CN101723413A - Method for preparing lithium fluoride - Google Patents
Method for preparing lithium fluoride Download PDFInfo
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- CN101723413A CN101723413A CN200910221557A CN200910221557A CN101723413A CN 101723413 A CN101723413 A CN 101723413A CN 200910221557 A CN200910221557 A CN 200910221557A CN 200910221557 A CN200910221557 A CN 200910221557A CN 101723413 A CN101723413 A CN 101723413A
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Abstract
The invention relates to a method for preparing lithium fluoride, which is characterized by comprising the following steps of: mixing high-purity lithium carbonate with pure water, and introducing carbon dioxide gas to carry out the carburization reaction for obtaining a lithium bicarbonate solution; precisely filtering the lithium bicarbonate solution; introducing hydrofluoric acid gas into the lithium bicarbonate solution, stirring to carry out the neutralization reaction, and controlling the pH value to be 0.5-3 to prepare lithium fluoride slurry; centrifugally separating the lithium fluoride slurry to separate solid from liquid of the lithium fluoride slurry; and drying the separated solid lithium fluoride to obtain a finished product. The method of the invention has the advantage of simple technology; the prepared lithium fluoride has the advantages of high purity, good liquidity, no alkaline impurities and neutral state; and the product can achieve the lithium fluoride grade of battery levels.
Description
Technical field
The invention belongs to Chemicals production method technical field, be specifically related to a kind of preparation method of lithium fluoride, the preparation method who particularly produces battery-grade lithium fluoride.
Background technology
Expansion along with the lithium fluoride Application Areas, demand to lithium fluoride also rises increasing, also more and more higher to its specification of quality, the lithium fluoride that for example is used for industries such as lithium cell, stupalith, opticglass requires purity very high, and the method for existing production lithium fluoride is a lot, all comes with some shortcomings, the purity that the lithium fluoride of making has does not reach requirement, have to contain alkaline impurities defeated higher, what have is mobile bad, is difficult to satisfy some product innovations and prepares the raw-material requirement of lithium fluoride.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method of lithium fluoride, and it is simple that this method has technology, lithium fluoride purity height, the good fluidity of making, is advantage neutral, that product can reach battery-grade lithium fluoride.
The technical scheme that addresses the above problem is that the inventive method comprises following content:
(1), pure Lithium Carbonate is mixed with pure water, feed carbon dioxide, carry out carburizing reagent, obtain lithia water;
(2), lithia water is carried out secondary filter;
(3), feed hydrofluoric acid gas in the lithia water after filtering and stir and carry out neutralization reaction, last PH is controlled to be 0.5-3, makes the lithium fluoride slip;
(4), make lithium fluoride slip solid-liquid separation by centrifugation;
(5), with isolated solid-state lithium fluoride vacuum drying.
(6) sieve packing.
Preferably, when carrying out carburizing reagent pure Lithium Carbonate being mixed with pure water, the quality of pure Lithium Carbonate accounts for the 2-5% of pure Lithium Carbonate and pure water mixed solution total mass.
Preferably, when carrying out neutralization reaction, controlling last pH value is 1-1.5.
The final pH value of neutralization reaction is crossed conference and is caused may containing alkaline impurities in the product, pH value is too small can to cause the acid lithium fluoride to generate again and the water ratio when influencing product separation, so more suitable in the evidence pH value is controlled at the scope of 0.5-3, pH value is that 1-1.5 is a preferred version.
It is simple that the inventive method has technology, the lithium fluoride purity height of making, good fluidity, be neutral, product can reach the advantage of battery-grade lithium fluoride, wherein with lithium bicarbonate and gaseous hydrogen fluoride reaction, consequently can obtain the bigger crystal lithium fluoride of granularity, good fluidity, thereby reinforced when helping being the synthetic lithium hexafluoro phosphate of raw material with it, the present invention underway and when reaction, can guarantee that by the control pH value lithium fluoride product that obtains is the neutral products of alkali-free impurity, promptly do not contain unreacted carbonate or hydroxide radical, thereby can avoid when production cell-grade lithium hexafluoro phosphate, influencing quality product because of containing moisture.
Description of drawings
Fig. 1, the embodiment of the invention 1 process flow sheet
Embodiment
Embodiment 1
The reaction principle that this example is produced lithium fluoride is:
Li
2CO
3+H
2O+CO
2＝＝2LiHCO
3(P
CO2＝0.40～0.45MPa)
LiHCO
3+HF＝LiF↓+CO
2↑+H
2O
Main production process:
One, carburizing reagent
Add the 2.5m3 pure water in the carbonization still, the pure Lithium Carbonate that drops into 75kg again covers hand hole completely.Start and stir, open recirculated cooling water, slowly open the carbon dioxide control valve again, carbonization still internal pressure is risen to the 0.4MPa reaction, and continue to keep this pressure 3 hours, obtain lithia water.
The specification of above-mentioned used main raw material is
1, pure water specification of quality (ppm)
2, pure Lithium Carbonate specification of quality (ppm)
3, carbonic acid gas: technical grade, content is not less than 99.9%.
Two, filter:
After the carburizing reagent fully, the solution that carbonization is good is through the titanium rod strainer secondary filter of 1 μ m, and filtrate is pressed in the dosing vessel.
Three, neutralization reaction
Startup is opened recirculated cooling water to the stirring of dosing vessel intracellular bicarbonate lithium solution, opens the hydrofluoric acid valve again, feeds hydrofluoric acid gas and evenly carries out neutralization reaction, and last pH value is controlled at 1, makes the lithium fluoride slip;
The temperature of neutralization reaction is controlled at 40 ℃.
Four, centrifugation
1, open the dosing vessel bottom valve, the lithium fluoride slip is slowly put into whizzer, first low-speed running runs up again, and the liquid-solid separation in the feed liquid is clean;
Centrifugation will make lithium fluoride thoroughly separate with mother liquor, makes mother liquor residual in the product (also being attached liquid) few more good more.Because: the most impurity enriched of the first is in mother liquor, and mother liquor in the lithium fluoride (attached liquid) is few more, and quality product is good more; It two is the just easy more oven dry of the few more lithium fluoride product of attached liquid.
Centrifugation will guarantee that water dumping speed is fast, and this example adopts steel lining fluorine plastics whizzer because material is the single crystal particle shape, fine separation, centrifuge speed be 0-1200 rev/min adjustable, general 500 rev/mins of chargings, 1200 rev/mins of normal separation.The requirement cloth is even, the centrifuge speed height, and whizzer can produce high vibration when cloth was inhomogeneous, and rotating speed naturally can be slow, and material does not just get rid of and does; Whizzer itself go to work braving one's illness or belt loose, also can make rotating speed slack-off, cause material not get rid of and do.
2, then with pure water to isolated solid-state lithium fluoride drip washing 4～5 minutes, when the pH value of water outlet reaches 6～7, be transferred to again and run up, centrifugation to the water outlet globule does not become line to drip, and shuts down discharging.
Five, vacuum-drying
The solid material that centrifugation is gone out drops in the dryer, covers completely, connects good and connects vacuum, convinces deep fat by patient analysis and heats up 2 hours, closes thermal oil, take out 2 hours vacuum again after, close vacuum, and discharging is in feed bin.The feed bin chuck leads to water coolant, and material is cooled off.
Owing to adopted vacuum-drying, so the thermal medium more than 80 degrees centigrade is just passable.This example adopts 200 degrees centigrade thermal oil, and per tour can go out a batch of material like this.
Dry is exactly by the mode of heating heat to be passed to wet stock to remove the moisture in the solid materials, to guarantee that moisture is lower than 0.03% in the product.
Moisture contained in the lithium fluoride is attached water, when material is subjected to heated drying, at first is the attached water gasification on material surface, and the water that after then is material inside is to surface diffusion and gasification.Therefore, the thermal oil 2 hours time of feeding just can reach requirement.
Six, the packing of sieving
Dried product may still have blocky material, therefore need sieve processing to it, and this example is to sieve with reciprocating sieve (160 eye mesh screen), obtains evengranular lithium fluoride product after sieving.Package with double-deck high density polyethylene(HDPE) bag, be inserted in the fiber can, and got sample, tighten.Sample send the laboratory check, after the examination and test of products is qualified, seals again.
Product with method for preparing
Title: battery-grade lithium fluoride, chemical formula: LiF, molecular weight 26
Proterties: 848 ℃ of fusing points, 1676 ℃ of boiling points, relative density 2.653.Be the non-moisture absorption of a kind of white cube crystalline powder, be slightly soluble in water, in water, do not form hydrate, be insoluble to hydrochloric acid, be soluble in nitric acid and sulfuric acid, be insoluble in pure and mild other organic solvents.
The quality standard that product reaches:
End-use: be mainly used in the production of lithium cell, stupalith, and spectrometer and the prismatical manufacturing of x-ray monochromator.
The packing of product and storing:
In tighten with two hdpe layer bags, the external application fiber can cements, and preserves in shady and cool dry and locates.
Embodiment 2
Main production process:
One, carburizing reagent
In the carbonization still, add 2m
3Pure water, the pure Lithium Carbonate that drops into 100kg again covers hand hole completely.Start and stir, open recirculated cooling water, slowly open the carbon dioxide control valve again, carbonization still internal pressure is risen to the 0.45MPa reaction, and continue to keep this pressure 2.5 hours, obtain lithia water.
The purity of above-mentioned used main raw material pure water, pure Lithium Carbonate and carbonic acid gas raw material is all greater than 99.9%
Two, filter:
After the carburizing reagent fully, the solution that carbonization is good filters through the sintered ceramic accurate filter of 5 μ m, and filtrate is pressed in the dosing vessel.
Three, neutralization reaction:
Startup is opened recirculated cooling water to the stirring of dosing vessel intracellular bicarbonate lithium solution, opens the hydrofluoric acid valve again, feeds hydrofluoric acid gas and evenly carries out neutralization reaction, and temperature of reaction is controlled at 50 ℃, and last pH value is controlled at 1.5, makes the lithium fluoride slip;
Four, centrifugation
1, open the dosing vessel bottom valve, the lithium fluoride slip is slowly put into whizzer, first low-speed running runs up again, and the liquid-solid separation in the feed liquid is clean;
2, with pure water isolated solid-state lithium fluoride is carried out running up after drip washing, the drip washing then, drip washing again, run up, reach 6～7 until the pH value of water outlet, back discharging at last runs up.
Five, vacuum-drying
The solid material that centrifugation is gone out drops in the dryer, covers completely, connects thermal oil, carries out vacuum-drying, removes the moisture in the solid materials.
Six, the packing of sieving
This example is to sieve with reciprocating sieve (160 eye mesh screen), obtains evengranular lithium fluoride product after sieving.Package with double-deck high density polyethylene(HDPE) bag, be inserted in the fiber can, and got sample, tighten.Sample send the laboratory check, after the examination and test of products is qualified, seals again.The product that this example is produced is a lenticular, and is neutral, and moisture is less than 0.03%.
Be two preferred embodiments above.
Embodiment 3-5
| Embodiment 3 | Embodiment 2 | Embodiment 3 | |
| The carburizing reagent pure Lithium Carbonate quality that feeds intake accounts for the per-cent of pure Lithium Carbonate and pure water quality sum total | ??2％ | ??3.5％ | ??4.2％ |
| The pressure of carburizing reagent | ??0.35MPa | ??0.45MPa | ??0.5MPa |
| Carburizing reagent clamping time | 2 hours | 2.5 hour | 3 hours |
| The neutralization reaction controlled temperature | ??20℃ | ??30℃ | ??60℃ |
| The pH value that neutralization reaction is last | ??0.5 | ??2 | ??3 |
The lithium fluoride product that the foregoing description is produced all can reach the requirement of the object of the invention.
The above; it only is preferred embodiment of the present invention; be not that the present invention is done any pro forma restriction, every foundation technical spirit of the present invention all still belongs to the protection domain of technical solution of the present invention to any simple modification, equivalent variations and modification that above embodiment did.
Claims (9)
1. the preparation method of a lithium fluoride is characterized in that, comprises following content:
(1), pure Lithium Carbonate is mixed with pure water, feed carbon dioxide, carry out carburizing reagent, obtain lithia water;
(2), lithia water is carried out secondary filter;
(3), feed hydrofluoric acid gas in the lithia water after filtering and stir and carry out neutralization reaction, last pH value is controlled at 0.5-3, makes the lithium fluoride slip;
(4), make lithium fluoride slip solid-liquid separation by centrifugation;
(5), with isolated solid-state lithium fluoride oven dry, go out finished product.
2. the preparation method of kind of lithium fluoride according to claim 1 is characterized in that, when carrying out neutralization reaction, controls last pH value and is preferably 1-1.5.
3. the preparation method of kind of lithium fluoride according to claim 1 is characterized in that, the temperature of carrying out neutralization reaction is controlled at 20-60 ℃.
4. the preparation method of kind of lithium fluoride according to claim 3 is characterized in that, the temperature of carrying out neutralization reaction preferably is controlled at 40-50 ℃.
5. the preparation method of kind of lithium fluoride according to claim 1 is characterized in that, when carrying out carburizing reagent pure Lithium Carbonate being mixed with pure water, the quality of pure Lithium Carbonate accounts for the 2-5% of pure Lithium Carbonate and pure water mixed solution total mass.
6. the preparation method of kind of lithium fluoride according to claim 1 is characterized in that, the pressure that carries out carburizing reagent is 0.40～0.45Mpa, keeps this stress reaction 2-3 hour.
7. the preparation method of kind of lithium fluoride according to claim 1 is characterized in that, when carrying out carburizing reagent, the content that feeds carbon dioxide is not less than 99.9%.
8. the preparation method of kind of lithium fluoride according to claim 1, it is characterized in that, when making lithium fluoride slip solid-liquid separation with centrifugation, earlier the liquid-solid separation in the feed liquid is clean by running up, with pure water isolated solid-state lithium fluoride is carried out running up after drip washing, the drip washing again, drip washing again, run up, reach 6～7 until the pH value of water outlet, back discharging at last runs up.
9. the preparation method of kind of lithium fluoride according to claim 1 is characterized in that, the mode that isolated solid-state lithium fluoride is dried is the heating under vacuum oven dry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102215577A CN101723413B (en) | 2009-11-20 | 2009-11-20 | Method for preparing lithium fluoride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102215577A CN101723413B (en) | 2009-11-20 | 2009-11-20 | Method for preparing lithium fluoride |
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| CN101723413A true CN101723413A (en) | 2010-06-09 |
| CN101723413B CN101723413B (en) | 2012-02-29 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013174938A1 (en) | 2012-05-25 | 2013-11-28 | Lanxess Deutschland Gmbh | Production of high-purity lithium fluoride |
| CN103979581A (en) * | 2014-05-27 | 2014-08-13 | 甘孜州泸兴锂业有限公司 | Process for producing lithium fluoride by using spodumene concentrate |
| CN107043115A (en) * | 2017-05-05 | 2017-08-15 | 江西东鹏新材料有限责任公司 | A kind of production technology of lithium fluoride |
| CN108275702A (en) * | 2017-12-26 | 2018-07-13 | 衢州北斗星化学新材料有限公司 | A kind of preparation method for the high-purity lithium fluoride producing lithium hexafluoro phosphate |
| CN108545763A (en) * | 2018-06-27 | 2018-09-18 | 江苏九九久科技有限公司 | High purity lithium fluoride production method and dedicated unit |
| CN108654347A (en) * | 2018-04-17 | 2018-10-16 | 江苏金石稀土有限公司 | A kind of method that fluoride system electrolysis rare earth waste gas recovery utilizes |
| CN111559750A (en) * | 2020-03-27 | 2020-08-21 | 白银中天化工有限责任公司 | Efficient continuous electronic-grade lithium fluoride production process |
| CN111606336A (en) * | 2020-05-19 | 2020-09-01 | 百杰瑞(荆门)新材料有限公司 | Preparation method of lithium fluoride |
| CN115536044A (en) * | 2022-10-12 | 2022-12-30 | 新余赣锋锂业有限公司 | Method for preparing industrial-grade lithium fluoride by recycling lithium fluoride mother liquor |
| CN115650260A (en) * | 2022-12-13 | 2023-01-31 | 深圳新宙邦科技股份有限公司 | Preparation method of lithium hexafluorophosphate, electrolyte and lithium ion battery |
-
2009
- 2009-11-20 CN CN2009102215577A patent/CN101723413B/en active Active
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013174938A1 (en) | 2012-05-25 | 2013-11-28 | Lanxess Deutschland Gmbh | Production of high-purity lithium fluoride |
| CN104364198A (en) * | 2012-05-25 | 2015-02-18 | 朗盛德国有限责任公司 | Production of high-purity lithium fluoride |
| JP2015518811A (en) * | 2012-05-25 | 2015-07-06 | ランクセス・ドイチュランド・ゲーエムベーハー | Production of high purity lithium fluoride |
| CN104364198B (en) * | 2012-05-25 | 2016-07-06 | 朗盛德国有限责任公司 | The preparation of high-purity lithium fluoride |
| CN103979581A (en) * | 2014-05-27 | 2014-08-13 | 甘孜州泸兴锂业有限公司 | Process for producing lithium fluoride by using spodumene concentrate |
| CN103979581B (en) * | 2014-05-27 | 2015-10-14 | 甘孜州泸兴锂业有限公司 | A kind of triphane concentrate produces the technique of lithium fluoride |
| CN107043115A (en) * | 2017-05-05 | 2017-08-15 | 江西东鹏新材料有限责任公司 | A kind of production technology of lithium fluoride |
| CN108275702A (en) * | 2017-12-26 | 2018-07-13 | 衢州北斗星化学新材料有限公司 | A kind of preparation method for the high-purity lithium fluoride producing lithium hexafluoro phosphate |
| CN108654347A (en) * | 2018-04-17 | 2018-10-16 | 江苏金石稀土有限公司 | A kind of method that fluoride system electrolysis rare earth waste gas recovery utilizes |
| CN108545763A (en) * | 2018-06-27 | 2018-09-18 | 江苏九九久科技有限公司 | High purity lithium fluoride production method and dedicated unit |
| CN111559750A (en) * | 2020-03-27 | 2020-08-21 | 白银中天化工有限责任公司 | Efficient continuous electronic-grade lithium fluoride production process |
| CN111606336A (en) * | 2020-05-19 | 2020-09-01 | 百杰瑞(荆门)新材料有限公司 | Preparation method of lithium fluoride |
| CN115536044A (en) * | 2022-10-12 | 2022-12-30 | 新余赣锋锂业有限公司 | Method for preparing industrial-grade lithium fluoride by recycling lithium fluoride mother liquor |
| CN115536044B (en) * | 2022-10-12 | 2023-07-18 | 新余赣锋锂业有限公司 | Method for preparing industrial grade lithium fluoride by recycling lithium fluoride mother liquor |
| CN115650260A (en) * | 2022-12-13 | 2023-01-31 | 深圳新宙邦科技股份有限公司 | Preparation method of lithium hexafluorophosphate, electrolyte and lithium ion battery |
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| Publication number | Publication date |
|---|---|
| CN101723413B (en) | 2012-02-29 |
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Address after: 338015 Longteng Road, Xinyu Economic Development Zone, Jiangxi, Xinyu Patentee after: Jiangxi Ganfeng Lithium Industry Group Co.,Ltd. Address before: 338015 Longteng Road, Xinyu Economic Development Zone, Jiangxi, Xinyu Patentee before: JIANGXI GANFENG LITHIUM Co.,Ltd. |
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