CN104326482A - Lithium tetrafluoroborate preparation method - Google Patents
Lithium tetrafluoroborate preparation method Download PDFInfo
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- CN104326482A CN104326482A CN201310309457.6A CN201310309457A CN104326482A CN 104326482 A CN104326482 A CN 104326482A CN 201310309457 A CN201310309457 A CN 201310309457A CN 104326482 A CN104326482 A CN 104326482A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/06—Boron halogen compounds
- C01B35/063—Tetrafluoboric acid; Salts thereof
- C01B35/066—Alkali metal tetrafluoborates
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Abstract
The invention discloses a lithium tetrafluoroborate preparation method comprising the following steps: mixing lithium carbonate, lithium hydroxide monohydrate or anhydrous lithium hydroxide and boric acid and boric oxide to obtain lithium metaborate, crushing the lithium metaborate to obtain lithium metaborate powder, and mixing the lithium metaborate powder and ammonium fluoride or ammonium bifluoride for vacuum negative pressure burning reaction to obtain the lithium tetrafluoroborate product. The lithium tetrafluoroborate preparation method uses a solid lithium source and a solid boron source as raw materials for preparation of the lithium tetrafluoroborate, the process has the advantages that raw materials are easily obtained, non-toxic and non-corrosive, product quality is high, no side reaction is produced, and the method is environmentally friendly and high in efficiency, and the like.
Description
Technical field
Patent of the present invention relates to a kind of novel process preparing LiBF4.
Background technology
LiBF4 is mainly used in lithium battery electrolytes and medication chemistry.The preparation of LiBF4 has following several method, and method one is with hydrofluoric acid, lithium hydroxide, boric acid neutralization, after concentrated, crystallization, oven dry, obtains two water LiBF4s, then the LiBF4 that dewatered under vacuum to obtain by two water LiBF4s.Method two in organic medium, carries out complex reaction with boron trifluoride diethyl etherate and lithium fluoride to obtain LiBF4 through steps etc. such as vacuum-dryings again.Adopt in hydrofluoric acid, boric acid in method one and first generate fluoroboric acid, then neutralizing with lithium hydroxide, the production cycle is long, high to equipment requirements, and equipment easily corrodes.Method two is short for reaction time, but boron trifluoride diethyl etherate belongs to inflammable, explosive material, production safety coefficient is little, it could be produced under needing condition of high vacuum degree condition, the LiBF4 containing ether, unreacted raw material and dissolving in the remaining waste liquid of reaction, and not easily recycle, environmental pollution are large.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of LiBF4, to overcome the defect that prior art exists.
Method of the present invention, comprises the steps:
(1) preparation of lithium metaborate powder:
After Quilonum Retard, monohydrate lithium hydroxide or anhydrous lithium hydroxide and boric acid, boron oxide mixing, calcination, temperature of reaction is 1 ~ 250 DEG C, time 1 ~ 24h, lithium metaborate, pulverize and obtain lithium metaborate powder;
Preferred temperature of reaction is 150 ~ 250 DEG C, and the time is 8 ~ 16h.
The material ratio of reaction is (mass ratio):
Li
2CO
3: H
3BO
3= 1：1.68 ～1： 1.75
Li
2CO
3: B
2O
3 = 1：0.94 ～ 1： 0.98
LiOH·H
2O : H
3BO
3= 1：1.49 ～1： 1.54
LiOH·H
2O: B
2O
3 = 1：0.83 ～ 1： 0.86
(2) preparation of LiBF4:
By lithium metaborate powder and Neutral ammonium fluoride or ammonium bifluoride mixing, calcination, temperature of reaction 10 ~ 200 DEG C, time 1 ~ 24h, vacuum tightness pressure negative pressure-0.02 ~-0.098 MPa, after reaction terminates, LiBF4 product;
Preferred temperature of reaction 100 ~ 200 DEG C, the preferred reaction times is 8 ~ 24h, vacuum tightness pressure negative pressure-0.080 ~-0.098MPa;
The mass ratio of lithium metaborate powder and Neutral ammonium fluoride or ammonium bifluoride is:
Lithium metaborate powder: Neutral ammonium fluoride=1:3 ~ 1:3.11
Lithium metaborate powder: ammonium bifluoride=1:2.32 ~ 1:2.4
The present invention prepares LiBF4 with solid lithium source, solid boron source for raw material, and this technique has that raw material is easy to get, advantages of nontoxic raw materials, non-corrosiveness, product quality are high, without advantages such as side reaction generation, environment-friendly high-efficiencies.
Embodiment
The following example only in explanation the present invention, and does not limit the scope of the invention.
Embodiment 1
Quilonum Retard raw material in example is cell-grade, and content is 99.9%, and impurity is mainly as sodium, potassium, calcium, magnesium, sulfate radical, content is 1 ~ 10ppm, boric acid, Neutral ammonium fluoride are analytical pure, and impurity is mainly as sodium, potassium, calcium, magnesium, sulfate radical, and content is 5 ~ 20ppm.
(1), take the analytically pure boric acid of 650g in tetrafluoro beaker, then to add 422g cell-grade purity be the Quilonum Retard of 99.9%, fully mix;
(2), by tetrafluoro beaker be transferred to calcination 12h in the retort furnace of 200 DEG C, obtain white foam solid;
(3), white foam solid is cooled to room temperature after, obtain white powder lithium metaborate after pulverizing, weight is 495.2g, and yield is 99.04%, and quality analysis results is as follows:
(4), the lithium metaborate powder of the 495.2g in (3) is put into the tetrafluoro beaker of 2L, add the analytical pure Neutral ammonium fluoride of 1500g, be transferred in vacuum drying oven after two raw materials are fully mixed.
(5), open vacuum pump, control pressure-0.098 MPa of vacuum drying oven, start to pass into argon gas, the flow velocity of argon gas is 0.5L/min, keeps oven temperature 200 DEG C, reaction times 12h;
(6), in (5) reaction after terminating product LiBF4 solid is transferred to rapidly in glove box and cools and be weighed as 925.3g, yield is 99.12%.
Embodiment 2
Monohydrate lithium hydroxide in example is for being cell-grade, and content is 56.5%, and impurity is mainly as sodium, potassium, calcium, magnesium, sulfate radical, content is 1 ~ 10ppm, boron oxide, ammonium bifluoride are analytical pure, and impurity is sodium, potassium, calcium, magnesium, sulfate radical mainly, and content is 5 ~ 20ppm.
(1), take the battery-stage monohydrate lithium hydroxide of 1000g in tetrafluoro beaker, add 850g analytical pure boron oxide, two kinds of raw materials are fully uniformly mixed;
(2), by the raw material mixed be transferred to calcination 12h in the retort furnace of 200 DEG C, obtain white foam solid, pulverized by this white foam solid and namely obtain lithium metaborate powder, be weighed as 590.1g, yield is 99.54%;
(3) the lithium metaborate powder of the 590g, by (2) planted joins in 2L tetrafluoro beaker, adds the analytical pure ammonium bifluoride of 1360g, is fully stirred by two kinds of raw materials, mixes;
(4), be transferred in baking oven by tetrafluoro beaker, control pressure-0.097 MPa of vacuum drying oven, pass into argon gas, the flow velocity of argon gas is 0.8L/min, keeps oven temperature 200 DEG C, reaction times 18h;
(5), reaction terminate after the LiBF4 solid transfer obtained is cooled to glove box, be weighed as 1346.3g, yield is 99.50%, and quality analysis results is as follows:
Embodiment 3
The Quilonum Retard purity used in example is cell-grade, and content is 99.95%, and impurity is sodium, potassium, calcium, magnesium, sulfate radical mainly, content is 1 ~ 10ppm, boron oxide, Neutral ammonium fluoride are analytical pure, and impurity is sodium, potassium, calcium, magnesium, sulfate radical mainly, and content is 10 ~ 50ppm.
(1), take the analytically pure boron oxide of 370g in beaker, then add the battery-level lithium carbonate that 362g purity is 99.95%, be fully transferred in tetrafluoro beaker after mixing;
(2), be transferred in retort furnace by tetrafluoro beaker, control temperature 200 DEG C, the reaction times is 12h, and pressure is normal pressure, and after reaction terminates, obtain white foam solid, obtain white powdery solids after breaking into pieces, weight is 465.4g;
(3), by the lithium metaborate of the 465g obtained in (2) be transferred in the tetrafluoro beaker of 2L, add the analytical pure Neutral ammonium fluoride of 1400g, fully mix;
(4), be again transferred in vacuum drying oven by tetrafluoro beaker, pass into argon shield, the flow velocity of argon gas is 0.6L/min, controls pressure-0.098 MPa of vacuum drying oven, keeps oven temperature 220 DEG C, reaction times 16h;
(5), after reaction terminates, after breaking into pieces after being cooled to room temperature in the solid transfer obtained to glove box, be weighed as 871.3g, yield is 99.4%.
Embodiment 4
The micro mist Quilonum Retard used in example 4 is cell-grade, and content is 99.5%, boron oxide, ammonium bifluoride be analytical pure impurity mainly as sodium, potassium, calcium, magnesium, sulfate radical, content is 10 ~ 50ppm.
(1), take the battery-level lithium carbonate powder of 400g in 2L tetrafluoro beaker, add 380g boron oxide, stir, mix;
(2), be transferred in retort furnace by tetrafluoro beaker, the temperature controlling retort furnace is 250 DEG C, and the reaction times is 24h, and pressure is normal pressure;
(3), reaction terminate after, product is white foam, is broken into pieces and obtains 535.2g powder; Get 535g lithium metaborate powder again in 2L tetrafluoro beaker, then add the analytical pure Neutral ammonium fluoride of 1600g, stir;
(4), be again transferred in vacuum drying oven by tetrafluoro beaker, pass into argon shield, the flow velocity of argon gas is 0.5L/min, controls pressure-0.098 MPa of vacuum drying oven, keeps oven temperature 200 DEG C, reaction times 15h;
(5), after reaction terminates, after breaking into pieces after being cooled to room temperature in the solid transfer obtained to glove box, be weighed as 988.6g, yield is 98.07%:
Embodiment 5
Quilonum Retard raw material in example is cell-grade, and content is 99.9%, and impurity is mainly as sodium, potassium, calcium, magnesium, sulfate radical, content is 1 ~ 10ppm, boron oxide, Neutral ammonium fluoride are analytical pure, and impurity is mainly as sodium, potassium, calcium, magnesium, sulfate radical, and content is 10 ~ 50ppm.
(1), take the analytically pure boric acid of 1550g in beaker, then to add 925g cell-grade purity be the Quilonum Retard of 99.9%, fully mix;
(2), by the raw material mixed be transferred in tetrafluoro beaker, transfer to calcination 12h in the retort furnace of 200 DEG C, obtain white foam solid, after white foam solid is cooled to room temperature, pulverize and obtain white lithium metaborate powder, weight is 1184.7g;
(3), get the lithium metaborate powder of 1180g in the tetrafluoro beaker of 5L, add the analytically pure Neutral ammonium fluoride of 3600g, two kinds of raw materials are stirred;
(4), be transferred in vacuum drying oven by tetrafluoro beaker, pass into argon shield, the flow velocity of argon gas is 0.5L/min, controls pressure-0.098 MPa of vacuum drying oven, keeps oven temperature 240 DEG C, reaction times 24h;
(5), reaction terminate after, cool in tetrafluoro beaker fast transfer to glove box, be weighed as 2246.5g, yield is 99.51%.
Embodiment 6
In example 6, monohydrate lithium hydroxide is cell-grade, and content is 56.5%, and boric acid, Neutral ammonium fluoride are analytical pure impurity mainly as sodium, potassium, calcium, magnesium, sulfate radical, and content is 10 ~ 50ppm.
(1), take in the monohydrate lithium hydroxide of 2000g cell-grade and the tetrafluoro beaker of 5L, add the analytical pure boric acid of 3000g, after two kinds of raw materials are fully stirred, be transferred in retort furnace and react;
(2), by the raw material mixed be transferred to calcination 12h in the retort furnace of 220 DEG C, obtain white foam solid, after white foam solid is cooled to room temperature, pulverize and obtain white lithium metaborate powder, weight is 2352.1g;
(3), take the lithium metaborate powder of 2350g in the tetrafluoro beaker of 5L, add 7050g Neutral ammonium fluoride, be fully uniformly mixed;
(4), be again transferred in vacuum drying oven by tetrafluoro beaker, pass into argon shield, the flow velocity of argon gas is 0.8L/min, controls pressure-0.098 MPa of vacuum drying oven, keeps oven temperature 250 DEG C, reaction times 18h;
(5), after reaction terminates, after breaking into pieces after being cooled to room temperature in the solid transfer obtained to glove box, be weighed as 4402.3g, yield is 99.41%.
Embodiment 7
In example 7, monohydrate lithium hydroxide is cell-grade, its impurity is sodium, potassium, calcium, magnesium, sulfate radical, chlorine etc. mainly, content is at 10-20ppm, and boron oxide, ammonium bifluoride are analytical pure impurity mainly as sodium, potassium, calcium, magnesium, sulfate radical, and content is 10 ~ 50ppm.
(1), take in the tetrafluoro beaker of 2000g cell-grade lithium hydroxide and 5L, then add 1700g boron oxide, fully mix;
(2), by the raw material mixed be transferred in tetrafluoro beaker, transfer to calcination 16h in the retort furnace of 250 DEG C, obtain white foam solid, after white foam solid is cooled to room temperature, pulverize and obtain white lithium metaborate powder, weight is 2355.8g;
(3), take the lithium metaborate powder of 2355g in beaker, add 5550g ammonium bifluoride, be fully transferred in tetrafluoro beaker after mixing;
(4), be again transferred in vacuum drying oven by tetrafluoro beaker, pass into argon shield, the flow velocity of argon gas is 0.7L/min, controls pressure-0.098 MPa of vacuum drying oven, keeps oven temperature 220 DEG C, reaction times 20h;
(3), after reaction terminates, after breaking into pieces after being cooled to room temperature in the solid transfer obtained to glove box, be weighed as 4415.1g, yield is 99.50%.
Claims (5)
1. prepare the method for LiBF4, it is characterized in that, comprise the steps:
(1) preparation of lithium metaborate powder:
After Quilonum Retard, monohydrate lithium hydroxide or anhydrous lithium hydroxide and boric acid, boron oxide mixing, calcination, lithium metaborate, pulverize and obtain lithium metaborate powder;
(2) preparation of LiBF4:
By lithium metaborate powder and Neutral ammonium fluoride or ammonium bifluoride mixing, calcination, vacuum tightness pressure negative reaction, LiBF4 product.
2. method according to claim 1, is characterized in that, in step (1), temperature of reaction is 1 ~ 250 DEG C, time 1 ~ 24h.
3. method according to claim 1, is characterized in that, in step (1), the material ratio of reaction is (mass ratio):
Li
2CO
3: H
3BO
3= 1：1.68 ～1： 1.75
Li
2CO
3: B
2O
3 = 1：0.94 ～ 1： 0.98
LiOH·H
2O : H
3BO
3= 1：1.49 ～1： 1.54
LiOH·H
2O: B
2O
3 = 1：0.83 ～ 1： 0.86。
4. method according to claim 1, is characterized in that, in step (2), and temperature of reaction 10 ~ 200 DEG C, time 1 ~ 24h, vacuum tightness pressure negative pressure-0.02 ~-0.098 MPa.
5. method according to claim 1, is characterized in that, in step (2), the material ratio of lithium metaborate powder and Neutral ammonium fluoride or ammonium bifluoride is (mass ratio):
Lithium metaborate powder: Neutral ammonium fluoride=1:3 ~ 1:3.11
Lithium metaborate powder: ammonium bifluoride=1:2.32 ~ 1:2.4.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109659608A (en) * | 2018-11-16 | 2019-04-19 | 湖北锂诺新能源科技有限公司 | A kind of preparation method and application of tetrafluoro lithium aluminate |
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|---|---|---|---|---|
| CN101318664A (en) * | 2008-05-09 | 2008-12-10 | 中国科学院青海盐湖研究所 | Method of preparing waterless lithium terafluoroborate |
| CN101696016A (en) * | 2009-09-30 | 2010-04-21 | 河南理工大学 | Hydrothermal synthesis method of alkaline lithium pentaborate |
| CN101863489A (en) * | 2010-06-11 | 2010-10-20 | 中国海洋石油总公司 | Method for preparing anhydrous high-purity lithium tetrafluoroborate |
| CN102030344A (en) * | 2009-09-25 | 2011-04-27 | 上海中锂实业有限公司 | Preparation method of lithium fluoride |
| CN102910638A (en) * | 2012-11-15 | 2013-02-06 | 湖北百杰瑞新材料有限公司 | Preparation method of anhydrous lithium metaborate |
-
2013
- 2013-07-23 CN CN201310309457.6A patent/CN104326482B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318664A (en) * | 2008-05-09 | 2008-12-10 | 中国科学院青海盐湖研究所 | Method of preparing waterless lithium terafluoroborate |
| CN102030344A (en) * | 2009-09-25 | 2011-04-27 | 上海中锂实业有限公司 | Preparation method of lithium fluoride |
| CN101696016A (en) * | 2009-09-30 | 2010-04-21 | 河南理工大学 | Hydrothermal synthesis method of alkaline lithium pentaborate |
| CN101863489A (en) * | 2010-06-11 | 2010-10-20 | 中国海洋石油总公司 | Method for preparing anhydrous high-purity lithium tetrafluoroborate |
| CN102910638A (en) * | 2012-11-15 | 2013-02-06 | 湖北百杰瑞新材料有限公司 | Preparation method of anhydrous lithium metaborate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109659608A (en) * | 2018-11-16 | 2019-04-19 | 湖北锂诺新能源科技有限公司 | A kind of preparation method and application of tetrafluoro lithium aluminate |
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Address after: 201417 Shanghai city Fengxian District Zhelin town science Road No. 1158 Applicant after: Shanghai China Lithium Industrial Co., Ltd. Address before: Fengxian District Zhelin Town East Zhongxing Road 201424 Shanghai City No. 8 Applicant before: Shanghai China Lithium Industrial Co., Ltd. |
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