CN115286017A - Preparation method of battery-grade lithium carbonate - Google Patents
Preparation method of battery-grade lithium carbonate Download PDFInfo
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- CN115286017A CN115286017A CN202211023595.3A CN202211023595A CN115286017A CN 115286017 A CN115286017 A CN 115286017A CN 202211023595 A CN202211023595 A CN 202211023595A CN 115286017 A CN115286017 A CN 115286017A
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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 190
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 171
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 105
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 65
- 239000000706 filtrate Substances 0.000 claims abstract description 56
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 42
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 39
- 238000001914 filtration Methods 0.000 claims abstract description 31
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims abstract description 28
- 238000001556 precipitation Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 24
- 239000002244 precipitate Substances 0.000 claims abstract description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000004537 pulping Methods 0.000 claims abstract description 12
- 238000002156 mixing 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
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 32
- 239000013078 crystal Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 20
- 239000012452 mother liquor Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 230000001351 cycling effect Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 57
- 239000010413 mother solution Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 23
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000000151 deposition Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 230000008901 benefit Effects 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009993 causticizing Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of battery-grade lithium carbonate, and relates to the technical field of battery-grade lithium carbonate. Adding a sodium carbonate solution into a lithium-containing mother solution to carry out high-temperature lithium precipitation to obtain crude lithium carbonate; and (3) carrying out multi-stage circulation operation of hydrogenation reaction and thermal decomposition reaction on the crude lithium carbonate: mixing the crude lithium carbonate and water to prepare pure water slurry, introducing carbon dioxide to carry out hydrogenation reaction until the lithium carbonate is completely dissolved, and filtering to obtain a lithium bicarbonate solution; heating the lithium bicarbonate solution until a precipitate is generated, and separating high-purity lithium carbonate and lithium-containing filtrate; returning the lithium-containing filtrate to mix with another part of crude lithium carbonate to carry out filtrate pulping to form filtrate slurry; the multi-stage circulation operation has at least 4 circulation times. The application can greatly reduce the pure water consumption by repeatedly using the lithium-containing filtrate after the thermal decomposition reaction for pulping. Due to the problem of the solubility of the lithium carbonate, the less the pure water is used, the less the lithium carbonate is correspondingly dissolved, and the conversion rate of the solid lithium carbonate is greatly improved.
Description
Technical Field
The invention relates to the technical field of battery-grade lithium carbonate, in particular to a preparation method of battery-grade lithium carbonate.
Background
Lithium carbonate is used as an important compound of lithium salt, is widely used in the new energy automobile industry, and lithium cobaltate, lithium nickelate, lithium nickel cobaltate, lithium iron phosphate, lithium nickel cobalt manganese oxide and other positive electrode materials are mostly prepared by using lithium carbonate as a raw material.
The current production methods of battery-grade lithium carbonate mainly comprise a high-temperature lithium precipitation method, an electrolytic method, a causticizing method, a hydrogenation decomposition method and the like. The common high-temperature lithium precipitation method is characterized in that a lithium-containing solution and a sodium carbonate solution are subjected to precipitation reaction at high temperature to generate lithium carbonate, and the method has the advantages of high conversion rate, high reaction speed and the like, but also has the problem of overhigh content of sodium impurities in the product; the electrolysis method mainly comprises electrolyzing saturated lithium salt solution to obtain high-purity lithium hydroxide, and introducing appropriate amount of CO 2 The gas generates battery-grade lithium carbonate, and the method has the advantage of high product purity, but the production cost is higher; the causticization method is to react high-purity lithium carbonate with calcium hydroxide aqueous solution, obtain high-purity lithium hydroxide after separation and impurity removal, and then introduce a proper amount of CO 2 The gas generates battery-grade lithium carbonate, and the method has the advantage of high product purity, but has longer production flow and higher operation cost; the hydrogenation decomposition method is to introduce excessive CO into the insoluble lithium carbonate solution 2 The gas generates lithium bicarbonate with higher solubility, the lithium bicarbonate solution is easy to decompose by heating, and the lithium bicarbonate can be decomposed in a heating mode to generate battery-grade lithium carbonate.
At present, chinese patent 200710019052.3, a process for preparing high-purity lithium carbonate by using salt lake lithium resources, which adopts a hydrogenation process, prepares industrial-grade lithium carbonate by using salt lake brine as a raw material and introducing CO 2 Gas hydrogenation, after the relevant impurity removal process, decomposing lithium bicarbonate under the negative pressure condition, and washing for multiple times to prepare battery-grade lithium carbonate; preparation of battery-grade lithium carbonate in patent CN106517258BMethod' obtains lithium bicarbonate solution by hydrogenating industrial-grade lithium carbonate, obtains lithium carbonate solid with higher purity by reheating the lithium bicarbonate solution, prepares lithium hydroxide by causticizing the obtained lithium carbonate and calcium hydroxide, and finally introduces CO into the lithium hydroxide causticizing solution 2 Preparing high-purity lithium carbonate solid, and washing for multiple times to obtain the battery-grade lithium carbonate. Most of lithium carbonate products prepared by the methods need to be washed for many times to ensure that the products are qualified, and the consumption of pure water is high, so that a large amount of lithium carbonate products are dissolved in water, and the conversion rate of lithium carbonate is low.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of battery-grade lithium carbonate.
The invention is realized by the following steps:
in a first aspect, the present invention provides a method for preparing battery-grade lithium carbonate, comprising:
and (3) high-temperature lithium deposition: adding a sodium carbonate solution into the lithium-containing mother liquor to carry out high-temperature lithium precipitation to obtain crude lithium carbonate;
carrying out multi-stage circulation operation of hydrogenation reaction and thermal decomposition reaction on the crude lithium carbonate;
wherein the multi-stage cyclical operation comprises:
hydrogenation reaction: dividing the crude lithium carbonate into multiple parts, mixing one part of the crude lithium carbonate with water to prepare pure water slurry, continuously introducing carbon dioxide into the pure water slurry to perform hydrogenation reaction until lithium carbonate solids are completely dissolved, and filtering insoluble impurities to obtain a lithium bicarbonate solution;
thermal decomposition reaction: heating the lithium bicarbonate solution, gradually becoming turbid, generating white lithium carbonate precipitate, and separating high-purity lithium carbonate and lithium-containing filtrate;
the hydrogenation reaction and the thermal decomposition reaction are used as a primary cycle, and in the subsequent cycle, the lithium-containing filtrate is returned to be mixed with another part of the crude lithium carbonate for filtrate pulping to form filtrate slurry; the circulation times of the multi-stage circulation operation are at least 4 times;
and directly drying the high-purity lithium carbonate without washing to obtain battery-grade lithium carbonate powder.
The invention has the following beneficial effects: according to the preparation method of the battery-grade lithium carbonate, the lithium-containing filtrate obtained after the thermal decomposition reaction is repeatedly utilized for pulping, so that the consumption of pure water is greatly reduced. Due to the problem of the solubility of the lithium carbonate, the less the pure water is used, the less the lithium carbonate is correspondingly dissolved, and the conversion rate of the solid lithium carbonate is greatly improved. Through the microporous filtration impurity removal reaction in the hydrogenation reaction, the problem of enrichment of P, si, ca and other metal ions in the multi-stage circulation hydrogenation reaction is ingeniously avoided, the circulation times of lithium-containing filtrate are improved, and the purity and the conversion rate of the lithium carbonate product are greatly improved. Through two-step lithium precipitation reaction: the high-temperature lithium deposition of sodium carbonate and the high-temperature decomposition of lithium bicarbonate are beneficial to reducing the impurity content of the lithium carbonate product. The lithium carbonate product prepared by the process flow has high one-time qualification rate, can reach the standard of battery-grade lithium carbonate without filter pressing and washing, and greatly shortens the production flow. The process has no complicated parameter adjusting steps and distinct experimental phenomenon, and is beneficial to industrial production operation; the requirement on equipment is not high, and impurity removal reaction is performed through precipitation and impurity removal, so that the production cost is reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a process flow chart of a method for preparing battery grade lithium carbonate according to the present invention;
fig. 2 is an SEM image of a lithium carbonate product in example 1 of the present invention;
FIG. 3 is an SEM image of a lithium carbonate product of comparative example 1 in accordance with the invention;
FIG. 4 is a diagram showing the inner wall of the beaker after the reaction of precipitating lithium in example 1 of the present invention;
FIG. 5 is a diagram showing the inner wall of the beaker after the reaction for precipitating lithium in comparative example 1 according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Referring to fig. 1, the present invention provides a method for preparing battery-grade lithium carbonate, which comprises the following steps:
s1, impurity removal reaction.
Concentrating the lithium-containing solution to remove impurities (P, mg, fe, al, ni, co, mn and the like) to obtain a lithium-containing mother solution, wherein the impurities removal comprises the steps of adjusting the pH value of the concentrated lithium-containing solution to 10-14, adding a calcium hydroxide solution, controlling the lithium content in the concentrated lithium-containing solution to be 15-25g/L, and controlling the molar ratio of the addition amount of the calcium hydroxide solution to the P content in the concentrated lithium-containing solution to be 1-1.5:1, stirring and reacting for 15-45min at 50-80 ℃, precipitating phosphorus and various metal ions, and filtering and removing.
Preferably, the lithium content of the concentrated solution is between 20 and 25g/L; adjusting the pH value of the lithium-containing mother liquor to between 10 and 12; the molar ratio of the calcium hydroxide dosage to the P content in the solution is (1-1.2): 1; the reaction temperature is between 60 and 70 ℃, the reaction time is between 15 and 20min, and the stirring speed is between 300 and 500rpm.
The reaction mechanism of impurity removal is that
Conversion to Ca 3 (PO 4 ) 2 Precipitating, and generating corresponding precipitates by other metal ions under alkaline conditions, and filtering to remove the precipitates, wherein the reaction formula is as follows:
M n+ +nOH - →M(OH) n ↓(M n+ is a metal ionSon)
And S2, depositing lithium at high temperature.
And adding a sodium carbonate solution into the lithium-containing mother liquor to carry out high-temperature lithium precipitation separation to obtain crude lithium carbonate and a coarse filtrate, and returning the coarse filtrate to the evaporation concentration system.
Specifically, in the high-temperature lithium precipitation process, the mass ratio of sodium carbonate in a sodium carbonate solution is 10-30%, and the molar ratio of the consumption of the sodium carbonate solution to the Li content in the lithium-containing mother liquor is 0.5-0.8:1; the reaction temperature of high-temperature lithium deposition is 60-90 ℃, the reaction time is 30-120min, and the stirring speed is 300-700rpm; during the reaction, white precipitate is continuously generated in the solution, and crude lithium carbonate is obtained by filtering, wherein the reaction formula is as follows:
preferably, in the high-temperature lithium precipitation process, the mass ratio of sodium carbonate in the sodium carbonate solution is 20-30%, the molar ratio of the usage of the sodium carbonate solution to the content of Li in the lithium-containing mother liquor is 0.5-0.6:1; the reaction temperature of high-temperature lithium precipitation is 80-90 ℃, the reaction time is 90-120min, and the stirring speed is 400-600rpm.
Further, adding battery grade lithium carbonate powder serving as a reaction second seed crystal into the system during high-temperature lithium precipitation; the addition amount of the second crystal seed is 2-8% of the theoretical crude lithium carbonate; further preferably 4% to 8%. It should be noted that the addition of the seed crystal is beneficial to reducing the content of impurities in the crude lithium carbonate, and effectively avoids the phenomenon that the lithium carbonate sticks to the wall in the reactor.
And S3, performing multi-stage circulation operation.
Carrying out multi-stage circulation operation of hydrogenation reaction and thermal decomposition reaction on the crude lithium carbonate; wherein the multi-stage cyclic operation comprises:
hydrogenation reaction: dividing the crude lithium carbonate into multiple parts, mixing one part of the crude lithium carbonate with water to prepare pure water slurry, continuously introducing carbon dioxide into the pure water slurry to perform hydrogenation reaction until lithium carbonate solids are completely dissolved, and filtering insoluble impurities to obtain a lithium bicarbonate solution; the reaction temperature of the hydrogenation reaction is 20-40 ℃, and the reaction time is 60-120min; filtering in hydrogenation reaction by 0.5-2 μm microporous filterThe impurities such as Si, ca and the like can be removed by filtering with a microporous filter, the one-time qualification rate of the product is greatly improved, multiple times of washing is not needed, and CO after the reaction is collected in the hydrogenation reaction 2 Gas is introduced into the next stage of hydrogenation reaction, so that CO is greatly improved 2 The cyclic utilization of. Impurity removal reaction is carried out before high-temperature lithium precipitation reaction, so that PO in subsequent multi-stage hydrogenation reaction is avoided 4 3- Enrichment, metal ion precipitation and the like, and is beneficial to improving the purity of the final product.
Thermal decomposition reaction: heating the lithium bicarbonate solution, gradually becoming turbid and generating white lithium carbonate precipitate, separating high-purity lithium carbonate from lithium-containing filtrate, wherein the content of Li in the lithium-containing filtrate is 2.5-4g/L, and the content of Na and S is lower than 0.6g/L.
In the thermal decomposition reaction, adding battery-grade lithium carbonate powder serving as first crystal seeds into a lithium bicarbonate solution, wherein the addition amount of the first crystal seeds is 2% -8% of the theoretical crude lithium carbonate amount, heating to 70-95 ℃, stirring for reaction for 30-120min, and filtering while hot to obtain high-purity lithium carbonate and lithium-containing filtrate.
The hydrogenation reaction and the thermal decomposition reaction are used as a primary cycle, and in the subsequent cycle, the lithium-containing filtrate is returned to be mixed with the other part of crude lithium carbonate for filtrate pulping to form filtrate slurry; the lithium-containing filtrate obtained after the thermal decomposition reaction is repeatedly utilized for pulping, so that the consumption of pure water is greatly reduced. Due to the problem of the solubility of the lithium carbonate, the less pure water is used, the less lithium carbonate is correspondingly dissolved, and the conversion rate of the solid lithium carbonate is greatly improved.
The cycle number of the multi-stage cycle operation is at least 4; because the filtrate of the thermal decomposition reaction is continuously recycled, the content of Na and S in the filtrate is continuously enriched, and the content of Na and S impurities in the lithium carbonate product is continuously increased, the cycle times of hydrogenation and thermal decomposition reaction of crude lithium carbonate are 4-5 times, and are preferably 5 times.
And directly drying the high-purity lithium carbonate without washing to obtain the battery-grade lithium carbonate powder. Greatly reduces the consumption of pure water. In the multi-stage circulation operation, the addition amount of pure water, lithium-containing filtrate or crude lithium carbonate solid is controlled by controlling the Li content, in the application, the Li content in pure water pulping is 8.5-9.5g/L, and the Li content in each stage of filtrate pulp in subsequent circulation is 6.5-9.5g/L.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment of the invention provides a preparation method of battery-grade lithium carbonate, which comprises the following specific steps:
s1, impurity removal reaction and filtration:
taking a certain amount of concentrated lithium-containing mother liquor, wherein the lithium content is 21.3g/L, adding sodium hydroxide into the lithium-containing mother liquor to adjust the pH value to 12, then adding a small amount of calcium hydroxide solution into the solution, wherein the molar ratio of the calcium hydroxide usage to the P content in the solution is 1.2:1, stirring and reacting for 30min at 60 ℃ and 300rpm, and filtering to obtain qualified lithium-containing mother liquor.
S2, high-temperature lithium precipitation reaction and filtration:
taking a certain amount of qualified lithium-containing mother liquor, dropwise adding a sodium carbonate solution with the concentration of 30wt% into the lithium-containing mother liquor, wherein the molar ratio of the sodium carbonate consumption to the Li content in the solution is 0.6:1, adding a proper amount of battery-grade lithium carbonate powder into the mixed solution to serve as reaction seed crystals, wherein the addition amount of the seed crystals is 4% of the theoretical amount of the coarse lithium carbonate, stirring and reacting at 85 ℃ and 400rpm for 120min, filtering to obtain coarse lithium carbonate solid, and returning the filtrate to an evaporation and concentration system. It should be noted that the addition of the seed crystal is beneficial to reducing the content of impurities in the coarse lithium carbonate, and the phenomenon that the lithium carbonate is adhered to the wall in the reactor is effectively avoided.
S3, multi-stage hydrogenation and thermal decomposition reaction cyclic operation:
(1) First-stage hydrogenation and thermal decomposition reaction:
mixing a certain amount of unwashed crude lithium carbonate solid with pure water to prepare slurry, wherein the Li content is 8.5g/L, and continuously introducing excessive CO into the slurry 2 Stirring and reacting for 120min at 25 ℃ until white precipitate in the solution is completely decomposed to obtain a relatively clear lithium bicarbonate solution; collecting CO after reaction 2 Introducing gas into a two-stage hydrogenation reaction kettle; filtering the solution after hydrogenation reaction by a 0.5 mu m microporous filter to remove impurities such as insoluble Si, ca and the like; filtered hydrogen carbonateAdding a proper amount of battery-grade lithium carbonate powder into the lithium solution to serve as reaction seed crystals, wherein the addition amount of the seed crystals is 4% of the theoretical amount of crude lithium carbonate, heating to 90 ℃, stirring at 400rpm for reaction for 120min, filtering while hot to obtain high-purity lithium carbonate precipitate and lithium-containing filtrate, directly obtaining the battery-grade lithium carbonate powder from the high-purity lithium carbonate precipitate without washing and drying, and using the lithium-containing filtrate as secondary hydrogenation pulping.
(2) Second-stage hydrogenation and thermal decomposition reaction:
adding a certain amount of unwashed crude lithium carbonate solid, mixing with lithium-containing filtrate after a first-stage thermal decomposition reaction for pulping, wherein the Li content is kept at 8.5g/L, and continuously introducing excessive CO into the slurry 2 Stirring and reacting for 120min at 25 ℃ until white precipitate in the solution is completely decomposed to obtain a relatively clear lithium bicarbonate solution; collecting CO after reaction 2 Introducing gas into the three-stage hydrogenation reaction kettle; filtering the solution after hydrogenation reaction by a 0.5 mu m microporous filter to remove impurities such as insoluble Si, ca and the like; adding a proper amount of battery-grade lithium carbonate powder into the filtered lithium bicarbonate solution to serve as reaction seed crystal, heating the mixture to 90 ℃, stirring and reacting the mixture at 400rpm for 120min, filtering the mixture while the mixture is hot to obtain high-purity lithium carbonate precipitate and lithium-containing filtrate, directly obtaining the battery-grade lithium carbonate powder from the high-purity lithium carbonate precipitate without washing and drying, and using the lithium-containing filtrate as three-stage hydrogenation pulping.
(3) Three-stage hydrogenation and thermal decomposition reaction:
adding a certain amount of unwashed crude lithium carbonate solid, mixing with lithium-containing filtrate after secondary thermal decomposition reaction to prepare slurry, wherein the Li content is kept at 8.5g/L, and continuously introducing excessive CO into the slurry 2 Stirring and reacting for 120min at 25 ℃ until white precipitate in the solution is completely decomposed to obtain a relatively clear lithium bicarbonate solution; collecting CO after reaction 2 Introducing gas into a four-section hydrogenation reaction kettle; filtering the solution after hydrogenation reaction by a 0.5 mu m microporous filter to remove impurities such as insoluble Si, ca and the like; adding appropriate amount of battery grade lithium carbonate powder into the filtered lithium bicarbonate solution to serve as reaction seed crystal, heating the seed crystal to 90 ℃ and the temperature of the seed crystal to 40 DEG, wherein the addition amount of the seed crystal is 4 percent of the theoretical amount of crude lithium carbonateStirring at 0rpm for reaction for 120min, filtering while hot to obtain high-purity lithium carbonate precipitate and lithium-containing filtrate, directly obtaining battery-grade lithium carbonate powder without washing and drying the high-purity lithium carbonate precipitate, and using the lithium-containing filtrate as four-stage hydrogenation pulping.
(4) Four-stage hydrogenation and thermal decomposition reaction:
adding a certain amount of unwashed crude lithium carbonate solid, mixing with lithium-containing filtrate obtained after three-stage thermal decomposition reaction to prepare slurry, wherein the Li content is kept at 8.5g/L, and continuously introducing excessive CO into the slurry 2 Stirring and reacting for 120min at 25 ℃ until white precipitate in the solution is completely decomposed to obtain a relatively clear lithium bicarbonate solution; collecting CO after reaction 2 Introducing gas into a five-section hydrogenation reaction kettle; filtering the solution after hydrogenation reaction by a 0.5 mu m microporous filter to remove impurities such as insoluble Si, ca and the like; adding a proper amount of battery-grade lithium carbonate powder into the filtered lithium bicarbonate solution to serve as reaction seed crystals, heating the seed crystals to 90 ℃, stirring at 400rpm for reaction for 120min, filtering while hot to obtain high-purity lithium carbonate precipitate and lithium-containing filtrate, directly obtaining the battery-grade lithium carbonate powder from the high-purity lithium carbonate precipitate without washing and drying, and using the lithium-containing filtrate as slurry for five-stage hydrogenation reaction.
(5) Five-stage hydrogenation and thermal decomposition reaction:
adding a certain amount of unwashed crude lithium carbonate solid, mixing with lithium-containing filtrate obtained after four-stage thermal decomposition reaction to prepare slurry, wherein the Li content is kept between 8.5g/L, and continuously introducing excessive CO into the slurry 2 Stirring and reacting for 120min at 25 ℃ until white precipitate in the solution is completely decomposed to obtain a relatively clear lithium bicarbonate solution; collecting CO after reaction 2 Gas, return CO 2 And a gas storage tank. Filtering the solution after hydrogenation reaction by a 0.5 mu m microporous filter to remove impurities such as insoluble Si, ca and the like; adding a proper amount of battery-grade lithium carbonate powder into the filtered lithium bicarbonate solution to serve as reaction crystal seeds, heating the crystal seeds to 90 ℃, stirring the mixture for reaction for 120min, filtering the mixture while the mixture is hot to obtain high-purity lithium carbonate precipitate and lithium-containing filtrate, and directly obtaining the high-purity lithium carbonate precipitate without washing and dryingAnd battery-grade lithium carbonate powder and lithium-containing filtrate are returned to a concentration system.
Wherein, the calculation formula of the lithium carbonate conversion rate is as follows:
and (3) carrying out high-temperature lithium deposition reaction on sodium carbonate in the step (2):
wherein: c. C 1 Mass concentration of Li in qualified lithium solution, c 2 The mass concentration of Li in the filtrate after the high-temperature lithium precipitation reaction; v 1 Volume of qualified lithium liquor, V 2 The volume of the filtrate after the high-temperature lithium precipitation reaction.
Hydrogenation and thermal decomposition reaction in the step (3):
wherein: w is the mass fraction of Li in the crude lithium carbonate; m is a unit of 1 M is the added mass of crude lithium carbonate in the first-stage hydrogenation reaction 2 M is the added mass of crude lithium carbonate in the two-stage hydrogenation reaction 3 Adding mass m of crude lithium carbonate in three-stage hydrogenation reaction 4 M is the added mass of crude lithium carbonate in the four-stage hydrogenation reaction 5 Adding mass of crude lithium carbonate in the five-stage hydrogenation reaction; c. C 5 The mass concentration of Li in the lithium-containing filtrate after the five-stage thermal decomposition reaction; v 5 The volume of the lithium-containing filtrate after the five-stage thermal decomposition reaction.
Example 2
This example provides a process for preparing lithium carbonate of battery grade, which differs from example 1 only in that: and in the step S2, the reaction temperature of the sodium carbonate high-temperature lithium deposition is 60 ℃.
Example 3
This example provides a process for preparing lithium carbonate of battery grade, which differs from example 1 only in that: and the reaction time of high-temperature lithium deposition in the step S2 is 60min.
Example 4
This example provides a process for preparing lithium carbonate of battery grade, which differs from example 1 only in that: in the step S2, the molar ratio of the sodium carbonate dosage to the Li content in the solution is 0.5:1.
the conversion of lithium carbonate in step S2 of examples 1-4 above was calculated.
See table 1 for calculation results:
TABLE 1 statistical table of lithium carbonate conversion in step S2 of examples 1-4
Example 5
This example provides a process for preparing lithium carbonate of battery grade, which differs from example 1 only in that: the hydrogenation reaction time in step S3 was 60min.
Example 6
This example provides a process for preparing lithium carbonate of battery grade, which differs from example 1 only in that: the hydrogenation reaction temperature in step S3 is 40 DEG C
Example 7
This example provides a process for preparing lithium carbonate of battery grade, which differs from example 1 only in that: the thermal decomposition reaction time in step S3 is 60min
Example 8
This example provides a process for preparing lithium carbonate of battery grade, which differs from example 1 only in that: the thermal decomposition reaction temperature in step S3 was 70 ℃.
The lithium carbonate conversion in step S3 of examples 1, 5-8 was calculated.
See table 2 for the calculation results:
TABLE 2 statistical table of lithium carbonate conversion in example 1, 5-8, step S3
Example 9
This example provides a process for preparing lithium carbonate of battery grade, which differs from example 1 only in that: only four stages of hydrogenation and thermal decomposition reactions are carried out.
Comparative example 1
The present comparative example provides a process for preparing battery-grade lithium carbonate, which differs from example 1 only in that: in steps S2 and S3, no battery-grade lithium carbonate powder is added as a seed crystal.
The lithium carbonate products prepared in example 1 and comparative example 1 were compared in terms of data and results, see table 3.
TABLE 3 statistical table of impurity contents of lithium carbonate products of example 1 and comparative example 1
| Content of impurities% | Na | S | Si | Ca | P |
| The national standard is less than or equal to | 0.0250 | 0.0300 | 0.0030 | 0.0050 | / |
| Example 1 | 0.0235 | 0.0267 | 0.0018 | 0.0047 | 0.0136 |
| Comparative example 1 | 0.0430 | 0.0326 | 0.0021 | 0.0038 | 0.0123 |
Comparing the morphology effect of the lithium carbonate product prepared in example 1 with that of the lithium carbonate product prepared in comparative example 1 with fig. 2 and fig. 3, it can be seen that the lithium carbonate particle prepared in example 1 with the seed crystal added has a smoother surface and better particle consistency. As can be seen from FIGS. 4 and 5, after the seed crystal is added, the inner wall of the beaker after the lithium precipitation reaction is clean and has no sticky wall phenomenon.
Comparative example 2
This comparative example provides a process for preparing battery grade lithium carbonate, differing from example 1 only in that: the two impurity removal reactions were not performed.
The lithium carbonate products prepared in example 1 and comparative example 2 were compared in terms of data and results, see table 4.
TABLE 4 statistical table of impurity contents of lithium carbonate products of example 1 and comparative example 2
It can be seen from table 4 that after twice impurity removal, the lithium carbonate product reaches the battery grade standard, and the contents of Si and Ca impurities in the lithium carbonate product without impurity removal obviously exceed the standard.
Comparative example 3
This comparative example provides a process for preparing battery grade lithium carbonate, differing from example 1 only in that: and (4) filtering the impurity removing section in the step (3) by using common filter paper without using microporous filtration, wherein the pore diameter is 40 microns.
The data and effect of the lithium bicarbonate filtrate obtained after impurity removal and filtration in the step (3) are compared with those in the following table 5:
TABLE 5 statistical table of impurity contents of lithium carbonate products of example 1 and comparative example 3
| Impurity content mg/L | Na | S | Si | Ca | P |
| Example 1 | 379.6 | 360.7 | 3.56 | 1.18 | 12.63 |
| Comparative example 3 | 397.7 | 351.3 | 12.82 | 4.19 | 12.90 |
It can be seen that: the content of Si and Ca in the filtrate can be obviously reduced by using microporous filtration, and the purity of the product is favorably improved.
Comparative example 4
This comparative example provides a process for preparing battery grade lithium carbonate, differing from example 1 only in that: only one-stage hydrogenation and thermal decomposition reaction is carried out.
Comparative example 5:
this comparative example provides a process for preparing battery grade lithium carbonate, differing from example 1 only in that: only two-stage hydrogenation and thermal decomposition reactions are carried out.
Comparative example 6:
this comparative example provides a process for preparing battery grade lithium carbonate, differing from example 1 only in that: only three-stage hydrogenation and thermal decomposition reactions are carried out.
Comparative example 7:
this comparative example provides a process for preparing battery grade lithium carbonate, differing from example 1 only in that: carrying out six-stage hydrogenation and thermal decomposition reaction.
The impurity levels and conversion rates of the lithium carbonate product of example 1, example 9, and comparative examples 4-7 were compared and the results are shown in table 6.
TABLE 6 statistical tables of impurity levels and conversion rates for lithium carbonate products of examples 1 and 9 and comparative examples 4-7
It can be seen that: along with the increase of the number of the hydrogenation and thermal decomposition reaction stages, the conversion rate of the lithium carbonate is continuously increased, and the Na and S contents in the product are also continuously increased. And when the circulation times exceed five times, the Na and S contents in the product exceed the standard and do not meet the standard of battery-grade lithium carbonate.
In summary, the preparation method of the battery-grade lithium carbonate provided by the application can be used for preparing the slurry by repeatedly utilizing the lithium-containing filtrate after the thermal decomposition reaction, so that the consumption of pure water is greatly reduced. Due to the problem of the solubility of the lithium carbonate, the less pure water is used, the less lithium carbonate is correspondingly dissolved, and the conversion rate of the solid lithium carbonate is greatly improved. The method is combined by a two-step impurity removal mode: impurity removal reaction before high-temperature lithium precipitation and microfiltration impurity removal reaction in hydrogenation reaction, and Ca impurity introduced in the impurity removal reaction in the first step can be removed in the form of calcium carbonate precipitation in the impurity removal in the second step, so that the problem of enrichment of P, si, ca and other metal ions in multi-stage cyclic hydrogenation reaction is ingeniously avoided, the cycle frequency of lithium-containing filtrate is improved, and the purity and the conversion rate of lithium carbonate products are greatly improved. Through two-step lithium precipitation reaction: the method comprises the steps of depositing lithium by using sodium carbonate at high temperature, depositing lithium by decomposing lithium bicarbonate at high temperature, and adding crystal seeds in the reaction process, thereby greatly improving the wall adhesion condition of the reactor and reducing the impurity content of the lithium carbonate product. The lithium carbonate product prepared by the process flow has high one-time qualification rate, can reach the standard of battery-grade lithium carbonate without filter pressing and washing, and greatly shortens the production flow. The process has no complicated parameter adjusting steps and distinct experimental phenomenon, and is beneficial to industrial production operation; the requirement on equipment is not high, and impurity removal reaction is performed through precipitation and impurity removal, so that the production cost is reduced.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of battery-grade lithium carbonate is characterized by comprising the following steps:
and (3) high-temperature lithium deposition: adding a sodium carbonate solution into the lithium-containing mother liquor to carry out high-temperature lithium precipitation to obtain crude lithium carbonate;
carrying out multi-stage circulation operation of hydrogenation reaction and thermal decomposition reaction on the crude lithium carbonate;
wherein the multi-stage cyclical operation comprises:
hydrogenation reaction: dividing the crude lithium carbonate into multiple parts, mixing one part of the crude lithium carbonate with water to prepare pure water slurry, continuously introducing carbon dioxide into the pure water slurry to perform hydrogenation reaction until lithium carbonate solids are completely dissolved, and filtering insoluble impurities to obtain a lithium bicarbonate solution;
thermal decomposition reaction: heating the lithium bicarbonate solution, gradually becoming turbid, generating white lithium carbonate precipitate, and separating high-purity lithium carbonate and lithium-containing filtrate;
the hydrogenation reaction and the thermal decomposition reaction are used as a primary cycle, and in the subsequent cycle, the lithium-containing filtrate is returned to be mixed with another part of the crude lithium carbonate for filtrate pulping to form filtrate slurry; the cycle number of the multi-stage cycle operation is at least 4;
and directly drying the high-purity lithium carbonate without washing to obtain the battery-grade lithium carbonate powder.
2. The method for preparing battery-grade lithium carbonate according to claim 1, wherein the multi-stage cycling operation is performed for 4 to 5 cycles, preferably for 5 cycles.
3. The method for preparing battery-grade lithium carbonate according to claim 1, wherein in the multi-stage circulation operation, the Li content in the pure water slurry is 8.5-9.5g/L, and the Li content in each stage of the filtrate slurry in the subsequent circulation is 6.5-9.5g/L.
4. The method for preparing battery-grade lithium carbonate according to claim 1, wherein the reaction temperature of the hydrogenation reaction is 20-40 ℃, and the reaction time is 60-120min;
preferably, the filtration in the hydrogenation reaction is performed by using a 0.5-2 μm microporous filter;
preferably, the CO after the reaction is collected in the hydrogenation reaction 2 And introducing the gas into the second-stage hydrogenation reaction.
5. The method for preparing battery-grade lithium carbonate according to claim 1, wherein the molar ratio of the usage amount of the sodium carbonate solution in the high-temperature lithium deposition to the Li content in the lithium-containing mother liquor is 0.5-0.8:1; further preferably 0.5 to 0.6:1;
preferably, the mass ratio of sodium carbonate in the sodium carbonate solution is 10-30%; further preferably 20% to 30%.
6. The method for preparing battery-grade lithium carbonate according to claim 5, wherein the reaction temperature of the high-temperature lithium precipitation is 60-90 ℃, the reaction time is 30-120min, and the stirring speed is 300-700rpm;
preferably, the reaction temperature of the high-temperature lithium precipitation is 80-90 ℃, the reaction time is 90-120min, and the stirring speed is 400-600rpm.
7. The preparation method of battery-grade lithium carbonate according to claim 5, characterized in that in the thermal decomposition reaction, battery-grade lithium carbonate powder serving as first seed crystals is added into the lithium bicarbonate solution, the addition amount of the first seed crystals is 2% -8% of the theoretical crude lithium carbonate amount, the mixture is heated to 70-95 ℃, and after the stirring reaction is carried out for 30-120min, the mixture is filtered while hot to obtain the high-purity lithium carbonate and the lithium-containing filtrate;
preferably, the Li content in the lithium-containing filtrate is 2.5-4g/L, and the Na and S contents are lower than 0.6g/L.
8. The method for preparing battery-grade lithium carbonate according to any one of claims 1 to 7, wherein battery-grade lithium carbonate powder serving as a second seed for reaction is further added to the system during the high-temperature lithium precipitation; the addition amount of the second crystal seed is 2% -8% of the theoretical crude lithium carbonate amount; further preferably 4% to 8%.
9. The method for preparing battery-grade lithium carbonate according to any one of claims 1 to 7, wherein the lithium-containing mother liquor is obtained by concentrating a lithium-containing solution and removing impurities; the impurity removal comprises the steps of adjusting the pH value of the concentrated lithium-containing solution to 10-14, adding a calcium hydroxide solution, stirring and reacting at 50-80 ℃ for 15-45min, precipitating phosphorus and various metal ions, and filtering to remove the phosphorus and the metal ions;
preferably, the lithium content in the lithium-containing solution after concentration is 15-25g/L, and more preferably 20-25g/L;
preferably, the molar ratio of the added amount of the calcium hydroxide solution to the content of P in the lithium-containing solution after concentration is 1-1.5:1, more preferably 1 to 1.2:1.
10. the method of any of claims 1-7, wherein the crude lithium carbonate is separated from the crude filtrate after the high temperature lithium precipitation, and the crude filtrate is returned to the evaporative concentration system.
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| CN116216749A (en) * | 2023-01-13 | 2023-06-06 | 广东邦普循环科技有限公司 | Method for preparing battery grade lithium carbonate by using salt lake lithium carbonate |
| CN116789153A (en) * | 2023-06-30 | 2023-09-22 | 江西金辉锂业有限公司 | Method for preparing high-purity lithium carbonate from crude lithium carbonate |
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