CN106800305A - A kind of method that multistep processes prepares battery-level lithium carbonate - Google Patents
A kind of method that multistep processes prepares battery-level lithium carbonate Download PDFInfo
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- CN106800305A CN106800305A CN201710019965.9A CN201710019965A CN106800305A CN 106800305 A CN106800305 A CN 106800305A CN 201710019965 A CN201710019965 A CN 201710019965A CN 106800305 A CN106800305 A CN 106800305A
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- lithium carbonate
- lithium
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- carbonate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of method that multistep processes prepares battery-level lithium carbonate, successively using hydro-thermal method, chemical subtraction, ion exchange, wherein impurity is progressively removed, obtain high-purity lithia water, lithia water hydrothermal decomposition obtains final product battery-level lithium carbonate.Effective effect of the invention is：Hydro-thermal method can remove most soluble-salt and complete the conversion of magnesium.Chemical subtraction can effectively remove insoluble impurities and most calcium, magnesium ion.Nonionic adsorption resin is further refined, and removes remaining impurity.By three kinds of combinations of impurity-removing method, on the basis of production cost is optimized, the impurity in thick level lithium carbonate can be to greatest extent removed, obtain battery-level lithium carbonate.
Description
Technical field
The present invention relates to pure Lithium Carbonate preparing technical field, mainly a kind of multistep processes prepares the side of battery-level lithium carbonate
Method.
Background technology
Lithium carbonate is the raw material for preparing various lithium compounds, is the product that yield is maximum in lithium salts product, purposes is most wide.Its
Middle pure Lithium Carbonate is in glass ceramics, petrochemical industry, organic synthesis, medicine, electronic material, light industrial materials, electrode material etc.
Aspect has important use.Additionally, lithium carbonate can also be used to produce lithium chloride, the bromine of high-purity as a kind of basic lithium salts
Change high-purity secondary lithium salt or the organo-lithium compounds such as lithium.
In recent years, both at home and abroad to lithium carbonate product quality requirement more and more higher, and primary product all do not reach requirement mostly,
So research lithium carbonate purification is necessary.At present, the purification process of pure Lithium Carbonate product is prepared by thick level lithium carbonate product
It is main to have causticizing process, recrystallization method, electrolysis, the hydrogenation precipitation method and hydrogenative decomposition method.Causticizing process can effectively remove deliming, magnesium
Ion, but need the milk of lime of high-purity；Recrystallization method is simple and easy to apply, but lithium carbonate solubility very little, and the production cycle is long, energy
Consumption is high；The lithium carbonate product purity that electrolysis is obtained is high and process is simple, but requirement of the method to film power consumptions higher
Compare high；The hydrogenation precipitation method can better control over product granularity, but in preparation process to the purity requirement of lithium hydroxide very
Height, this just increases production cost；Hydrogenative decomposition method has operation possibility higher, and the rate of recovery is high, and common use should at present
Technique.
But, it is limited in one's ability or higher to ingredient requirement that single method of purification removes impurity, causes impurity-eliminating effect not
Preferable or high expensive.
The content of the invention
It is an object of the invention to overcome the shortcomings of that prior art is present, and a kind of multistep processes is provided and prepares LITHIUM BATTERY carbonic acid
The method of lithium, successively using hydro-thermal method, chemical subtraction, ion exchange, progressively removes wherein impurity, obtains high-purity lithium bicarbonate molten
Liquid, lithia water hydrothermal decomposition obtains final product lithium carbonate.
The purpose of the present invention is completed by following technical solution.This multistep processes prepares the side of battery-level lithium carbonate
Method, including following steps：
A, the thick level lithium carbonate for weighing certain mass, are washed with unsaturated carbonate lithium solution and are made, and are stirred and are filtered, and take filter
Cake；Filtrate is cooled down, is concentrated, and is recycled；
B, the deionized water to addition certain mass in the filter cake of step a, are configured to suspension, the wherein solid-liquid of suspension
Than being 1:10~1:50；And carbon dioxide is passed through, filter to take filtrate after solution is clarified；
C, to appropriate unsaturated carbonate hydrogen barium solution is added dropwise in the filtrate in step b, a small amount of high-purity hydrogen-oxygen is then added dropwise
Change lithium solution, filter to take filtrate；Wherein, sulfate radical mol ratio is 1 in sample after the addition of barium bicarbonate is washed with hydro-thermal method
~1.1:1, the mol ratio of calcium in sample magnesium ion sum is 1~1.1 after addition and the hydro-thermal method washing of lithium hydroxide:1.
D, by the filtrate in step c by ion exchange resin, further adsorbing contaminant obtains final product high-purity lithium bicarbonate molten
Liquid；
Filtrate in e, heating stepses d, generates white precipitate, filters, dries, you can obtains battery-level lithium carbonate.
Further, washed using unsaturated carbonate lithium solution in step a, wherein the temperature of wash solution is 50~100
℃。
Further, lithium bicarbonate is made to decompose generation lithium carbonate using hydro-thermal method in step e, wherein, hydrothermal temperature is
60~100 DEG C.
Beneficial effects of the present invention are：Hydro-thermal method can remove most soluble-salt, while completing the conversion of magnesium.Change
Learning removal of impurities can effectively remove most calcium, magnesium ion and insoluble impurities.Nonionic adsorption resin is further refined, and is removed
Remaining impurity.By three kinds of combinations of impurity-removing method, on the basis of production cost is optimized, can remove to greatest extent thick
Impurity component in level lithium carbonate, obtains battery-level lithium carbonate.
Brief description of the drawings
Fig. 1 is process flow diagram of the invention.
Specific embodiment
Detailed introduction is done to the present invention below in conjunction with accompanying drawing：
Because solubility is larger in the water of sodium salt and sylvite, and it is easily detected by chemical method and removes, and lithium carbonate is in water
Middle solubility is smaller, therefore can wash thick level lithium carbonate with unsaturated carbonate lithium solution, can remove the soluble-salt impurity such as sodium, potassium,
The conversion of magnesium can be completed simultaneously.CO is passed through in lithium carbonate suspension after being processed to hydro-thermal method2, carbonic acid hydrogenation is carried out, then
Barium bicarbonate solution is added, unsegregated sulfate ion is removed, a small amount of high-purity lithium hydroxide solution is added, using OH-
With HCO3 -The CO of generation3 2-With the Ca in solution2+、Mg2+Plasma produces precipitation, then filters, you can remove insoluble impurities
And most impurity.Finally filtered fluid is refined by ion exchange resin, foreign ion is further removed, you can obtained
High-purity lithia water, lithia water hydrothermal decomposition obtains final product battery-level lithium carbonate.
The present invention is completed by following technical solution, a kind of method that multistep processes prepares battery-level lithium carbonate, bag
Include following steps：
A, the thick level lithium carbonate for weighing certain mass, are washed with unsaturated carbonate lithium solution and are made, and are stirred and are filtered, and take filter
Cake；Filtrate is cooled down, is concentrated, and is recycled；Using unsaturated carbonate lithium solution wash, wherein the temperature of wash solution be 50~
100℃.Hydro-thermal washing in, some soluble ions may recombine generation insoluble substance, it is understood that there may be chemistry
Reaction is as follows：Ca2++CO3 2-=CaCO3↓, Mg2++CO3 2-=MgCO3↓, Ca2++SO4 2-=CaSO4↓.Simultaneously as magnesium hydroxide
Solubility it is small compared with magnesium carbonate, in the hot water, following reaction can occur：MgCO3+H2O=Mg (OH)2↓+CO2。
B, the deionized water to addition certain mass in the filter cake of step a, are configured to suspension, the wherein solid-liquid of suspension
Than being 1:10~1:50；And carbon dioxide is passed through, filter to take filtrate after solution is clarified；Lead to in the suspension of lithium carbonate sample
Enter carbon dioxide, following reaction occurs：Li2CO3+CO2+H2O=2LiHCO3, CaCO3+CO2+H2O=Ca (HCO3)2。
C, to appropriate unsaturated carbonate hydrogen barium solution is added dropwise in the filtrate in step b, a small amount of high-purity hydrogen-oxygen is then added dropwise
Change lithium solution, filter to take filtrate；Wherein, depending on the addition of barium bicarbonate is according to sulfate ion content in step a filter cakes, its
Sulfate radical mol ratio is 1~1.1 in sample after addition and hydro-thermal method washing:1.The addition of lithium hydroxide is filtered according to step a
In cake depending on calcium ion and magnesium ion content, the mol ratio of calcium in sample magnesium ion sum is after its addition is washed with hydro-thermal method
1~1.1:1.
Add barium ions and the sulfate radical in solution of unsaturated carbonate hydrogen barium solution, dropwise addition to be combined into barium sulfate, occur as follows
Reaction：Ba2++SO4 2-=BaSO4↓.Lithium hydroxide solution is added, a part and bicarbonate in solution in a small amount of hydroxide ion
Radical ion generate carbanion, carbanion with residual calcium binding into calcium carbonate, another part directly with magnesium from
Son generation magnesium hydroxide, reaction equation is as follows：OH-+HCO3 -=CO3 2-+H2O, Ca2++CO3 2-=CaCO3↓, Mg2++OH-=Mg
(OH)2↓。
D, by the filtrate in step c by ion exchange resin, further adsorbing contaminant obtains final product high-purity lithium bicarbonate molten
Liquid；
Filtrate in e, heating stepses d, generates white precipitate, filters, dries, you can obtains battery-level lithium carbonate.Using
Hydro-thermal method makes lithium bicarbonate decompose generation lithium carbonate, wherein, hydrothermal temperature is 60~100 DEG C.
Embodiment 1
The thick level lithium carbonates of 20g are weighed, the unsaturated carbonate lithium solution for adding 50mL temperature to be 80 DEG C is stirred and filtered, and takes filter
Cake, filtrate cooling, concentration, recycles, residual sulphate ion concentration and calcium ions and magnesium ions content in measurement filter cake.To in filter cake
400mL deionized waters are added, solid-to-liquid ratio 1 is configured to:20 thick level lithium carbonate suspension, is passed through carbon dioxide to suspension and becomes clear
Clearly, filtrate is filtered to take.To unsaturated carbonate hydrogen barium solution is added dropwise in filtrate, dripping quantity is 1 with residual sulphate ion mol ratio:1；
Then to calcium in sample magnesium ion sum after adding a small amount of Lithium hydroxide solution, addition to be washed with hydro-thermal method in filtrate
Mol ratio is 1:1；Filtering, takes filtrate.By filtrate by ion exchange resin, high-purity lithia water is obtained final product, be heated to 90
DEG C, filtering is dried, and obtains final product battery-level lithium carbonate, weighs sample quality, and measure content of material in sample.
Embodiment 2
The thick level lithium carbonates of 20g are weighed, the unsaturated carbonate lithium solution for adding 50mL temperature to be 90 DEG C is stirred and filtered, and takes filter
Cake, filtrate cooling, concentration, recycles, residual sulphate ion concentration and calcium ions and magnesium ions content in measurement filter cake.To in filter cake
600mL deionized waters are added, solid-to-liquid ratio 1 is configured to:30 thick level lithium carbonate suspension, is passed through carbon dioxide to suspension and becomes clear
Clearly, filtrate is filtered to take.To unsaturated carbonate hydrogen barium solution is added dropwise in filtrate, dripping quantity is 1 with residual sulphate ion mol ratio:1；
Then to calcium in sample magnesium ion sum after adding a small amount of Lithium hydroxide solution, addition to be washed with hydro-thermal method in filtrate
Mol ratio is 1:1；Filtering, takes filtrate.By filtrate by ion exchange resin, high-purity lithia water is obtained final product, be heated to 90
DEG C, filtering is dried, and obtains final product battery-level lithium carbonate, weighs sample quality, and measure content of material in sample.
Embodiment 3
The thick level lithium carbonates of 20g are weighed, the unsaturated carbonate lithium solution for adding 50mL temperature to be 90 DEG C is stirred and filtered, and takes filter
Cake, filtrate cooling, concentration, recycles, residual sulphate ion concentration and calcium ions and magnesium ions content in measurement filter cake.To in filter cake
400mL deionized waters are added, solid-to-liquid ratio 1 is configured to:20 thick level lithium carbonate suspension, is passed through carbon dioxide to suspension and becomes clear
Clearly, filtrate is filtered to take.To unsaturated carbonate hydrogen barium solution is added dropwise in filtrate, dripping quantity is 1 with residual sulphate ion mol ratio:1；
Then to calcium in sample magnesium ion sum after adding a small amount of Lithium hydroxide solution, addition to be washed with hydro-thermal method in filtrate
Mol ratio is 1.05:1；Filtering, takes filtrate.By filtrate by ion exchange resin, high-purity lithia water is obtained final product, be heated to
90 DEG C, filtering is dried, and obtains final product battery-level lithium carbonate, weighs sample quality, and measure content of material in sample.
Embodiment result is as follows：
It is understood that the above-mentioned specific embodiment technical scheme that the invention is not limited in any way, every to adopt
The technical scheme obtained with the mode of equivalent or equivalent exchange belongs to protection scope of the present invention.
Claims (3)
1. a kind of method that multistep processes prepares battery-level lithium carbonate, it is characterised in that including following steps：
A, the thick level lithium carbonate for weighing certain mass, are washed with unsaturated carbonate lithium solution and are made, and are stirred and are filtered, and take filter cake；Filter
Liquid is cooled down, concentrated, and is recycled；
B, the deionized water to addition certain mass in the filter cake of step a, are configured to suspension, and the solid-to-liquid ratio of wherein suspension is
1:10~1:50；And carbon dioxide is passed through, filter to take filtrate after solution is clarified；
C, to appropriate unsaturated carbonate hydrogen barium solution is added dropwise in the filtrate in step b, a small amount of Lithium hydroxide is then added dropwise
Solution, filters to take filtrate；Wherein, after the washing of the addition of barium bicarbonate and hydro-thermal method in sample sulfate radical mol ratio be 1~
1.1:1, the mol ratio of calcium in sample magnesium ion sum is 1~1.1 after addition and the hydro-thermal method washing of lithium hydroxide:1.
D, by the filtrate in step c by ion exchange resin, further adsorbing contaminant obtains final product high-purity lithia water；
Filtrate in e, heating stepses d, generates white precipitate, filters, dries, you can obtains battery-level lithium carbonate.
2. the method that multistep processes according to claim 1 prepares battery-level lithium carbonate, it is characterised in that used in step a
Unsaturated carbonate lithium solution is washed, and wherein the temperature of wash solution is 50~100 DEG C.
3. the method that multistep processes according to claim 1 prepares battery-level lithium carbonate, it is characterised in that used in step e
Hydro-thermal method makes lithium bicarbonate decompose generation lithium carbonate, wherein, hydrothermal temperature is 60~100 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107416871A (en) * | 2017-08-31 | 2017-12-01 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of the battery-level lithium carbonate based on the secondary carbonization of carbon dioxide |
| CN109650417A (en) * | 2019-02-28 | 2019-04-19 | 长沙有色冶金设计研究院有限公司 | A kind of multistage of battery-level lithium carbonate washes and starches method of purification |
| CN109987619A (en) * | 2019-04-26 | 2019-07-09 | 核工业北京化工冶金研究院 | The method for preparing battery-level lithium carbonate from lepidolite leachate by strengthening washing |
| CN110713197A (en) * | 2018-07-11 | 2020-01-21 | 深圳市贝特瑞纳米科技有限公司 | Method for recovering lithium salt from mother liquor generated in preparation of lithium iron phosphate by hydrothermal method |
| CN111847486A (en) * | 2020-07-08 | 2020-10-30 | 四川大学 | Method for preparing battery-grade lithium carbonate from metal lithium slag |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432044A (en) * | 2011-09-26 | 2012-05-02 | 江苏海龙锂业科技有限公司 | Method for extracting ultrahigh-purity lithium carbonate from salt lake brine with high magnesium-lithium ratio |
| CN102531002A (en) * | 2011-12-23 | 2012-07-04 | 四川天齐锂业股份有限公司 | Method for purifying lithium carbonate |
| CN102583453A (en) * | 2011-08-31 | 2012-07-18 | 四川长和华锂科技有限公司 | Industrial method for producing battery-grade lithium carbonate or high-purity lithium carbonate |
-
2017
- 2017-01-11 CN CN201710019965.9A patent/CN106800305A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583453A (en) * | 2011-08-31 | 2012-07-18 | 四川长和华锂科技有限公司 | Industrial method for producing battery-grade lithium carbonate or high-purity lithium carbonate |
| CN102432044A (en) * | 2011-09-26 | 2012-05-02 | 江苏海龙锂业科技有限公司 | Method for extracting ultrahigh-purity lithium carbonate from salt lake brine with high magnesium-lithium ratio |
| CN102531002A (en) * | 2011-12-23 | 2012-07-04 | 四川天齐锂业股份有限公司 | Method for purifying lithium carbonate |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107416871A (en) * | 2017-08-31 | 2017-12-01 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of the battery-level lithium carbonate based on the secondary carbonization of carbon dioxide |
| CN110713197A (en) * | 2018-07-11 | 2020-01-21 | 深圳市贝特瑞纳米科技有限公司 | Method for recovering lithium salt from mother liquor generated in preparation of lithium iron phosphate by hydrothermal method |
| CN110713197B (en) * | 2018-07-11 | 2023-05-02 | 贝特瑞（天津）纳米材料制造有限公司 | Method for recovering lithium salt from mother solution generated in preparation of lithium iron phosphate by hydrothermal method |
| CN109650417A (en) * | 2019-02-28 | 2019-04-19 | 长沙有色冶金设计研究院有限公司 | A kind of multistage of battery-level lithium carbonate washes and starches method of purification |
| CN109650417B (en) * | 2019-02-28 | 2021-06-15 | 长沙有色冶金设计研究院有限公司 | Multi-stage slurry washing purification method for battery-grade lithium carbonate |
| CN109987619A (en) * | 2019-04-26 | 2019-07-09 | 核工业北京化工冶金研究院 | The method for preparing battery-level lithium carbonate from lepidolite leachate by strengthening washing |
| CN109987619B (en) * | 2019-04-26 | 2022-03-22 | 核工业北京化工冶金研究院 | Method for preparing battery-grade lithium carbonate from lepidolite leaching solution through intensive washing |
| CN111847486A (en) * | 2020-07-08 | 2020-10-30 | 四川大学 | Method for preparing battery-grade lithium carbonate from metal lithium slag |
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