CN115286017B - Preparation method of battery-grade lithium carbonate - Google Patents
Preparation method of battery-grade lithium carbonate Download PDFInfo
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- CN115286017B CN115286017B CN202211023595.3A CN202211023595A CN115286017B CN 115286017 B CN115286017 B CN 115286017B CN 202211023595 A CN202211023595 A CN 202211023595A CN 115286017 B CN115286017 B CN 115286017B
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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 196
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 177
- 238000002360 preparation method Methods 0.000 title abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 108
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000000706 filtrate Substances 0.000 claims abstract description 54
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 48
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 38
- 238000001914 filtration Methods 0.000 claims abstract description 32
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000004537 pulping Methods 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 16
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 14
- 238000001556 precipitation Methods 0.000 claims abstract description 14
- 238000010438 heat treatment 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
- 239000012452 mother liquor Substances 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 74
- 239000012535 impurity Substances 0.000 claims description 47
- 238000004519 manufacturing process Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- 239000013078 crystal Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000010413 mother solution Substances 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 26
- 239000002244 precipitate Substances 0.000 description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000009993 causticizing Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 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
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 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
- 239000011148 porous material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 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
- 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
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000012467 final product Substances 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
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 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
- 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
-
- 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
Abstract
The invention discloses a preparation method of battery-grade lithium carbonate, and relates to the technical field of battery-grade lithium carbonate. Adding sodium carbonate solution into lithium-containing mother liquor to carry out high Wen Chen lithium to obtain crude lithium carbonate; multistage cyclic operation of hydrogenation and thermal decomposition of crude lithium carbonate: mixing crude lithium carbonate with 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 lithium bicarbonate solution until precipitation is generated, and separating high-purity lithium carbonate and lithium-containing filtrate; returning the filtrate containing lithium to be mixed with another part of crude lithium carbonate for filtrate pulping to form filtrate slurry; the number of cycles of the multistage cyclic operation is at least 4. The lithium-containing filtrate after the thermal decomposition reaction is recycled for pulping, so that the pure water consumption is greatly reduced. Because of the problem of solubility of lithium carbonate, the less the pure water is used, the less the correspondingly dissolved lithium carbonate is, 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
The lithium carbonate is used as an important compound of lithium salt and is widely used in the new energy automobile industry, and most of positive electrode materials such as lithium cobaltate, lithium nickelate, lithium iron phosphate, lithium nickelate manganate and the like are prepared by using the lithium carbonate as a raw material.
The current production method of battery grade lithium carbonate mainly comprises a high Wen Chen lithium method, an electrolytic method, a causticizing method, a hydrogenation decomposition method and the like. The commonly used high Wen Chen lithium method is to precipitate a lithium-containing solution and a sodium carbonate solution at a high temperature to generate lithium carbonate, and has the advantages of high conversion rate, high reaction speed and the like, but also has the productionThe problem of excessive sodium impurity content in the product; the electrolysis method is mainly to electrolyze saturated lithium salt solution to obtain high-purity lithium hydroxide, and then to 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 higher production cost; the causticizing 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 the production flow is longer, and the operation cost is higher; the hydrogenation decomposition method refers to introducing excessive CO into a poorly soluble lithium carbonate solution 2 The lithium bicarbonate solution is heated and is easy to decompose, and the lithium bicarbonate can be decomposed in a heating mode to generate battery-grade lithium carbonate.
At present, a hydrogenation process is adopted in China patent 200710019052.3, namely a process method for preparing high-purity lithium carbonate by using salt lake lithium resources, industrial grade lithium carbonate is prepared by taking salt lake brine as a raw material, and CO is introduced 2 After gas hydrogenation and related impurity removal processes, decomposing lithium bicarbonate under the negative pressure condition, and washing for multiple times to prepare battery-grade lithium carbonate; patent CN106517258B, "preparation method of battery grade lithium carbonate", is characterized in that lithium bicarbonate solution is obtained by hydrogenating industrial grade lithium carbonate, lithium bicarbonate solution is heated to obtain higher purity lithium carbonate solid, the obtained lithium carbonate and calcium hydroxide are causticized to prepare lithium hydroxide, and finally CO is introduced into the lithium hydroxide causticizing solution 2 And 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 method can be qualified after being washed for many times, the consumption of pure water is large, 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 present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of battery-grade lithium carbonate.
The invention is realized in the following way:
in a first aspect, the present invention provides a method for preparing battery grade lithium carbonate, comprising:
high Wen Chenli: adding sodium carbonate solution into the lithium-containing mother solution to carry out high Wen Chen lithium to obtain crude lithium carbonate;
performing multistage cyclic operation of hydrogenation reaction and thermal decomposition reaction on the crude lithium carbonate;
wherein the multi-segment cyclic operation comprises:
hydrogenation reaction: dividing the crude lithium carbonate into a plurality of parts, mixing one part with water to prepare pure water slurry, continuously introducing carbon dioxide into the pure water slurry for hydrogenation reaction until the lithium carbonate solid is completely dissolved, and filtering insoluble impurities to obtain a lithium bicarbonate solution;
thermal decomposition reaction: heating the lithium bicarbonate solution, gradually clouding the solution, generating white precipitation of lithium carbonate, and separating high-purity lithium carbonate from a lithium-containing filtrate;
the hydrogenation reaction and the thermal decomposition reaction are used as a primary circulation, and in a subsequent circulation, the filtrate containing lithium is returned to be mixed with another part of crude lithium carbonate for filtrate pulping to form filtrate slurry; the number of cycles of the multistage cyclic operation is at least 4;
the high-purity lithium carbonate is directly dried without washing to obtain the 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 after the thermal decomposition reaction is recycled for pulping, so that the pure water consumption is greatly reduced. Because of the problem of solubility of lithium carbonate, the less the pure water is used, the less the correspondingly dissolved lithium carbonate is, and the conversion rate of the solid lithium carbonate is greatly improved. Through filtering and impurity removing reaction of the micropores in the hydrogenation reaction, the problem of enrichment of P, si, ca and other metal ions in the multistage cyclic hydrogenation reaction is skillfully avoided, the cycle times of the lithium-containing filtrate are improved, and the purity and conversion rate of the lithium carbonate product are greatly improved. Through two-step lithium precipitation reaction: the sodium carbonate is high in Wen Chen lithium, and the lithium bicarbonate is decomposed at high temperature to precipitate lithium, so that the impurity content of a lithium carbonate product is reduced. The lithium carbonate product prepared by the process flow disclosed by the invention 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 complex parameter adjusting step and clear experimental phenomenon, and is beneficial to industrial production operation; the equipment requirements are not high, and the impurity removal reaction is carried out through precipitation, 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 that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a method for preparing battery grade lithium carbonate provided by the invention;
FIG. 2 is an SEM image of a lithium carbonate product of example 1 of the present invention;
FIG. 3 is an SEM image of a lithium carbonate product of comparative example 1 of the present invention;
FIG. 4 is a diagram of the inner wall of a beaker after the lithium precipitation reaction in example 1 of the present invention;
FIG. 5 is a diagram of the inner wall of a beaker after the lithium precipitation reaction according to comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
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 lithium-containing mother liquor, wherein the impurity removal comprises the steps of adjusting the pH of the concentrated lithium-containing solution to be between 10 and 14, adding a calcium hydroxide solution, wherein the lithium content in the concentrated lithium-containing solution is 15-25g/L, and the molar ratio of the addition of the calcium hydroxide solution to the P content in the concentrated lithium-containing solution is 1-1.5:1, stirring and reacting for 15-45min at 50-80 ℃, precipitating phosphorus and various metal ions, and filtering to remove.
Preferably, the lithium content of the concentrated solution is between 20 and 25 g/L; regulating the pH value of the lithium-containing mother solution to be between 10 and 12; the molar ratio of the dosage of the calcium hydroxide to the content of P 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 thatConversion to Ca 3 (PO 4 ) 2 The corresponding sediment is generated by other metal ions under alkaline condition, and is removed by filtration, and the reaction formula is as follows:
M n+ +nOH - →M(OH) n ↓(M n+ is metal ion)
S2, high Wen Chen lithium.
Adding sodium carbonate solution into the lithium-containing mother solution for high-temperature lithium precipitation and separation to obtain crude lithium carbonate and crude filtrate, and returning the crude filtrate to an evaporation concentration system.
Specifically, in the high Wen Chen lithium process, the mass ratio of sodium carbonate in the sodium carbonate solution is 10% -30%, and the molar ratio of the dosage of the sodium carbonate solution to the Li content in the lithium-containing mother solution is 0.5-0.8:1, a step of; the reaction temperature of high Wen Chen lithium is 60-90 ℃, the reaction time is 30-120min, and the stirring speed is 300-700rpm; in the reaction process, white precipitate is generated in the solution continuously, and crude lithium carbonate is obtained by filtering, wherein the reaction formula is as follows:
preferably, in the high Wen Chen lithium process, the mass ratio of sodium carbonate in the sodium carbonate solution is 20-30%, and the molar ratio of the dosage of the sodium carbonate solution to the Li content in the lithium-containing mother solution is 0.5-0.6:1, a step of; the reaction temperature of high Wen Chen lithium is 80-90 ℃, the reaction time is 90-120min, and the stirring speed is 400-600rpm.
Further, a battery grade lithium carbonate powder was also added to the system at high Wen Chen lithium, which served as a second seed for the reaction; the addition amount of the second seed crystal is 2% -8% of the theoretical coarse lithium carbonate amount; further preferably 4% to 8%. It is noted that the addition of the seed crystal is favorable for reducing the impurity content in the crude lithium carbonate, and effectively avoids the phenomenon that the lithium carbonate in the reactor adheres to the wall.
S3, multi-section circulation operation.
Performing multistage circulation operation of hydrogenation reaction and thermal decomposition reaction on the crude lithium carbonate; wherein the multi-segment cyclic operation comprises:
hydrogenation reaction: dividing crude lithium carbonate into a plurality of parts, mixing one part with water to prepare pure water slurry, continuously introducing carbon dioxide into the pure water slurry for hydrogenation reaction until lithium carbonate solid is completely dissolved, and filtering insoluble impurities to obtain lithium bicarbonate solution; the reaction temperature of the hydrogenation reaction is 20-40 ℃ and the reaction time is 60-120min; the filtration in the hydrogenation reaction adopts a microporous filter of 0.5-2 mu m, the microporous filter can remove Si, ca and other impurities, the primary qualification rate of the product is greatly improved, the repeated washing is not needed, and the CO after the reaction is collected in the hydrogenation reaction 2 The gas is introduced into the next hydrogenation reaction, so that CO is greatly improved 2 Is used for recycling the waste water. Impurity removal reaction is carried out before high Wen Chen lithium reaction, and 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 lithium bicarbonate solution, gradually clouding the solution, generating white precipitation of lithium carbonate, separating high-purity lithium carbonate from lithium-containing filtrate, wherein the Li content in the lithium-containing filtrate is 2.5-4g/L, and the Na and S content is lower than 0.6g/L.
In the thermal decomposition reaction, adding battery grade lithium carbonate powder serving as a first seed crystal into the lithium bicarbonate solution, wherein the addition amount of the first seed crystal is 2% -8% of the theoretical coarse lithium carbonate, heating to 70-95 ℃, stirring and reacting for 30-120min, and filtering while the solution is hot to obtain high-purity lithium carbonate and lithium-containing filtrate.
The hydrogenation reaction and the thermal decomposition reaction are used as a primary circulation, and in the subsequent circulation, the filtrate containing lithium is returned to be mixed with another part of crude lithium carbonate for filtrate pulping to form filtrate slurry; the lithium-containing filtrate after the thermal decomposition reaction is recycled for pulping, so that the pure water consumption is greatly reduced. Because of the problem of solubility of lithium carbonate, the less the pure water is used, the less the correspondingly dissolved lithium carbonate is, 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; the filtrate of the thermal decomposition reaction is continuously recycled, and the Na and S contents are continuously enriched, so that the Na and S impurity contents in the product lithium carbonate are continuously increased, and the cycle times of the hydrogenation and thermal decomposition reaction of the crude lithium carbonate are 4-5 times, preferably 5 times.
And directly drying the high-purity lithium carbonate without washing to obtain the battery grade lithium carbonate powder. The consumption of pure water is greatly reduced. In the multistage 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 filtrate slurry in the subsequent circulation is 6.5-9.5g/L.
The features and capabilities of the present invention are described in further detail below in connection with the 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 solution, wherein the lithium content is 21.3g/L, adding sodium hydroxide into the lithium-containing mother solution to adjust the pH value to 12, and then adding a small amount of calcium hydroxide solution into the solution, wherein the molar ratio of the calcium hydroxide consumption 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 Wen Chen lithium reaction and filtration:
taking a certain amount of qualified lithium-containing mother liquor, and 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: and 1, adding a proper amount of battery grade lithium carbonate powder into the mixed solution to serve as a reaction seed crystal, wherein the addition amount of the seed crystal is 4% of the theoretical crude lithium carbonate, stirring and reacting for 120min at 85 ℃ and 400rpm, filtering to obtain crude lithium carbonate solid, and returning filtrate to an evaporation concentration system. It is noted that the addition of the seed crystal is favorable for reducing the impurity content in the crude lithium carbonate, and effectively avoids the phenomenon that the lithium carbonate in the reactor adheres to the wall.
S3, performing multistage hydrogenation and thermal decomposition reaction cyclic operation:
(1) And (3) a 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, so as to obtain a relatively clear lithium bicarbonate solution; collecting the reacted CO 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 insoluble Si, ca and other impurities; and adding a proper amount of battery grade lithium carbonate powder into the filtered lithium bicarbonate solution to serve as a reaction seed crystal, wherein the addition amount of the seed crystal is between 4% of the theoretical coarse lithium carbonate amount, heating to 90 ℃, stirring at 400rpm for reaction for 120min, and filtering while the solution is hot to obtain high-purity lithium carbonate precipitate and lithium-containing filtrate, wherein the high-purity lithium carbonate precipitate can be directly used for preparing battery grade lithium carbonate powder without washing and drying, and the lithium-containing filtrate is used for preparing slurry by two-stage hydrogenation reaction.
(2) Two-stage hydrogenation and thermal decomposition reaction:
adding a certain amount of unwashed crude lithium carbonate solid, mixing with a section of filtrate containing lithium after thermal decomposition reaction, pulping, wherein 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, so as to obtain a relatively clear lithium bicarbonate solution; collecting the reacted CO 2 Introducing gas into a three-section hydrogenation reaction kettle; after hydrogenation reactionFiltering the solution of (2) by a 0.5 mu m microporous filter to remove insoluble Si, ca and other impurities; and adding a proper amount of battery grade lithium carbonate powder into the filtered lithium bicarbonate solution to serve as a reaction seed crystal, wherein the adding amount of the seed crystal is between 4% of the theoretical coarse lithium carbonate amount, heating to 90 ℃, stirring at 400rpm for reaction for 120min, and filtering while the solution is hot to obtain high-purity lithium carbonate precipitate and lithium-containing filtrate, wherein the high-purity lithium carbonate precipitate can be directly used for preparing battery grade lithium carbonate powder without washing and drying, and the lithium-containing filtrate is used for three-stage hydrogenation pulping.
(3) Three-stage hydrogenation and thermal decomposition reaction:
adding a certain amount of unwashed crude lithium carbonate solid, mixing with the lithium-containing filtrate after the two-stage thermal decomposition reaction, 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, so as to obtain a relatively clear lithium bicarbonate solution; collecting the reacted CO 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 insoluble Si, ca and other impurities; and adding a proper amount of battery grade lithium carbonate powder into the filtered lithium bicarbonate solution to serve as a reaction seed crystal, wherein the adding amount of the seed crystal is between 4% of the theoretical coarse lithium carbonate amount, heating to 90 ℃, stirring at 400rpm for reaction for 120min, and filtering while the solution is hot to obtain high-purity lithium carbonate precipitate and lithium-containing filtrate, wherein the high-purity lithium carbonate precipitate can be directly used for preparing battery grade lithium carbonate powder without washing and drying, and the lithium-containing filtrate is used for four-stage hydrogenation pulping.
(4) Four-stage hydrogenation and thermal decomposition reaction:
adding a certain amount of unwashed crude lithium carbonate solid, mixing with the lithium-containing filtrate after three-stage thermal decomposition reaction, 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, so as to obtain a relatively clear lithium bicarbonate solution; collecting the reacted CO 2 Introducing gas into a five-stage hydrogenation reaction kettle; filtering the solution after hydrogenation reaction by a 0.5 mu m microporous filter to remove insoluble Si, ca and other impurities; adding a proper amount of battery grade lithium carbonate powder into the filtered lithium bicarbonate solutionThe high-purity lithium carbonate precipitate and a lithium-containing filtrate are obtained by filtering while the high-purity lithium carbonate precipitate is hot after the reaction is carried out for 120min by heating to 90 ℃ and stirring at 400rpm, and the high-purity lithium carbonate precipitate can be directly obtained into battery-grade lithium carbonate powder after being dried without washing, and the lithium-containing filtrate is used for pulping by five-stage hydrogenation.
(5) Five-stage hydrogenation and thermal decomposition reaction:
adding a certain amount of unwashed crude lithium carbonate solid, mixing with the lithium-containing filtrate after four-stage thermal decomposition reaction, pulping, 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, so as to obtain a relatively clear lithium bicarbonate solution; collecting the reacted CO 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 insoluble Si, ca and other impurities; and adding a proper amount of battery grade lithium carbonate powder into the filtered lithium bicarbonate solution to serve as reaction seed crystals, wherein the addition amount of the seed crystals is between 4% of the theoretical coarse lithium carbonate amount, heating to 90 ℃, stirring and reacting for 120min, filtering while the solution is hot to obtain high-purity lithium carbonate precipitate and lithium-containing filtrate, and directly obtaining the battery grade lithium carbonate powder after the high-purity lithium carbonate precipitate is not washed and dried, and returning the lithium-containing filtrate to a concentration system.
The calculation formula of the lithium carbonate conversion rate is as follows:
sodium carbonate high Wen Chen lithium reaction in step (2):
wherein: c 1 C, the mass concentration of Li in the qualified lithium liquid 2 The mass concentration of Li in the filtrate after the reaction of the high Wen Chen lithium is as follows; v (V) 1 For qualified lithium liquid volume, V 2 Is as high as Wen Chen lithium reaction filtrate volume.
In the step (3), hydrogenation and thermal decomposition reactions:
wherein: w is the mass fraction of Li in the crude lithium carbonate; m is m 1 Adding mass, m to crude lithium carbonate in a first hydrogenation reaction 2 Adding mass, m to the crude lithium carbonate in the second-stage hydrogenation reaction 3 Adding mass, m to crude lithium carbonate in three-stage hydrogenation reaction 4 Adding mass, m to crude lithium carbonate in four-stage hydrogenation reaction 5 Adding mass to crude lithium carbonate in five-stage hydrogenation reaction; c 5 The mass concentration of Li in the lithium-containing filtrate after five-stage thermal decomposition reaction; v (V) 5 The volume of the filtrate containing lithium after five-stage thermal decomposition reaction is five.
Example 2
This example provides a process for preparing battery grade lithium carbonate, which differs from example 1 only in that: the sodium carbonate in step S2 had a lithium reaction temperature of Wen Chen ℃up to 60 ℃.
Example 3
This example provides a process for preparing battery grade lithium carbonate, which differs from example 1 only in that: the high Wen Chen lithium reaction time in step S2 was 60min.
Example 4
This example provides a process for preparing battery grade lithium carbonate, which differs from example 1 only in that: in the step S2, the molar ratio of the sodium carbonate to the Li content in the solution is 0.5:1.
the lithium carbonate conversion in step S2 of the above examples 1 to 4 was calculated.
The calculation results are shown in Table 1:
TABLE 1 statistical Table of lithium carbonate conversion in examples 1-4 step S2
Example 5
This example provides a process for preparing battery grade lithium carbonate, which differs from example 1 only in that: the hydrogenation time in step S3 was 60min.
Example 6
This example provides a process for preparing battery grade lithium carbonate, which differs from example 1 only in that: the hydrogenation reaction temperature in the step S3 is 40 DEG C
Example 7
This example provides a process for preparing battery grade lithium carbonate, which differs from example 1 only in that: the thermal decomposition reaction time in the step S3 is 60min
Example 8
This example provides a process for preparing battery grade lithium carbonate, 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 example 1, examples 5-8 was calculated.
Please refer to table 2 for the calculation results:
TABLE 2 statistical Table of lithium carbonate conversion in step S3 of examples 1, 5-8
Example 9
This example provides a process for preparing battery grade lithium carbonate, which differs from example 1 only in that: only four-stage hydrogenation and thermal decomposition reactions are carried out.
Comparative example 1
This comparative example provides a process for preparing battery grade lithium carbonate, which differs from example 1 only in that: in both steps S2 and S3, no battery grade lithium carbonate powder was added as seed crystal.
The lithium carbonate products prepared in example 1 and comparative example 1 were subjected to data effect comparison, and the comparison results are shown in Table 3.
TABLE 3 impurity content statistics for lithium carbonate products of example 1 and comparative example 1
| Impurity content% | Na | S | Si | Ca | P |
| 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 |
As can be seen from comparing the morphological effects of the lithium carbonate products prepared in example 1 with those of comparative example 1 with reference to fig. 2 and 3, the surface of the lithium carbonate particles prepared in example 1 with seed crystal added is smoother, and the uniformity of the particles is better. As can be seen from fig. 4 and 5, after the seed crystal is added, the inner wall of the beaker is clean and has no wall sticking phenomenon after the lithium precipitation reaction.
Comparative example 2
This comparative example provides a process for preparing battery grade lithium carbonate, which differs from example 1 only in that: neither impurity removal reaction was performed.
The lithium carbonate products prepared in example 1 and comparative example 2 were subjected to data effect comparison, and the comparison results are shown in Table 4.
TABLE 4 impurity content statistics for lithium carbonate products of example 1 and comparative example 2
As can be seen from Table 4, after two times of impurity removal, the lithium carbonate product reaches the battery grade standard, and the impurity content of Si and Ca in the lithium carbonate product without impurity removal is obviously over-standard.
Comparative example 3
This comparative example provides a process for preparing battery grade lithium carbonate, which differs from example 1 only in that: the filtration and impurity removal section in the step (3) does not use micro-pore filtration, and only uses common filter paper for filtration, and the pore size is 40 microns.
Comparison of data effects of lithium bicarbonate filtrate after impurity removal and filtration in step (3) is shown in table 5:
TABLE 5 impurity content statistics for 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, which is beneficial to improving the purity of the product.
Comparative example 4
This comparative example provides a process for preparing battery grade lithium carbonate, which differs from example 1 only in that: only one stage of hydrogenation and thermal decomposition reaction is carried out.
Comparative example 5:
this comparative example provides a process for preparing battery grade lithium carbonate, which differs 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, which differs 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, which differs from example 1 only in that: carrying out six-stage hydrogenation and thermal decomposition reaction.
The impurity content and conversion of the lithium carbonate products of example 1, example 9 and comparative examples 4 to 7 were compared, and the comparison results are shown in Table 6.
TABLE 6 statistical tables of impurity levels and conversions for the 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 hydrogenation and thermal decomposition reaction sections, the conversion rate of lithium carbonate is continuously increased, and the Na and S contents in the product are also continuously increased. When the cycle times exceeds five times, the Na and S contents in the product exceed the standard, and the standard of the battery grade lithium carbonate is not met.
In summary, the preparation method of the battery grade lithium carbonate provided by the application greatly reduces the consumption of pure water by pulping through recycling the lithium-containing filtrate after the thermal decomposition reaction. Because of the problem of solubility of lithium carbonate, the less the pure water is used, the less the correspondingly dissolved lithium carbonate is, and the conversion rate of the solid lithium carbonate is greatly improved. The two steps of impurity removal modes are combined: the impurity removing reaction before the lithium is high Wen Chen, the microporous filtering impurity removing reaction in the hydrogenation reaction is performed, meanwhile, ca impurities introduced in the impurity removing reaction in the first step can be removed in the form of calcium carbonate precipitation in the impurity removing reaction in the second step, the problem of P, si, ca and other metal ions enrichment in the multi-stage cyclic hydrogenation reaction is skillfully avoided, the cycle times of the 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 sodium carbonate is Wen Chen lithium and lithium bicarbonate are decomposed at high temperature to precipitate lithium, and seed crystals are added in the reaction process, so that the wall sticking condition of the reactor is greatly improved, and the impurity content of a lithium carbonate product is reduced. The lithium carbonate product prepared by the process flow disclosed by the invention 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 complex parameter adjusting step and clear experimental phenomenon, and is beneficial to industrial production operation; the equipment requirements are not high, and the impurity removal reaction is carried out through precipitation, so that the production cost is reduced.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (17)
1. A method for preparing battery grade lithium carbonate, comprising the steps of:
high Wen Chenli: adding sodium carbonate solution into the lithium-containing mother solution to carry out high Wen Chen lithium to obtain crude lithium carbonate, wherein the reaction temperature of Gao Wenchen lithium is 80-90 ℃ and the reaction time is 90-120min; adding battery grade lithium carbonate powder serving as a second seed for reaction to the system at the time of Gao Wenchen lithium; the addition amount of the second seed crystal is 2% -8% of the theoretical coarse lithium carbonate amount; the lithium-containing mother solution is obtained by concentrating and removing impurities from lithium-containing solution; the impurity removal comprises the steps of adjusting the pH value of the concentrated lithium-containing solution to be between 10 and 14, adding a calcium hydroxide solution, stirring and reacting for 15 to 45 minutes at the temperature of between 50 and 80 ℃, precipitating phosphorus and various metal ions, and filtering and removing the phosphorus and the various metal ions;
performing multistage cyclic operation of hydrogenation reaction and thermal decomposition reaction on the crude lithium carbonate;
wherein the multi-segment cyclic operation comprises:
hydrogenation reaction: dividing the crude lithium carbonate into a plurality of parts, mixing one part with water to prepare pure water slurry, continuously introducing carbon dioxide into the pure water slurry to carry out hydrogenation reaction until lithium carbonate solid is completely dissolved, filtering insoluble impurities to obtain lithium bicarbonate solution, and filtering in the hydrogenation reaction by adopting a 0.5-2 mu m microporous filter; the reaction temperature of the hydrogenation reaction is 20-40 ℃ and the reaction time is 60-120min;
thermal decomposition reaction: heating the lithium bicarbonate solution, adding battery grade lithium carbonate powder serving as a first seed crystal into the lithium bicarbonate solution, wherein the addition amount of the first seed crystal is 2% -8% of the theoretical crude lithium carbonate amount, heating to 70-95 ℃, stirring and reacting for 30-120min, gradually clouding the solution, generating white precipitation of lithium carbonate, and filtering and separating to obtain high-purity lithium carbonate and lithium-containing filtrate;
the hydrogenation reaction and the thermal decomposition reaction are used as a primary circulation, and in a subsequent circulation, the filtrate containing lithium is returned to be mixed with another part of crude lithium carbonate for filtrate pulping to form filtrate slurry; the number of cycles of the multistage cyclic operation is at least 4;
the high-purity lithium carbonate is directly dried without washing to obtain battery grade lithium carbonate powder;
in the multi-stage circulation operation, the Li content in the pure water pulping is 8.5-9.5g/L, and the Li content in the filtrate slurry in each stage of the subsequent circulation is 6.5-9.5g/L.
2. The method for producing battery grade lithium carbonate according to claim 1, wherein the number of cycles of the multistage cyclic operation is 4 to 5.
3. The method for producing battery grade lithium carbonate according to claim 1, wherein the number of cycles of the multistage cyclic operation is 5.
4. The method for producing battery grade lithium carbonate according to claim 1, wherein CO after the reaction is collected in the hydrogenation reaction 2 And introducing 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 amount of sodium carbonate solution in Gao Wenchen lithium to the Li content in the lithium-containing mother liquor is 0.5 to 0.8:1.
6. the method for preparing battery grade lithium carbonate according to claim 1, wherein the molar ratio of the amount of sodium carbonate solution in Gao Wenchen lithium to the Li content in the lithium-containing mother liquor is 0.5 to 0.6:1.
7. the method for preparing battery grade lithium carbonate according to claim 5, wherein the mass ratio of sodium carbonate in the sodium carbonate solution is 10% -30%.
8. The method for preparing battery grade lithium carbonate according to claim 5, wherein the mass ratio of sodium carbonate in the sodium carbonate solution is 20% -30%.
9. The method for producing battery grade lithium carbonate according to claim 5, wherein the stirring speed of Gao Wenchen lithium is 300 to 700rpm.
10. The method of claim 5, wherein the stirring speed of Gao Wenchen lithium is 400-600rpm.
11. The method for preparing battery grade lithium carbonate according to claim 1, wherein the Li content in the lithium-containing filtrate is 2.5-4g/L, and the Na and S contents are less than 0.6g/L.
12. The method for producing battery grade lithium carbonate according to any one of claims 1 to 11, wherein the second seed crystal is added in an amount of 4% to 8% of the theoretical crude lithium carbonate amount.
13. The method for producing a battery grade lithium carbonate according to any one of claims 1 to 11, wherein the lithium content in the concentrated lithium-containing solution is 15 to 25g/L.
14. The method for producing a battery grade lithium carbonate according to any one of claims 1 to 11, wherein the lithium content in the concentrated lithium-containing solution is 20 to 25g/L.
15. The method for producing a battery grade lithium carbonate according to any one of claims 1 to 11, wherein the molar ratio of the addition amount of the calcium hydroxide solution to the P content in the concentrated lithium-containing solution is 1 to 1.5:1.
16. the method for producing a battery grade lithium carbonate according to any one of claims 1 to 11, wherein the molar ratio of the amount of the calcium hydroxide solution added to the P content in the concentrated lithium-containing solution is 1 to 1.2:1.
17. the method of any one of claims 1-11, wherein the crude lithium carbonate and the crude filtrate are separated after passing through the Gao Wenchen lithium, and the crude filtrate is returned to an evaporation concentration system.
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| CN103318925A (en) * | 2013-06-19 | 2013-09-25 | 海门容汇通用锂业有限公司 | Method for producing high-purity lithium carbonate by using lithium concentrate |
| CN103833053A (en) * | 2014-01-21 | 2014-06-04 | 四川天齐锂业股份有限公司 | Method of preparing high-purity lithium carbonate of the 5 N grade |
| CN106276988A (en) * | 2016-08-12 | 2017-01-04 | 青海大学 | A kind of method preparing battery-level lithium carbonate for precipitant with potassium carbonate |
| CN109368671A (en) * | 2018-12-06 | 2019-02-22 | 东营石大胜华新能源有限公司 | A kind of preparation method of high purity lithium fluoride |
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| CN202438320U (en) * | 2011-08-31 | 2012-09-19 | 四川长和华锂科技有限公司 | Reaction kettle for industrial producing high-purity lithium carbonate |
| CN106365182B (en) * | 2016-08-30 | 2017-09-29 | 荆门市格林美新材料有限公司 | The method that the industrial level lithium carbonate of pulsed hydrogenation prepares battery-level lithium carbonate |
| CN106315629B (en) * | 2016-08-30 | 2018-01-30 | 山东瑞福锂业有限公司 | A kind of technique for preparing pure Lithium Carbonate using battery-level lithium carbonate sinker disposing mother liquor |
| CN106517258B (en) * | 2016-11-23 | 2017-09-29 | 荆门市格林美新材料有限公司 | The preparation method of battery-level lithium carbonate |
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| CN103318925A (en) * | 2013-06-19 | 2013-09-25 | 海门容汇通用锂业有限公司 | Method for producing high-purity lithium carbonate by using lithium concentrate |
| CN103833053A (en) * | 2014-01-21 | 2014-06-04 | 四川天齐锂业股份有限公司 | Method of preparing high-purity lithium carbonate of the 5 N grade |
| CN106276988A (en) * | 2016-08-12 | 2017-01-04 | 青海大学 | A kind of method preparing battery-level lithium carbonate for precipitant with potassium carbonate |
| CN109368671A (en) * | 2018-12-06 | 2019-02-22 | 东营石大胜华新能源有限公司 | A kind of preparation method of high purity lithium fluoride |
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