CN113461035A - Method for preparing battery-grade lithium carbonate from high-calcium crude lithium carbonate - Google Patents
Method for preparing battery-grade lithium carbonate from high-calcium crude lithium carbonate Download PDFInfo
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- CN113461035A CN113461035A CN202110895040.7A CN202110895040A CN113461035A CN 113461035 A CN113461035 A CN 113461035A CN 202110895040 A CN202110895040 A CN 202110895040A CN 113461035 A CN113461035 A CN 113461035A
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- Prior art keywords
- lithium carbonate
- hydrogenation
- namely
- liquid
- hydrogenated
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 53
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 53
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 22
- 239000011575 calcium Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 238000003825 pressing Methods 0.000 claims abstract description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing battery-grade lithium carbonate from high-calcium crude lithium carbonate, which comprises the following steps: s1: mixing slurry, namely mixing and stirring the selected crude lithium carbonate, oxalic acid and water to obtain slurry; s2: hydrogenation reaction, namely feeding the slurry into a hydrogenation tower, and introducing carbon dioxide gas for hydrogenation to obtain hydrogenation liquid containing impurities; s3: performing filter pressing, namely performing filter pressing on the impurity-containing hydrogenated liquid by using a filter press to obtain hydrogenated liquid after the filter pressing; s4: fine filtering, fine filtering the hydrogenated liquid with filter membrane for 25-35min to obtain hydrogenated clear liquid, wherein the pore diameter of the filter membrane is controlled at 0.01 μm; s5: pyrolyzing; s6: and (5) finishing. According to the invention, the battery-grade lithium carbonate meeting the industrial standard requirements is prepared by removing calcium from the high-calcium crude lithium carbonate by oxalic acid and purifying, the production process is simple, the production cost is low, and the prepared lithium carbonate meets the requirements of the battery-grade lithium carbonate.
Description
Technical Field
The invention belongs to the field of lithium carbonate refining, and particularly relates to a method for preparing battery-grade lithium carbonate from high-calcium crude lithium carbonate.
Background
The lithium carbonate is mainly derived from salt lake lithium resources, and due to the limitation of production technology and salt lake brine, the primary product is mainly industrial-grade lithium carbonate with low cost and large yield. While a large amount of calcium ions are generated in the process of preparing battery-grade lithium carbonate by using crude lithium carbonate, the method of ion exchange is commonly used for removing the calcium ions, and the method generates a large amount of waste water and has high treatment cost. We therefore propose a method of treating calcium ions with oxalic acid to produce battery grade lithium carbonate from crude lithium carbonate.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing battery-grade lithium carbonate from high-calcium crude lithium carbonate, aiming at the defects of the prior art, the method removes calcium by oxalic acid, and has good calcium removal effect and lower production cost.
The technical scheme adopted by the invention is as follows: a method for preparing battery-grade lithium carbonate from high-calcium crude lithium carbonate comprises the following steps:
s1: mixing slurry, namely selecting crude lithium carbonate and water according to the mass ratio of 1:20-25, selecting oxalic acid with the molar ratio of 1:1 to the calcium content in the crude lithium carbonate, and mixing and stirring the crude lithium carbonate, the oxalic acid and the water to obtain slurry;
s2: hydrogenation reaction, namely feeding the slurry into a hydrogenation tower, and introducing carbon dioxide gas for hydrogenation to obtain impurity-containing hydrogenation liquid, wherein the hydrogenation temperature is controlled at 17 ℃, the hydrogenation pressure is controlled at 10Mpa, and the hydrogenation time is 4.5-5.5 hours;
s3: performing filter pressing, namely performing filter pressing on the impurity-containing hydrogenated liquid by using a filter press for 25-35min to obtain hydrogenated liquid;
s4: fine filtering, fine filtering the hydrogenated liquid with filter membrane for 25-35min to obtain hydrogenated clear liquid, wherein the pore diameter of the filter membrane is controlled at 0.01 μm;
s5: pyrolyzing, namely pyrolyzing the hydrogenated clear liquid in a constant-temperature water bath kettle at the temperature of 90 ℃, wherein 2-3h of pyrolysis time is needed to obtain a lithium carbonate wet product;
s6: and (5) obtaining a finished product, namely centrifuging and drying the lithium carbonate wet product to obtain the battery-grade lithium carbonate.
Preferably, the water temperature selected in step S1 is controlled at 30-35 deg.C, the mixing and stirring time is 50-70min, the stirring speed is 40r/S, and the pH value of the obtained slurry is 8-9.
The invention has the beneficial effects that:
(1) oxalic acid is used as a precipitator, so that the effect of calcium precipitation in the hydrogenation reaction of the high-calcium crude lithium carbonate is good, and meanwhile, oxalate can be decomposed to generate carbonate after the temperature is higher than 150 ℃, or can generate carbonate and water with hydrogen peroxide, so that new anions can not be introduced;
(2) because oxalic acid is used as a precipitator, the precipitate particles generated by the combination of oxalic acid and calcium are finer, filter pressing is carried out by adopting filter cloth after hydrogenation reaction, and then the collected hydrogenated clear liquid is finely filtered by adopting a filter membrane with the micropore of 0.01 mu m, the precipitate containing calcium particles can be effectively filtered, and the aim of removing calcium is fulfilled.
According to the invention, the battery-grade lithium carbonate meeting the industrial standard requirements is prepared by removing calcium from the high-calcium crude lithium carbonate by oxalic acid and purifying, the production process is simple, the production cost is low, and the prepared lithium carbonate meets the requirements of the battery-grade lithium carbonate.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The method for preparing battery-grade lithium carbonate from high-calcium crude lithium carbonate provided by the embodiment includes the following steps:
s1: mixing slurry, namely selecting 5400kg of water, 230kg of crude lithium carbonate and 14kg of oxalic acid, controlling the temperature of the selected water to be 32 ℃, adding the crude lithium carbonate and the oxalic acid into the water for mixing and stirring, and stirring at the speed of 40r/s for 60min to obtain slurry with the pH value of 8;
s2: hydrogenation reaction, namely feeding the slurry into a hydrogenation tower, and introducing carbon dioxide gas for hydrogenation to obtain impurity-containing hydrogenation liquid, wherein the hydrogenation temperature is controlled at 17 ℃, the hydrogenation pressure is controlled at 10Mpa, and the hydrogenation time is 4.5-5.5 hours;
s3: performing filter pressing, namely performing filter pressing on the impurity-containing hydrogenated liquid by using a filter press, wherein the filter press cloth is selected from 108C type, the filter pressing time is 25-35min, and obtaining hydrogenated liquid after filter pressing;
s4: fine filtering, fine filtering the hydrogenated liquid with filter membrane for 25-35min to obtain hydrogenated clear liquid, wherein the pore diameter of the filter membrane is controlled at 0.01 μm;
s5: pyrolyzing, namely pyrolyzing the hydrogenated clear liquid in a constant-temperature water bath kettle at the temperature of 90 ℃, wherein 2-3h of pyrolysis time is needed to obtain a lithium carbonate wet product;
s6: and (5) obtaining a finished product, namely centrifuging and drying the lithium carbonate wet product to obtain the battery-grade lithium carbonate.
Example 2
This example was substantially the same as example 1 except that the amount of the raw material used in step S1 was changed to 1000g of water, 40g of crude lithium carbonate and 0.228g of oxalic acid.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification and replacement based on the technical solution and inventive concept provided by the present invention should be covered within the scope of the present invention.
Claims (2)
1. A method for preparing battery-grade lithium carbonate from high-calcium crude lithium carbonate is characterized by comprising the following steps: the method comprises the following steps:
s1: mixing slurry, namely selecting crude lithium carbonate and water according to the mass ratio of 1:20-25, selecting oxalic acid with the molar ratio of 1:1 to the calcium content in the crude lithium carbonate, and mixing and stirring the crude lithium carbonate, the oxalic acid and the water to obtain slurry;
s2: hydrogenation reaction, namely feeding the slurry into a hydrogenation tower, and introducing carbon dioxide gas for hydrogenation to obtain impurity-containing hydrogenation liquid, wherein the hydrogenation temperature is controlled at 17 ℃, the hydrogenation pressure is controlled at 10Mpa, and the hydrogenation time is 4.5-5.5 hours;
s3: performing filter pressing, namely performing filter pressing on the impurity-containing hydrogenated liquid by using a filter press for 25-35min to obtain hydrogenated liquid;
s4: fine filtering, fine filtering the hydrogenated liquid with filter membrane for 25-35min to obtain hydrogenated clear liquid, wherein the pore diameter of the filter membrane is controlled at 0.01 μm;
s5: pyrolyzing, namely pyrolyzing the hydrogenated clear liquid in a constant-temperature water bath kettle at the temperature of 90 ℃, wherein 2-3h of pyrolysis time is needed to obtain a lithium carbonate wet product;
s6: and (5) obtaining a finished product, namely centrifuging and drying the lithium carbonate wet product to obtain the battery-grade lithium carbonate.
2. The method for preparing battery-grade lithium carbonate from high-calcium crude lithium carbonate according to claim 1, wherein the method comprises the following steps: the temperature of the water selected in the step S1 is controlled at 30-35 ℃, the mixing and stirring time is 50-70min, the stirring speed is 40r/S, and the pH value of the obtained slurry is 8-9.
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| CN202110895040.7A CN113461035A (en) | 2021-08-03 | 2021-08-03 | Method for preparing battery-grade lithium carbonate from high-calcium crude lithium carbonate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110895040.7A CN113461035A (en) | 2021-08-03 | 2021-08-03 | Method for preparing battery-grade lithium carbonate from high-calcium crude lithium carbonate |
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| Publication Number | Publication Date |
|---|---|
| CN113461035A true CN113461035A (en) | 2021-10-01 |
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| CN202110895040.7A Pending CN113461035A (en) | 2021-08-03 | 2021-08-03 | Method for preparing battery-grade lithium carbonate from high-calcium crude lithium carbonate |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020295A (en) * | 2010-12-22 | 2011-04-20 | 四川天齐锂业股份有限公司 | Preparation method of high-purity lithium carbonate |
| 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 |
| CN103708508A (en) * | 2014-01-17 | 2014-04-09 | 长沙有色冶金设计研究院有限公司 | Method for producing cell-grade lithium carbonate from lithium concentrate |
| CN106365181A (en) * | 2016-08-26 | 2017-02-01 | 成都开飞高能化学工业有限公司 | Method of preparing battery-grade lithium carbonate from lithium-rich solution being high in content of impurities |
-
2021
- 2021-08-03 CN CN202110895040.7A patent/CN113461035A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020295A (en) * | 2010-12-22 | 2011-04-20 | 四川天齐锂业股份有限公司 | Preparation method of high-purity 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 |
| 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 |
| CN103708508A (en) * | 2014-01-17 | 2014-04-09 | 长沙有色冶金设计研究院有限公司 | Method for producing cell-grade lithium carbonate from lithium concentrate |
| CN106365181A (en) * | 2016-08-26 | 2017-02-01 | 成都开飞高能化学工业有限公司 | Method of preparing battery-grade lithium carbonate from lithium-rich solution being high in content of impurities |
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Application publication date: 20211001 |