CN101723415B - Novel process for producing cell-grade lithium fluoride - Google Patents
Novel process for producing cell-grade lithium fluoride Download PDFInfo
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- CN101723415B CN101723415B CN2010101067782A CN201010106778A CN101723415B CN 101723415 B CN101723415 B CN 101723415B CN 2010101067782 A CN2010101067782 A CN 2010101067782A CN 201010106778 A CN201010106778 A CN 201010106778A CN 101723415 B CN101723415 B CN 101723415B
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Abstract
The invention provides a novel process for producing cell-grade lithium fluoride, which comprises the following steps: putting high-purity lithium carbonate, deionized water and carbon dioxide into an absorptive reaction tower for hydrogenation reaction, filtering generated solution of lithium bicarbonate by a plate frame, filtering aluminum, silicon, iron and other impurities off, putting the solution of lithium bicarbonate and anhydrous hydrogen fluoride into a plastic-lined reaction kettle for synthetic reaction of crystal lithium fluoride for 1 to 5 hours, wherein the ratio of the inside diameter to the stirring diameter of the reaction kettle is 3-7:1, filtering a solid mixture of the reacted lithium fluoride liquid by a centrifuge, and drying the solid mixture to obtain a finished product. The novel process has the advantages that: (1) the product has large granularity; and a nozzle cannot be blocked in the lithium hexafluorophosphate production process; and (2) the purity of the product can reach up to 99.95 percent, and meets the purity requirement of the cell-grade lithium fluoride production.
Description
Technical field: the present invention relates to a kind of technology of producing battery-grade lithium fluoride, particularly a kind of novel process of producing battery-grade lithium fluoride.
Background technology: existing technical process of producing battery-grade lithium fluoride is: pure Lithium Carbonate (purity 99.99%), anhydrous hydrogen fluoride and deionized water are moulded synthetic battery-grade lithium fluoride in the reactor at lining; Separate by whizzer, produce battery-grade lithium fluoride wet feed and lithium fluoride mother liquor, the lithium fluoride mother liquor adds lime through the neutralization discharging, and battery-grade lithium fluoride wet feed drying operation generates battery-grade lithium fluoride.The deficiency that in use has the following aspects by the battery-grade lithium fluoride of this explained hereafter: 1, product be Powdered, particle diameter is little, median size is about 17.6 μ m, the lithium fluoride that uses this small particle size is in producing the lithium hexafluoro phosphate process, be easy to plug nozzle, make to produce and interrupt, influence is produced; Cause product cut size to be for a short time because the reactor stirring intensity is excessive, solution saturation ratio and hydrogen fluoride ventilation speed control when lining is moulded in the reactor synthetic battery-grade lithium fluoride reaction are improper.2, product purity is difficult to reach the purity requirement (99.95%) of battery-grade lithium fluoride, only has 99.9%, its reason be product be Powdered, particle diameter is little, its surfactivity is stronger, can carry more water and impurity, thereby makes product purity be difficult to improve; In addition, when lining is moulded in the reactor synthetic battery-grade lithium fluoride, reaction process is gas-liquid-solid three-phase, and Quilonum Retard particle and water-soluble hydrogen fluoride react, and the lithium fluoride small-particle of generation is attached on the unreacted Quilonum Retard particle, stoped the further reaction of Quilonum Retard and hydrofluoric acid, after the oven dry of lithium fluoride product, still have unreacted Quilonum Retard in the lithium fluoride product, behind the dropping phenolphthalein solution, solution shows red, and product is an alkalescence.
Summary of the invention: the objective of the invention is to, produce the deficiency that product cut size is little, purity is not high that battery-grade lithium fluoride technology in use exists at having now, and propose that a kind of product cut size is big, purity is high, can satisfy a kind of novel process of producing battery-grade lithium fluoride of battery-grade lithium fluoride purity requirement.
Can realize purpose of the present invention by following technical proposals, a kind of novel process of producing battery-grade lithium fluoride, it is characterized in that, with pure Lithium Carbonate (purity 99.99%), deionized water and carbonic acid gas place the absorption reaction tower to carry out hydrogenation, with the lithia water Plate Filtration that generates, elimination aluminium, silicon, impurity such as iron, place lining to mould the building-up reactions that reactor carries out the crystallization lithium fluoride lithia water and anhydrous hydrogen fluoride again, the reactor internal diameter is 3～7: 1 with stirring diameter ratio, 1～5 hour reaction times, the liquid-solid batch mixing of the lithium fluoride that has reacted is filtered through whizzer, and drying obtains finished product again.
The rotating speed of stirrer is 200～400 rev/mins in the reactor;
Whipped form is downward propelling screws formula;
Solution saturation ratio 2.7～3.8g/l during the control reaction;
Lithium bicarbonate input speed control=reactor effective volume 2.5m
3/ 1～5h, pH value of solution=2-7 in the reaction process.
Effect of the present invention is: 1, product cut size is big, and median size is about 71.42 μ m, in producing the lithium hexafluoro phosphate process, the situation of plug nozzle can not take place, can make production steady running; Product cut size is greatly because reduced the reactor stirring intensity, measure is that reactor internal diameter and stirring diameter ratio are decided to be 3～7: 1, the rotating speed of stirrer is decided to be 200～400 rev/mins in the reactor, and the solution saturation ratio in the time of will reacting is controlled at 2.7～3.8g/l, hydrogen fluoride ventilation speed is controlled by the pH value of solution in lithium bicarbonate input speed, the reaction process, and this makes particle in the building-up process than the grown up several times of existing technology.2, product purity height can reach 99.95%, satisfies the purity requirement that battery-grade lithium fluoride is produced; The raising of product purity is because when lining is moulded in the reactor synthetic battery-grade lithium fluoride, reaction process is liquid-liquid two-phase, be that pure Lithium Carbonate is behind hydrogenation, generated lithia water, lithium bicarbonate and anhydrous hydrogen fluoride are the liquid-liquid phase reaction, sufficient reacting can not occur still having unreacted Quilonum Retard in the product in the existing technology, thereby improve the purity of product; In addition, the particle diameter of product is big, and its surfactivity greatly reduces, and this makes the attached water of product and impurity greatly reduce, and attached water content drops to 4% by original 15%, and this is also with regard to the corresponding purity that improves product.
Below in conjunction with embodiment the present invention is further set forth:
Embodiment:
Embodiment 1: a kind of novel process of producing battery-grade lithium fluoride, place the absorption reaction tower to carry out hydrogenation pure Lithium Carbonate (purity 99.99%), deionized water and carbonic acid gas, pure Lithium Carbonate and deionized water are put into from absorption reaction tower top, down operation, carbonic acid gas enters from the absorption reaction tower bottom, up operation, reaction equation is: Li
2CO
3+ CO
2+ H
2O=LiHCO
3The lithia water Plate Filtration that will in the absorption reaction tower, generate, impurity such as elimination aluminium, silicon, iron.Place lining to mould the building-up reactions that reactor carries out the crystallization lithium fluoride lithia water and anhydrous hydrogen fluoride again, the reactor internal diameter is 4: 1 with stirring diameter ratio, 1 hour reaction times, the rotating speed of stirrer is 250 rev/mins in the reactor, whipped form is downward propelling screws formula, solution saturation ratio control 2.8g/l during reaction, lithium bicarbonate input speed control=reactor effective volume 2.5m
3/ 1h controls hydrogen fluoride ventilation speed simultaneously, keeps pH value of solution=2 in the reaction process, and the liquid-solid batch mixing of the lithium fluoride that has reacted is filtered through whizzer, and drying obtains finished product again.
Embodiment 2: a kind of novel process of producing battery-grade lithium fluoride, place the absorption reaction tower to carry out hydrogenation pure Lithium Carbonate (purity 99.99%), deionized water and carbonic acid gas, pure Lithium Carbonate and deionized water are put into from absorption reaction tower top, down operation, carbonic acid gas enters from the absorption reaction tower bottom, up operation, reaction equation is: Li
2CO
3+ CO
2+ H2O=LiHCO
3The lithia water Plate Filtration that will in the absorption reaction tower, generate, impurity such as elimination aluminium, silicon, iron.Place lining to mould the building-up reactions that reactor carries out the crystallization lithium fluoride lithia water and anhydrous hydrogen fluoride again, the reactor internal diameter is 5: 1 with stirring diameter ratio, 2 hours reaction times, the rotating speed of stirrer is 300 rev/mins in the reactor, whipped form is downward propelling screws formula, solution saturation ratio control 3.2g/l during reaction, lithium bicarbonate input speed control=reactor effective volume 2.5m
3/ 2h keeps pH value of solution=4.5 in the reaction process, controls hydrogen fluoride ventilation speed simultaneously, and the liquid-solid batch mixing of the lithium fluoride that has reacted is filtered through whizzer, and drying obtains finished product again.
Embodiment 3: a kind of novel process of producing battery-grade lithium fluoride, place the absorption reaction tower to carry out hydrogenation pure Lithium Carbonate (purity 99.99%), deionized water and carbonic acid gas, pure Lithium Carbonate and deionized water are put into from absorption reaction tower top, down operation, carbonic acid gas enters from the absorption reaction tower bottom, up operation, reaction equation is: Li
2CO
3+ CO
2+ H2O=LiHCO
3The lithia water Plate Filtration that will in the absorption reaction tower, generate, impurity such as elimination aluminium, silicon, iron.Place lining to mould the building-up reactions that reactor carries out the crystallization lithium fluoride lithia water and anhydrous hydrogen fluoride again, the reactor internal diameter is 6.5: 1 with stirring diameter ratio, 3 hours reaction times, the rotating speed of stirrer is 370 rev/mins in the reactor, whipped form is downward propelling screws formula, solution saturation ratio control 3.6g/l during reaction, lithium bicarbonate input speed control=reactor effective volume 2.5m
3/ 3h keeps pH value of solution=6 in the reaction process, controls hydrogen fluoride ventilation speed simultaneously, and the liquid-solid batch mixing of the lithium fluoride that has reacted is filtered through whizzer, and drying obtains finished product again.
Claims (4)
1. novel process of producing battery-grade lithium fluoride, it is characterized in that, place the absorption reaction tower to carry out hydrogenation pure Lithium Carbonate, deionized water and carbonic acid gas, with the lithia water Plate Filtration that generates, impurity such as elimination aluminium, silicon, iron, place lining to mould the building-up reactions that reactor carries out the crystallization lithium fluoride lithia water and anhydrous hydrogen fluoride again, the reactor internal diameter is 3～7: 1 with stirring diameter ratio, 1～5 hour reaction times, the liquid-solid batch mixing of the lithium fluoride that has reacted is filtered through whizzer, and drying obtains finished product again.
2. by the described a kind of novel process of producing battery-grade lithium fluoride of claim 1, it is characterized in that the rotating speed of stirrer is 200～400 rev/mins in the reactor.
3. by the described a kind of novel process of producing battery-grade lithium fluoride of claim 1, it is characterized in that whipped form is downward propelling screws formula.
4. by the described a kind of novel process of producing battery-grade lithium fluoride of claim 1, it is characterized in that solution saturation ratio 2.7～3.8g/l during the control reaction.
5. by claim 1 or 2 or 3 or 4 described a kind of novel procesies of producing battery-grade lithium fluoride, it is characterized in that lithium bicarbonate input speed control=reactor effective volume 2.5m
3/ 1～5h, pH value of solution=2-7 in the reaction process.
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| CN2010101067782A CN101723415B (en) | 2010-02-04 | 2010-02-04 | Novel process for producing cell-grade lithium fluoride |
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| CN2010101067782A CN101723415B (en) | 2010-02-04 | 2010-02-04 | Novel process for producing cell-grade lithium fluoride |
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| CN101723415B true CN101723415B (en) | 2011-12-28 |
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Families Citing this family (7)
| 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 |
| 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 |
| CN107902680A (en) * | 2017-11-15 | 2018-04-13 | 天元锂电材料河北有限公司 | A kind of method of industry level lithium carbonate refined raw production battery-level lithium carbonate |
| 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 |
| CN111994924A (en) * | 2020-09-09 | 2020-11-27 | 江西云锂材料股份有限公司 | Novel method for producing high-purity lithium fluoride by taking industrial-grade lithium carbonate as raw material |
| CN115138317A (en) * | 2022-07-13 | 2022-10-04 | 新余赣锋锂业有限公司 | Production device and method for preparing neutral large-granularity battery-grade lithium fluoride by continuously precipitating lithium |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3326631A (en) * | 1963-03-02 | 1967-06-20 | Metallgesellschaft Ag | Method of producing lithium fluoride |
| JP2001106524A (en) * | 1999-10-08 | 2001-04-17 | Nippon Telegr & Teleph Corp <Ntt> | Producing method of alkaline fluoride |
| CN101074103A (en) * | 2006-05-19 | 2007-11-21 | 比亚迪股份有限公司 | Production of lithium fluoride |
-
2010
- 2010-02-04 CN CN2010101067782A patent/CN101723415B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3326631A (en) * | 1963-03-02 | 1967-06-20 | Metallgesellschaft Ag | Method of producing lithium fluoride |
| JP2001106524A (en) * | 1999-10-08 | 2001-04-17 | Nippon Telegr & Teleph Corp <Ntt> | Producing method of alkaline fluoride |
| CN101074103A (en) * | 2006-05-19 | 2007-11-21 | 比亚迪股份有限公司 | Production of lithium fluoride |
Non-Patent Citations (1)
| Title |
|---|
| 刘妙根等.高纯氟化锂的制备与分析.《中国核科技报告》.1999,(第00期),381-395. * |
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