter mistake
Filter, the accurate filter aperture are 0.1um, take filtrate to enter crystallizer stirring evaporative crystallization, after the completion by difluoro oxalate boron
Sour lithium product sampling analysis, drying effect reach requirement.Total 35.9Kg, (39.0 Kg of theory) yield 92.1%.
Difluorine oxalic acid boracic acid lithium product purity analysis result see the table below 2:
Table 2
| Serial number | Project | Unit | Specification | Remarks |
| 1 | LiBF2(CO2)2 | wt.% | 99.82 | |
| 2 | LiBF4 | wt.% | 0.02 | |
| 3 | DMC | wt.% | 0.16 | |
| 4 | Free acid (as HF) | wt.ppm | 152 | |
| 5 | Moisture | wt.ppm | 16 | |
| 6 | Metal ion | wt.ppm | / |
Embodiment 3
The preparation method of the present embodiment difluorine oxalic acid boracic acid lithium, includes the following steps:
Configuration lithium tetrafluoroborate solution: it takes 800Kg dimethyl carbonate liquid to be added in reactor, is slowly added to 230Kg tetrafluoro boron
Sour lithium stirs 60min after the completion, and adjusts solution temperature to 45 DEG C.
Anhydrous oxalic acid is added: taking 215.8Kg anhydrous oxalic acid to be slowly added in lithium tetrafluoroborate solution, stirs after the completion
30min, and solution temperature is adjusted to 40 DEG C.
189.2Kg boron triflouride gas is passed through in previous solu by the speed of 100L/min, is during which kept stirring, is ventilated
Process needs about 2-3 hours altogether, continues to be stirred solution 1.5 hours after the completion of ventilation, be reacted.
Difluorine oxalic acid boracic acid lithium solution is obtained after the reaction was completed, and difluorine oxalic acid boracic acid lithium solution passes through accurate filter mistake
Filter, the accurate filter aperture are 0.1um, take filtrate to enter crystallizer stirring evaporative crystallization, after the completion by difluoro oxalate boron
Sour lithium product sampling analysis, drying effect reach requirement.Total 321.1Kg, (345.3 Kg of theory) yield 93.0%.
Difluorine oxalic acid boracic acid lithium product purity analysis result see the table below 3:
Table 3
| Serial number | Project | Unit | Specification | Remarks |
| 1 | LiBF2(CO2)2 | wt.% | 99.66 | |
| 2 | LiBF4 | wt.% | 0.10 | |
| 3 | DMC | wt.% | 0.24 | |
| 4 | Free acid (as HF) | wt.ppm | 234 | |
| 5 | Moisture | wt.ppm | 29 | |
| 6 | Metal ion | wt.ppm | / |
Embodiment 4
The preparation method of the present embodiment difluorine oxalic acid boracic acid lithium, includes the following steps:
Configuration lithium tetrafluoroborate solution: it takes 360Kg dimethyl carbonate liquid to be added in reactor, is slowly added to 100Kg tetrafluoro boron
Sour lithium stirs 30min after the completion, and adjusts solution temperature to 40 DEG C.
Anhydrous oxalic acid is added: taking 93.8Kg anhydrous oxalic acid to be slowly added in lithium tetrafluoroborate solution, stirs after the completion
30min, and solution temperature is adjusted to 40 DEG C.
82.3Kg boron triflouride gas is passed through in previous solu by the speed of 60L/min, during which keeps stirring, ventilated
Journey needs about 1.5-2.5 hours altogether, continues to be stirred solution 1 hour after the completion of ventilation, be reacted.
Difluorine oxalic acid boracic acid lithium solution is obtained after the reaction was completed, and difluorine oxalic acid boracic acid lithium solution passes through accurate filter mistake
Filter, the accurate filter aperture are 0.5um, take filtrate to enter crystallizer stirring evaporative crystallization, after the completion by difluoro oxalate boron
Sour lithium product sampling analysis, drying effect reach requirement.Total 131.6Kg, (143.7 Kg of theory) yield 91.6%.
Difluorine oxalic acid boracic acid lithium product purity analysis result see the table below 4:
Table 4
| Serial number | Project | Unit | Specification | Remarks |
| 1 | LiBF2(CO2)2 | wt.% | 99.71 | |
| 2 | LiBF4 | wt.% | 0.18 | |
| 3 | DMC | wt.% | 0.11 | |
| 4 | Free acid (as HF) | wt.ppm | 282 | |
| 5 | Moisture | wt.ppm | 32 | |
| 6 | Metal ion | wt.ppm | / |
Technical solution in above-mentioned the embodiment of the present application, at least have the following technical effects or advantages:
Raw material LiBF4 batch high conversion rate of the present invention, non-reacted parts enter the production of next batch with solvent,
It is recycled, the more theoretical usage amount of anhydrous oxalic acid is slightly lower, therefore reaction completely, therefore does not have wastage of material；Made using boron chloride
It participates in reacting for auxiliary agent, ultimately generates boron trifluoride (BF3) and hydrogen chloride (HCL) gas evolution reaction solution, so that reacting
Journey does not introduce other impurity substances, and product purity is high, and guiding target reaction, stable reaction are easy to control well；Production makes
Organic solvent can be recycled, and not be related to water, therefore not have the generation of waste water in production process, Materials Absolute oxalic acid and
LiBF4 is high-purity grade of raw material, rarely solid waste, therefore sheet after being filtered after the reaction was completed by accurate filter
The preparation method of invention is very environmentally friendly.
Although preferred embodiments of the present invention have been described, it is created once a person skilled in the art knows basic
Property concept, then additional changes and modifications may be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as
It selects embodiment and falls into all change and modification of the scope of the invention.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (8)
1. a kind of preparation method of difluorine oxalic acid boracic acid lithium, characterized by the following steps:
1) temperature in organic solvent by LiBF4 dissolution, adjusting solution is 35-45 DEG C；
2) anhydrous oxalic acid is added in Xiang Suoshu solution, the temperature for controlling solution is 35-45 DEG C；
3) it is slowly introducing boron trichloride gas in Xiang Suoshu solution, is reacted, obtains reactant；
4) reactant is filtered, separates solid impurity, obtain difluorine oxalic acid boracic acid lithium solution；
5) it crystallizes the difluorine oxalic acid boracic acid lithium solution to obtain difluorine oxalic acid boracic acid lithium crystal, is dried to obtain finished product.
2. the preparation method of difluorine oxalic acid boracic acid lithium according to claim 1, it is characterised in that: described to have in step 1)
Solvent is dimethyl carbonate.
3. the preparation method of difluorine oxalic acid boracic acid lithium according to claim 1, it is characterised in that: described molten in step 1)
The concentration of LiBF4 is 20-25%(Wt% in liquid).
4. the preparation method of difluorine oxalic acid boracic acid lithium according to claim 1, it is characterised in that: in step 2, the nothing
The additional amount of water plant acid is that the molar ratio of itself and LiBF4 is 0.98:1.
5. the preparation method of difluorine oxalic acid boracic acid lithium according to claim 1, it is characterised in that: described logical in step 3)
Enter gas to solvent bottom, when ventilatory response is kept stirring state, and the speed of agitator is 20-40r/min.
6. the preparation method of difluorine oxalic acid boracic acid lithium according to claim 1, it is characterised in that: described logical in step 3)
The speed for entering gas is 50L-100L/min, and ventilation total amount is 1:1 by the molar ratio of itself and LiBF4, is stirred after the completion of ventilation
The 1-2h that mixes that the reaction was continued.
7. the preparation method of difluorine oxalic acid boracic acid lithium according to claim 1, it is characterised in that: in step 4), the mistake
Filter uses material for the accurate filter of PP, PTFE, and the accurate filter aperture is 0.1~1um.
8. the preparation method of difluorine oxalic acid boracic acid lithium according to claim 7, it is characterised in that: in step 4), the essence
Close filter pore size is 0. 1um.
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