CN102398910B - Method for removing cationic impurities of calcium, magnesium, iron, sodium and potassium from cell grade lithium carbonate - Google Patents
Method for removing cationic impurities of calcium, magnesium, iron, sodium and potassium from cell grade lithium carbonate Download PDFInfo
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- CN102398910B CN102398910B CN201010559282.0A CN201010559282A CN102398910B CN 102398910 B CN102398910 B CN 102398910B CN 201010559282 A CN201010559282 A CN 201010559282A CN 102398910 B CN102398910 B CN 102398910B
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- lithium carbonate
- lithium
- propylhomoserin
- potassium
- sodium
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Abstract
The invention discloses a method for removing cationic impurities of calcium, magnesium, iron, sodium and potassium from cell grade lithium carbonate. The method comprises the following steps: 1, accessing a gas containing more than 99.5% of carbon dioxide to a mixed system of industrial lithium carbonate and redistilled water, and dissolving the carbon dioxide solid; 2, adding a lithium-containing amino acid chelating agent with the molar amount of 1-3 times a molar mount needed by the removal of the total content of the cationic impurities, reacting for several minutes with stirring, heating the obtained solution to decompose LiHCO3 into Li2CO3 which can be precipitated, filtering, and calcinating to obtain the cell grade lithium carbonate. The method has the following advantages: the chelating agent, which contains no impurity ions which contain sodium ions, potassium ions and the like and can cause secondary pollution, can be repeatedly used; contents of various cationic impurities in the prepared cell grade lithium carbonate are lower than standards of the cell grade lithium carbonate; and after the impurity removal, Li2CO3 generated by the decomposition of LiHCO3 cannot be washed or can be directly calcinated after washing once or twice, so the lithium loss caused by repeated product washing is reduced, and the lithium recovery rate in the impurity removal process can reach above 95%.
Description
Technical field
The present invention relates to a kind of method of removing foreign ion, specifically refer to a kind of method of removing the cation impurities such as calcium in battery-level lithium carbonate, magnesium, iron, sodium, potassium, the field that is applied to prepare battery-level lithium carbonate.
Background technology
Li
2cO
3being most important lithium salts in lithium compound, is the main raw material of other high purity lithium compound of preparation and lithium alloy.Thereby Li
2cO
3production be the link of the most basic a, most critical in lithium industry.Lithium cell Industry Quick Development, impels the main raw material Li that produces anode material of lithium battery in recent years
2cO
3demand significantly increase.
At present, lithium compound all extracts from contain lithium salts lake or lithium ore both at home and abroad.Although because salt lake is different with composition of ores, the extraction process of lithium is different, the primary process of preparing Quilonum Retard can be summarized as successively:
Evaporate brine after concentrated or ore decomposition be precipitated as enrichment method Li → removal of impurities (removing successively the impurity such as Fe, Mn, Pb, Ca, Mg, Na, K) → transition Crude lithium Carbonate → dissolving afterwards deep impurity-removing → secondary sedimentation be Quilonum Retard.
In this process, mainly adopted precipitator method removal of impurities, effect is subject to the impact of formed difficulty soluble salt solubleness larger.Because partly precipitated has formed solubility colloid, make it remove effect and conventionally can only reach 10 simultaneously
2the order of magnitude of ppm.Especially the character of Ca, Mg and Li are quite similar, very obstinate.Therefore can only obtain industrial lithium carbonate, wherein still have the multiple cation impurities such as Ca, Mg, Fe, Na, K of certain content, can not be directly used in the preparation of lithium battery material.
Common battery-level lithium carbonate preparation method is by industrial lithium carbonate acidifying or logical CO at present
2make it form LiHCO
3solution, utilizes the further deep impurity-removing of various ion exchange resin or all ingredients, by heating, makes LiHCO
3decompose, recrystallization becomes Li
2cO
3after, then washing, purifying forms.The impurity-eliminating effect of these methods is unsatisfactory, and the various chemicals self that especially added also need to remove by washing, makes in large-scale industrial production, and in Quilonum Retard, the content of foreign ion is difficult to control, and quality product can not guarantee.
Summary of the invention
For the problems referred to above, the object of the invention is to design and a kind ofly by industrial lithium carbonate, prepared the method for effectively removing of multiple cation impurity in battery-level lithium carbonate technique.
Technical scheme of the present invention is:
A method of removing the cation impurities such as calcium in battery-level lithium carbonate, magnesium, iron, sodium, potassium, realizes by the following method:
1, after the ratio of 33-100:1 is uniformly mixed in mass ratio by redistilled water and industrial lithium carbonate, pass into content higher than 99.5%CO
2gas, hydrogenation forms LiHCO
3solution;
2, containing lithium propylhomoserin complexing agent can by polynary amino carboxy chelating agent as diethylenetriamine pentaacetic acid, ethylenediamine tetraacetic acid (EDTA), teiethylene tetramine-hexacetic acid etc. and lithium hydroxide reaction make;
Can be by the polynary amino carboxy chelating agent of the analytical pure of easily buying as diethylenetriamine pentaacetic acid, ethylenediamine tetraacetic acid (EDTA), teiethylene tetramine-hexacetic acid etc. containing the polynary complexone of lithium, 1:7.5 is dispersed in water in mass ratio, be heated to 60 ℃ above after, then to add mass percentage concentration be that 10% analytical pure lithium hydroxide aqueous solution dissolves completely it.
Volumetric molar concentration C=W/(M * the V of polynary propylhomoserin sequestrant in this solution), wherein W is the polynary amino carboxy chelating agent total mass number taking, and M is its molecular weight, and V is with dm
3overall solution volume for unit.
3, according to the composition analysis result of industrial lithium carbonate, to add in this solution want decationize content of impurities 1～3 times of molar weight containing the polynary aminocarboxylate chelator of lithium, after stirring reaction 1-10 minute, heat this solution and make LiHCO to 80-100 ℃
3decompose and generate Li
2cO
3and separate out, take advantage of heat to filter with sintered glass funnel decompression, after then filtering, gained solid is dried, and in 400-600 ℃ of calcination 0.5-3 hour, can obtain battery-level lithium carbonate;
4, it be acid the filtrate of above-mentioned filtration gained being regulated to pH, and preferably pH is less than 3, makes the soluble chelating agent that combines foreign ion again change the polynary aminocarboxylic acid that is insoluble in water into, after filtration, can be recycled after washing.
The invention has the advantages that: the foreign ion that can not cause secondary pollution in sequestrant containing Na, K etc.; The Li of preparation
2cO
3in various impurity ion content all lower than battery-level lithium carbonate standard; After removal of impurities by LiHCO
3decompose the Li generating
2cO
3can be without direct calcination after washing or washing 1-2 time, thus reduced because cleaning product repeatedly causes the loss of lithium, and the rate of recovery of Li can reach more than 95%; Sequestrant can Reusability.
Embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein, only for description and interpretation the present invention, is not intended to limit the present invention.
embodiment 1
Water and industrial lithium carbonate blending ratio 33:1
The industrial lithium carbonate and the 500ml water that take 15.1 gram 99% mix, and under room temperature, pass into CO
2to system clarification, ethylenediamine tetraacetic acid (EDTA) three lithium salt solutions to the 0.34mol/L that adds in solution 25ml to make, stir 30min post-heating to 85 ℃, the Quilonum Retard filtration under diminished pressure of separating out.Gained solid is in 550 ℃ of dry 3h, product foreign matter content analysis in table 1.
embodiment 2
Water and industrial lithium carbonate blending ratio 100:1
The industrial lithium carbonate and the 500ml water that take 5 gram 99% mix, and under room temperature, pass into CO
2to clarification, to ethylenediamine tetraacetic acid (EDTA) three lithium salt solutions of the 0.34mol/L that adds in solution 10ml to make, stir 30min post-heating to 85 ℃, the Quilonum Retard filtration under diminished pressure of separating out, 20ml water washing is once.Gained solid is in 550 ℃ of dry 3h.Product foreign matter content analysis in table 1.
Table 1. product foreign matter content analytical table
embodiment 3
Ethylenediamine tetraacetic acid (EDTA) three lithium salt solution preparations
Take 14.6 grams of ethylenediamine tetraacetic acid (EDTA)s and be scattered in 110ml water, under stirring, be heated to 60 ℃, then add the lithium hydroxide solution of 36ml 10%, obtain ethylenediamine tetraacetic acid (EDTA) three lithium salt solutions of clear.
The volumetric molar concentration of this solution is 14.6g/(292g/mol * 0.146L)=0.34mol/L.
Finally it should be noted that: the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (2)
1. a method of removing the cation impurities such as calcium in battery-level lithium carbonate, magnesium, iron, sodium, potassium, realizes by following steps:
(1), after the ratio of 33～100:1 is uniformly mixed in mass ratio by redistilled water and industrial lithium carbonate, pass into content higher than 99.5% CO
2gas, hydrogenation forms LiHCO
3solution;
(2), containing lithium propylhomoserin complexing agent, by polynary propylhomoserin sequestrant and lithium hydroxide reaction, made;
(3), to add in the solution of above-mentioned steps (1) want 1-3 times of molar weight of decationize content of impurities containing lithium propylhomoserin sequestrant, after stirring reaction 1-10 minute, heat this solution and make LiHCO
3decompose and generate Li
2cO
3and separate out, after filtration, at 400-600 ℃ of calcination 0.5-3 hour, can obtain battery-level lithium carbonate;
(4), the filtrate after filtering in above-mentioned steps (3) is regulated to pH be acid, makes the soluble chelating agent that combines foreign ion again change the polynary propylhomoserin that is insoluble in water into, after filtration, can be recycled after washing;
Describedly containing lithium propylhomoserin complexing agent preparation process be: by polynary propylhomoserin sequestrant in mass ratio 1:7.5 be dispersed in water, be heated to 60 ℃ above after, then to add mass percentage concentration be that 10% analytical pure lithium hydroxide aqueous solution dissolves completely it;
Described polynary propylhomoserin sequestrant is diethylenetriamine pentaacetic acid or ethylenediamine tetraacetic acid (EDTA).
2. a kind of method of removing the cation impurities such as calcium in battery-level lithium carbonate, magnesium, iron, sodium, potassium according to claim 1, is characterized in that described step (4) regulates filtrate pH to be less than 3.
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|---|---|---|---|
| CN201010559282.0A CN102398910B (en) | 2010-11-25 | 2010-11-25 | Method for removing cationic impurities of calcium, magnesium, iron, sodium and potassium from cell grade lithium carbonate |
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|---|---|---|---|
| CN201010559282.0A CN102398910B (en) | 2010-11-25 | 2010-11-25 | Method for removing cationic impurities of calcium, magnesium, iron, sodium and potassium from cell grade lithium carbonate |
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| CN102398910A CN102398910A (en) | 2012-04-04 |
| CN102398910B true CN102398910B (en) | 2014-07-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111186849A (en) * | 2019-12-30 | 2020-05-22 | 江西赣锋循环科技有限公司 | Method for recovering organic complexing agent from lithium precipitation mother liquor |
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| IN2015DN00532A (en) * | 2012-07-05 | 2015-06-26 | Aisin Seiki | |
| CN103351010B (en) * | 2013-06-29 | 2015-10-28 | 西北矿冶研究院 | Preparation process of battery-grade lithium carbonate |
| CN105036159A (en) * | 2015-07-23 | 2015-11-11 | 韦海棉 | Method for preparing lithium carbonate with high-lithium salt lake bittern |
| KR101956355B1 (en) * | 2018-01-17 | 2019-03-11 | 에스케이이노베이션 주식회사 | Method of preparing lithium metal oxide and method of manufacturing lithium secondary battery |
| CN108484818A (en) * | 2018-05-09 | 2018-09-04 | 合肥国轩高科动力能源有限公司 | Preparation of maleic anhydride-acrylic acid copolymer and application of maleic anhydride-acrylic acid copolymer in removing calcium and magnesium ions |
| CN110357129B (en) * | 2019-07-30 | 2021-08-13 | 广西融兴沃能锂业科技有限公司 | Method for preparing battery-grade lithium carbonate by purifying crude lithium carbonate |
| CN110980777B (en) * | 2019-12-25 | 2022-09-09 | 青海奥瑞泰克化工科技有限公司 | Method for preparing purification additive and purification additive prepared by the method |
| CN110937614B (en) * | 2019-12-25 | 2022-09-20 | 青海奥瑞泰克化工科技有限公司 | Method for preparing purification additive and purification additive prepared by the method |
| CN115286017B (en) * | 2022-08-25 | 2024-03-12 | 广东邦普循环科技有限公司 | Preparation method of battery-grade lithium carbonate |
| CN115504490B (en) * | 2022-09-29 | 2023-12-19 | 江西闪凝科技有限公司 | Method for preparing battery-grade lithium carbonate by external field assistance |
| CN115872379B (en) * | 2022-12-21 | 2024-06-18 | 佛山市德方纳米科技有限公司 | Method for removing calcium in solid lithium phosphate |
| CN116022831A (en) * | 2022-12-29 | 2023-04-28 | 武汉中科先进材料科技有限公司 | Preparation method of high-purity lithium carbonate |
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| WO2010131664A1 (en) * | 2009-05-15 | 2010-11-18 | 日本化学工業株式会社 | High purity lithium carbonate and method for producing same |
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| CN101177288A (en) * | 2007-10-30 | 2008-05-14 | 中国科学院青海盐湖研究所 | Process for preparing high-purity lithium carbonate by using saline lithium resource |
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| CN111186849A (en) * | 2019-12-30 | 2020-05-22 | 江西赣锋循环科技有限公司 | Method for recovering organic complexing agent from lithium precipitation mother liquor |
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