CN117566771A - Method for preparing lithium carbonate based on supergravity reactor and lithium carbonate - Google Patents
Method for preparing lithium carbonate based on supergravity reactor and lithium carbonate Download PDFInfo
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- CN117566771A CN117566771A CN202311620811.7A CN202311620811A CN117566771A CN 117566771 A CN117566771 A CN 117566771A CN 202311620811 A CN202311620811 A CN 202311620811A CN 117566771 A CN117566771 A CN 117566771A
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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 69
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 47
- 239000013078 crystal Substances 0.000 claims abstract description 25
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 103
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 60
- 239000012267 brine Substances 0.000 claims description 53
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 53
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000009826 distribution Methods 0.000 claims description 18
- 238000004537 pulping Methods 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 abstract description 29
- 238000002425 crystallisation Methods 0.000 abstract description 8
- 230000008025 crystallization Effects 0.000 abstract description 8
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 16
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 16
- 239000012535 impurity Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005086 pumping Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 description 4
- 235000011151 potassium sulphates Nutrition 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000013049 sediment Substances 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002332 oil field water Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012795 verification Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of new energy, and discloses a method for preparing lithium carbonate based on a hypergravity reactor, which comprises the following steps: step 1: adding a soluble carbonate solution as a base solution into a hypergravity reactor; step 2: continuously adding a first solution containing lithium ions into a hypergravity reactor; step 3: and (3) introducing the product obtained in the step (2) into a reaction kettle, continuously adding a second solution containing lithium ions while stirring, and obtaining lithium carbonate after the reaction is completed. The method adopts a hypergravity reactor to perform preliminary crystallization operation to obtain liquid with uniform initial particle size, and then the liquid after preliminary crystallization is transferred into a reaction kettle to further enlarge crystals. Meanwhile, the invention also discloses lithium carbonate.
Description
Technical Field
The invention relates to the field of new energy, in particular to a method for preparing lithium carbonate based on a hypergravity reactor and lithium carbonate.
Background
The uniformity of particles and the particle size of the lithium battery cathode material directly influence the battery performance, so that manufacturers of the lithium battery cathode material reduce the content of large particles in lithium carbonate from several aspects such as shearing, sieving, jet milling and the like in order to improve the quality of lithium carbonate products. The prior art discloses a method for preparing high-quality lithium carbonate by adopting a hypergravity reactor, for example, CN110817907A discloses a treatment method for purifying high-purity lithium carbonate, the proposal only discloses that impurities are removed by the hypergravity reactor, the hypergravity reactor does not participate in any crystallization process, and the particle size distribution of the prepared lithium carbonate is wider; CN110304643a discloses a supergravity preparation method of battery-grade superfine lithium carbonate, the preparation of battery-grade superfine lithium carbonate takes brine with high lithium content and sodium carbonate aqueous solution as raw materials, a supergravity reactor is started, the rotating speed of a turntable is regulated, and the supergravity acceleration is controlled; the dispersed materials are radially thrown away under the action of centrifugal force and then impact on the inner wall of the reactor, finally the converged liquid flows out from a liquid outlet under the action of a gravity field and is collected in a product storage tank, and after aging, alcohol washing and filtering, the battery-grade superfine lithium carbonate powder can be obtained. However, only the hypergravity reactor participates in the crystallization process, and the sodium ion and potassium ion contents are higher, so that the purity of the prepared lithium carbonate is lower.
Therefore, the technical problem solved by the scheme is as follows: and preparing the lithium carbonate with high purity and narrow particle size distribution.
Disclosure of Invention
The invention mainly aims to provide a method for preparing lithium carbonate based on a hypergravity reactor, which adopts the hypergravity reactor to perform preliminary crystallization operation to obtain liquid with uniform initial particle size, and then transfers the liquid subjected to preliminary crystallization into a reaction kettle to further enlarge crystals.
Meanwhile, the invention also discloses lithium carbonate.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for preparing lithium carbonate based on a hypergravity reactor, comprising the following steps:
step 1: adding a soluble carbonate solution as a base solution into a hypergravity reactor;
step 2: continuously adding the first solution containing lithium ions into a hypergravity reactor to obtain a solution containing seed crystals;
step 3: and (3) introducing the solution obtained in the step (2) into a reaction kettle, continuously adding a second solution containing lithium ions while stirring, and obtaining lithium carbonate after the reaction is completed.
Preferably, the molar amount of carbonate in the soluble carbonate solution is 0.5 to 0.8 times the sum of the molar amounts of lithium ions in the first solution and lithium ions in the second solution; the molar ratio of lithium ions in the first solution to lithium ions in the second solution is 5-60: 40-95%.
In some embodiments of the invention, the molar amount of carbonate in the soluble carbonate solution may be selected to be 0.5, 0.6, 0.7, or 0.8 times the sum of the molar amounts of lithium ions in the first solution and lithium ions in the second solution;
the molar amount of lithium ions in the first solution and the molar ratio of lithium ions in the second solution may be selected to be 5:95, 10:90, 15:85, 20:80, 25:75, 30:70, 35:65 or 40:60, 60:40;
in the method for preparing lithium carbonate based on the hypergravity reactor, the first solution and the second solution are lithium-containing brine;
as the brine commonly used in the field, salt lake brine, salt lake intercrystalline brine and underground brine can be selected;
as possible potential raw materials, brine can also be selected from lithium-rich eluent after extraction treatment of oilfield water, coalbed methane field produced water, salt lake brine, salt lake intercrystalline brine, geothermal water, underground brine, seawater and hot spring water in the oilfield exploration process;
regardless of the raw materials, the impurities in the brine are mainly sodium ions and/or potassium ions;
if the raw materials contain metal ions which are easy to react with carbonate to generate carbonate sediment, the metal ions should be removed in advance (such as sediment by oxalic acid or oxalate, complexation by complexing agent or the like or the combination of a plurality of means) so as to ensure the normal proceeding of the subsequent reaction.
In the above method for preparing lithium carbonate based on the hypergravity reactor, the first solution is a lithium salt solution, more specifically, metal ions in the lithium salt solution are only lithium ions, and the "only" includes the situation that trace amounts of other metal elements which cannot be removed are present; the second solution is brine.
During the experiment it was found that if the metal ions in the first solution were lithium ions only, the particle size distribution would be narrower, probably due to the fact that: under the condition of no interference of other impurity metal ions, the seed crystals are purer, the particle size distribution is more uniform, the particle size of the particles with uniform particle size distribution in the reaction kettle is increased along with the increase of the particle size of the crystals, the particle size distribution is narrower, and the specification of the obtained product is more excellent.
In the method for preparing lithium carbonate based on the hypergravity reactor, the concentration of sodium ions in the brine is 0-70 g/L, the concentration of potassium ions is 0-15 g/L, and/or the concentration of lithium ions in the brine is 0.01-8 g/L.
In some embodiments of the invention, the concentration of sodium ions in the brine may be selected to be 5g/L, 10g/L, 15g/L, 20g/L, 30g/L, 40g/L, 50g/L, 60g/L, or 70g/L;
in some embodiments of the invention, the concentration of potassium ions may be selected to be 1g/L, 2g/L, 3g/L, 4g/L, 5g/L, 8g/L, 10g/L, 12g/L, or 15g/L;
in the method for preparing lithium carbonate based on the hypergravity reactor, the independent reaction temperature in each of the steps 2 to 3 is 50 to 99 ℃; preferably, the independent reaction temperature in the steps 2 to 3 is 55 to 95 ℃; more preferably, the reaction temperature in each of the steps 2 to 3 is 70 to 90 ℃.
Preferably, the first solution is filled for 0.1-2 hours;
preferably, the filling time of the second solution is 0.5-3h;
and/or, in the step 3, after the second solution is added, continuing to react for 1-3 hours;
in some embodiments of the present invention, the first solution filling time of step 2 may be selected to be 0.1h, 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, or 2.0h;
in some embodiments of the invention, the second solution of step 3 may be added for a period of time selected from 0.5h, 1h, 1.5h, 2h, 2.5h, or 3h;
in some embodiments of the invention, the independent reaction temperatures in steps 2-3 are 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 99 ℃.
In the method for preparing lithium carbonate based on the hypergravity reactor, the concentration of carbonate in the base solution is 10-32 wt%; preferably, the concentration of carbonate in the base liquid is 12-30wt%; more preferably, the concentration of carbonate in the base liquid is 15 to 25wt%.
In some embodiments of the invention, the concentration of carbonate in the base liquid may be selected to be 10wt%, 15wt%, 20wt%, 25wt%, 30wt% or 32wt%;
the carbonate is sodium carbonate and/or potassium carbonate.
In the method for preparing lithium carbonate based on the hypergravity reactor, the stirring speed of the hypergravity reactor is 2000-5000 r/min. Preferably, the stirring speed of the hypergravity reactor is 2500-4500 r/min; more preferably, the stirring speed of the hypergravity reactor is 3000-4000 r/min.
In the method for preparing lithium carbonate based on the hypergravity reactor, the molar quantity of carbonate in the soluble carbonate solution is 0.55-0.75 times of the sum of the molar quantity of lithium ions in the first solution and the molar quantity of lithium ions in the second solution; the molar ratio of lithium ions in the first solution to lithium ions in the second solution is 10-25: 75-90.
In the above method for preparing lithium carbonate based on the hypergravity reactor, in the step 3, after the reaction is completed, a slurry containing lithium carbonate is obtained;
the specific operation of separating lithium carbonate solids from a slurry containing lithium carbonate is:
filtering the slurry containing lithium carbonate, pulping and washing filter residues for 2-4 times, wherein the solid ratio of the slurry is 2:1 to 10:1, pulping water temperature is 50-99 ℃ and washing time is 0.5-3h;
after washing, the solid is dispersed into water, and is subjected to secondary stirring washing, then is filtered and is rinsed once by clean water, the temperature of the washing water is 50-99 ℃, and finally the lithium carbonate is prepared.
Meanwhile, the invention also discloses lithium carbonate, the particle size distribution of which is D10 is more than or equal to 1 mu m, D50 is more than or equal to 5 mu m and less than or equal to 90 mu m, D90 is less than or equal to 200 mu m, and the purity is battery grade lithium carbonate.
Preferably, the grain size distribution is D10 is more than or equal to 2 mu m, D50 is more than or equal to 5 mu m and less than or equal to 50 mu m, and D90 is more than or equal to 100 mu m;
preferably, the particle size distribution is D10.gtoreq.2 μm, D50.ltoreq.8μm, and D90.ltoreq.30μm.
The lithium carbonate is prepared by any one of the methods.
One of the above technical solutions of the present invention has at least one of the following advantages or beneficial effects:
in the invention, the hypergravity reactor is adopted to perform preliminary crystallization operation to obtain liquid with uniform initial particle size, and then the liquid subjected to preliminary crystallization is transferred into the reaction kettle to further enlarge crystals, so that the particle size distribution range of lithium carbonate can be effectively controlled, and the impurity content is low.
In a further preferred scheme of the invention, a purer lithium salt solution is added into a hypergravity reactor for reaction, so that the obtained seed crystals are purer, the grain size distribution is narrower after the grain size of the crystals in the reaction kettle is increased, and the specification of the obtained product is more excellent.
In the invention, the grain size distribution and impurity content of the product are optimized by controlling the distribution proportion of the first solution and the second solution, and experiments prove that the grain size control is better and the impurity content is less when the proportion of the first solution and the second solution is closer to 25:75, and the reason is that: in the hypergravity reactor, sodium carbonate reacts with lithium ions to obtain seed crystal grains, the seed crystal grains enter a reaction kettle to grow and increase, if the lithium ions occupy a relatively high proportion in the step 3, the seed crystal grains are fewer, and when the seed crystal grains grow in the reaction kettle, the grain size of the seed crystal grains is overlarge; if the lithium ion content is low in step 3, too many small-sized crystals have an aggregated property, and the particle size is increased, and in this process, since the particle size is not increased normally, a large amount of impurities are contained therein.
In the invention, a plurality of reaction kettles can be matched through the hypergravity reactor, so that the expanded production is realized, and the production efficiency is effectively improved.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
First part
The part takes brine as a raw material for preparing seed crystals to produce lithium carbonate.
Example 1
A method for preparing lithium carbonate, comprising the following steps:
step 1: reaction kettle base solution: sodium carbonate is used as base solution, and sodium carbonate solution with the concentration of 25 weight percent is prepared in a reaction kettle; the temperature of the sodium carbonate solution is 60 ℃;
step 2: adding the base solution into a hypergravity reactor;
the specification of the hypergravity reactor is as follows: 500L,1500L/h;
parameters of the hypergravity reactor are controlled as follows: 4000r/min, 60 ℃ and normal pressure;
the molar quantity of sodium carbonate in the base solution added into the hypergravity reactor is 0.6 times of the molar quantity of lithium ions in the step 3 and the step 4; the reaction temperature in the hypergravity reactor is 60 ℃;
step 3: pumping brine into a supergravity reactor through a metering pump, wherein the feeding time is 1h; directly pumping the reacted solution into the reaction kettle in the step 4 at one time after the charging is finished;
step 4: taking the solution after the reaction in the step 3 as a base solution, and adding the rest brine by a metering pump; the charging time is 1.5h, and the temperature is kept for 2h after the charging is completed; the reaction temperature in the reaction kettle is controlled at 90 ℃;
the main components of the brine in the step 3 and the step 4 are as follows:
lithium sulfate 1mol/L;
sodium sulfate 1.2mol/L;
potassium sulfate 0.12mol/L;
the molar ratio of the brine in the step 3 to the brine in the step 4 is 2:8, and the molar ratio of the brine to the lithium ion is 2:8.
Step 5: and (3) filtering the product obtained in the step (4) through a plate frame, pulping and washing filter residues for 3 times, wherein the pulping liquid consists of lithium carbonate and pure water, and the solid ratio (weight ratio) is 5:1, pulping water at 60 ℃ and washing for 2 hours; and (3) washing the plate frame for the first time after the plate frame is stirred and washed for the second time, wherein water used for washing is pure water with the temperature of 60 ℃, and finally, the high-quality lithium carbonate with low potassium and low sodium is prepared.
Example 2
Substantially the same as in example 1, the difference is that: the molar ratio of the brine in the step 3 to the brine in the step 4 is 5:95, and the molar ratio of the brine to the lithium ion is 5:95.
Example 3
Substantially the same as in example 1, the difference is that: the molar ratio of the brine in the step 3 to the brine in the step 4 is 1:9, and the molar ratio of the brine to the lithium ion is 1:9.
Example 4
Substantially the same as in example 1, the difference is that: the molar ratio of the brine in the step 3 to the brine in the step 4 is 25:75, and the molar ratio of the brine to the lithium ion is 25:75.
Example 5
Substantially the same as in example 1, the difference is that: the molar ratio of the brine in the step 3 to the brine in the step 4 is 3:7, and the molar ratio of the brine to the lithium ion is 3:7.
Example 6
Substantially the same as in example 1, the difference is that: the molar ratio of brine in the step 3 to brine in the step 4 is 4:6, and the molar ratio of lithium ions contained in the step 3 to brine in the step 4:6.
Example 7
Substantially the same as in example 2, except that: the sodium carbonate in the base solution is replaced by potassium carbonate with the concentration of 32 weight percent, and the molar quantity of the potassium carbonate and the sodium carbonate is equal; the reaction temperature of the steps 1 to 5 is adjusted to 60 ℃; the feeding time in the step 3 is 0.1h; the charging time in the step 4 is 0.5h, and the heat preservation time is 1h; the stirring speed of the hypergravity reactor is 2000r/min.
Example 8
Substantially the same as in example 2, except that: the concentration of sodium carbonate in the base solution is 10wt%; the reaction temperature of the steps 1 to 5 is adjusted to 50 ℃; the feeding time in the step 3 is 2 hours; the charging time in the step 4 is 3 hours, and the heat preservation time is 3 hours; the stirring speed of the hypergravity reactor is 5000r/min; .
Example 9
Substantially the same as in example 2, except that: the molar ratio of sodium carbonate to lithium was 0.8:1.
Example 10
Substantially the same as in example 2, except that: the molar ratio of sodium carbonate to lithium was 0.5:1.
Second part
The part takes lithium sulfate solution as the preparation raw material of seed crystal to produce lithium carbonate.
Example 11
A method for preparing lithium carbonate, comprising the following steps:
step 1: reaction kettle base solution: sodium carbonate is used as base solution, and sodium carbonate solution with the concentration of 25 weight percent is prepared in a reaction kettle; the temperature of the sodium carbonate solution is 90 ℃;
step 2: adding the base solution into a hypergravity reactor;
the specification of the hypergravity reactor is as follows: 500L,1500L/h;
parameters of the hypergravity reactor are controlled as follows: 4000r/min, 90 ℃ and normal pressure;
the molar quantity of sodium carbonate in the base solution added into the hypergravity reactor is 0.6 times of the molar quantity of lithium ions in the step 3 and the step 4; the reaction temperature in the hypergravity reactor is 90 ℃;
step 3: pumping lithium sulfate solution into a supergravity reactor through a metering pump, wherein the charging time is 1h; directly pumping the reacted solution into the reaction kettle in the step 4 at one time after the charging is finished;
the concentration of lithium sulfate is 1mol/L;
step 4: taking the reacted slurry in the step 3 as a base solution, and adding brine by a metering pump; the charging time is 1.5h, and the temperature is kept for 2h after the charging is completed; the reaction temperature in the reaction kettle is controlled at 90 ℃;
the main components of the brine in the step 4 are as follows:
lithium sulfate 1mol/L;
sodium sulfate 1.2mol/L;
potassium sulfate 0.12mol/L;
the ratio of lithium sulfate in the step 3 to the step 4 is 2:8.
Step 5: filtering the product in the step 4 through a plate frame, pulping and washing filter residues for 3 times, wherein the pulping liquid-solid ratio is 5:1, pulping water at 90 ℃ and washing for 2 hours; and (3) washing the plate frame by secondary stirring, and then leaching for the first time, wherein the washing water temperature is 90 ℃, so that the low-potassium and low-sodium high-quality lithium carbonate is finally prepared.
Example 12
Substantially the same as in example 11, except that: the ratio of lithium sulfate in the step 3 to the step 4 is 5:95.
Example 13
Substantially the same as in example 11, except that: the ratio of lithium sulfate in the step 3 to the step 4 is 1:9.
Example 14
Substantially the same as in example 11, except that: the ratio of lithium sulfate in step 3 to that in step 4 was 25:75.
Example 15
Substantially the same as in example 11, except that: the ratio of lithium sulfate in the step 3 to the step 4 is 3:7.
Comparative example 1
Step 1: reaction kettle base solution: sodium carbonate is used as base solution, and sodium carbonate solution with the concentration of 25 weight percent is prepared in a reaction kettle; the temperature of the sodium carbonate solution is 60 ℃;
step 2: adding the base solution into a hypergravity reactor;
the specification of the hypergravity reactor is as follows: 500L,1500L/h;
parameters of the hypergravity reactor are controlled as follows: 4000r/min, 60 ℃ and normal pressure;
the reaction temperature in the hypergravity reactor is 90 ℃; the molar quantity of sodium carbonate in the base solution added into the hypergravity reactor is 0.6 times of the molar quantity of lithium ions in the step 3;
step 3: pumping the brine solution into a supergravity reactor through a metering pump, wherein the feeding time is 2 hours; directly pumping the reacted slurry into the reaction kettle in the step 4 at one time after the charging is finished;
the main components of the brine in the step 3 are as follows:
the concentration of lithium sulfate is 1mol/L;
sodium sulfate 1.2mol/L;
potassium sulfate 0.12mol/L;
step 4: keeping the reaction kettle for 1h, and controlling the reaction temperature at 90 ℃;
step 5: filtering the product in the step 4 through a plate frame, pulping and washing filter residues for 3 times, wherein the pulping liquid-solid ratio is 5:1, pulping water at 60 ℃ and washing for 2 hours; and (3) washing the plate frame by secondary stirring, and washing for one time, wherein the washing temperature is 60 ℃, so that the lithium carbonate is finally prepared.
Comparative example 2
Substantially the same as comparative example 1 except that potassium carbonate was used in place of sodium carbonate in the base solution, the molar amounts of the two being equal; the reaction temperature in the steps 1 to 5 was adjusted to 60 ℃.
Comparative example 3
The procedure is substantially as in comparative example 1, except that the molar amount of sodium carbonate in the base liquid fed into the hypergravity reactor is 0.5 times the molar amount of lithium ions in step 3.
Comparative example 4
Step 1: reaction kettle base solution: sodium carbonate is used as base solution, and sodium carbonate solution with the concentration of 25 weight percent is prepared in a reaction kettle; the temperature of the sodium carbonate solution is 60 ℃;
step 2: adding the base solution into a reaction kettle;
the molar quantity of sodium carbonate in the base solution added into the reaction kettle is 0.6 times of the molar quantity of lithium ions in the step 3; the reaction temperature in the reaction kettle is 60 ℃;
step 3: pumping the brine solution into a reaction kettle through a metering pump, wherein the feeding time is 2 hours; preserving heat for 1h after the charging is finished, and controlling the reaction temperature in the reaction kettle at 90 ℃;
the brine in the step 3 comprises the following components:
the concentration of lithium sulfate is 1mol/L;
sodium sulfate 1.2mol/L;
potassium sulfate 0.12mol/L;
step 4: and (3) filtering the product obtained in the step (3) through a plate frame, pulping and washing filter residues for 3 times, wherein the pulping liquid-solid ratio is 5:1, pulping water at 60 ℃ and washing for 2 hours; and (3) washing the plate frame by secondary stirring, and washing for one time, wherein the washing temperature is 60 ℃, so that the lithium carbonate is finally prepared.
Performance testing
Test item 1: the impurity content is mainly detected, and the content of K and Na in the dried lithium carbonate is mainly detected;
the specific method comprises the following steps: detecting by adopting an ICP detection method, adding 5ml of nitric acid into 1g of a sample for dissolution, and fixing the volume of pure water to 100ml;
detection conditions: argon inlet pressure is 0.6-0.8mpa, RF power is 1.2kw, stabilizing time is 15s, atomizer flow is 0.7L/min, plasma gas flow is 15L/min, correction fitting: linear, auxiliary air flow rate 1.0L/min, auxiliary air flow rate 0L/min, repeating times 3 times, pump speed 12rpm, lifting delay 15s, and reading time 5s;
test item 2: particle size detection mainly detects the particle size distribution of lithium carbonate.
The specific method comprises the following steps: 0.2g of the sample is added into 20ml of ethanol, the ultrasonic treatment is carried out for 2min, and the half sample is introduced into a laser particle size analyzer.
The detection results are referred to in the following table 1;
TABLE 1 detection results
Analysis of results:
1. by way of examples 1-6, as the ratio of lithium sulfate in step 3 and step 4 is changed, the particle size control is better and the impurity content is lower as the ratio is closer to 25:75, which is because: in the hypergravity reactor, if the ratio of lithium ions is higher, the number of the crystal grains is larger, and the grain size obtained by growth of the lithium ions is smaller and the grain size distribution is uniform; if the lithium ion occupation ratio in the step 3 is low, the seed crystal grains are few, and the grain size is overlarge when the seed crystal grains grow in the reaction kettle;
however, the ratio of lithium sulfate in step 3 and step 4 cannot exceed 4:6, and in the process approaching 4:6, the content of sodium ions and potassium ions in example 6 is drastically increased as compared with example 5, and the particle size is also significantly increased, possibly because too many small-sized crystals have an aggregation property during the particle size curing process in the reaction vessel, and the particle size is increased, and in this process, since the abnormal particle size increasing process is not included, more impurities are contained.
2. It can be seen from examples 1 to 6 and examples 11 to 15 that the lithium sulfate solution is generally superior in various aspects of performance in the case of a solution of lithium sulfate as a seed crystal, and that such a solution is advantageous in controlling the quality of the product although it may lower the productivity. The most probable reasons for this phenomenon are that the impurity metal ions are few, the impurity seeds are few, the crystal grows synchronously, and the impurities mixed in the crystal are further reduced.
3. It can be seen from examples 1, 7, 10 and comparative examples 1 to 3 that the trend of the performance change thereof was consistent with the change of the relevant process parameters.
4. It is clear from examples 2 and 7 to 10 that the more sodium carbonate, the narrower the particle size distribution range, the fewer impurities, and the reason for this is not clear. In a comparison of example 2 and example 7, it is seen that the base liquid is preferably sodium carbonate, and the reasons for the differences in properties of sodium carbonate and potassium carbonate are not clear.
3. As can be seen from comparative examples 1 and 4, the overall effect of the reactor using the hypergravity is superior to that of the common reactor. As can be seen from example 1, comparative example 1 and comparative example 4, the combination of the hypergravity reactor and the common reaction kettle adopts seed crystals for hatching grains, so that the grain size distribution range can be obviously reduced, and the impurity content can be reduced.
In addition, what needs to be additionally stated is: the brine adopted in the embodiment and the comparative example of the invention are the same brine, which is based on single source of raw materials, and is obtained by the first embodiment
Verification of the different ratios of brine used in the solution and brine used in the second solution can prove the trend of the influence of the related influencing factors of the invention on the reaction result, and similar trend changes can be generated by adopting the method of the invention for brine of different sources for those skilled in the art. The choice of brine in the examples is therefore not to be taken as any limitation of the process of the invention.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (12)
1. The method for preparing the lithium carbonate based on the hypergravity reactor is characterized by comprising the following steps of:
step 1: adding a soluble carbonate solution as a base solution into a hypergravity reactor;
step 2: continuously adding the first solution containing lithium ions into a hypergravity reactor to obtain a solution containing seed crystals;
step 3: and (3) introducing the solution obtained in the step (2) into a reaction kettle, continuously adding a second solution containing lithium ions while stirring, and obtaining lithium carbonate after the reaction is completed.
2. The method for preparing lithium carbonate based on the hypergravity reactor according to claim 1, wherein the molar amount of carbonate in the soluble carbonate solution is 0.5 to 0.8 times of the sum of the molar amounts of lithium ions in the first solution and lithium ions in the second solution; the molar ratio of lithium ions in the first solution to lithium ions in the second solution is 5-60: 40-95%.
3. The method for preparing lithium carbonate based on a hypergravity reactor according to claim 1, wherein the first solution and the second solution are lithium-containing brine.
4. The method for preparing lithium carbonate based on a hypergravity reactor according to claim 1, wherein the first solution is a lithium salt solution; the second solution is lithium-containing brine.
5. The method for preparing lithium carbonate based on a hypergravity reactor according to claim 3 or 4, wherein the concentration of sodium ions in brine is 0-70 g/L, and the concentration of potassium ions is 0-15 g/L;
and/or the concentration of lithium ions in the brine is 0.01-8 g/L.
6. The method for preparing lithium carbonate based on a hypergravity reactor according to claim 1, wherein the independent reaction temperature in each of the steps 2 to 3 is 50 to 99 ℃;
and/or the filling time of the first solution is 0.1-2 h;
and/or the filling time of the second solution is 0.5-3h;
and/or, in the step 3, after the second solution is added, continuing to react for 1-3h.
7. The method for preparing lithium carbonate based on a hypergravity reactor according to claim 1, wherein the concentration of carbonate in the base liquid is 10-32 wt%;
the carbonate is sodium carbonate and/or potassium carbonate.
8. The method for preparing lithium carbonate based on the hypergravity reactor according to claim 1, wherein the stirring speed of the hypergravity reactor is 2000-5000 r/min.
9. The method for preparing lithium carbonate based on a hypergravity reactor according to claim 1, wherein the molar amount of carbonate in the soluble carbonate solution is 0.55 to 0.75 times of the sum of the molar amounts of lithium ions in the first solution and lithium ions in the second solution; the molar ratio of lithium ions in the first solution to lithium ions in the second solution is 10-25: 75-90.
10. The method for preparing lithium carbonate based on a hypergravity reactor according to claim 1, wherein in the step 3, after the completion of the reaction, a slurry containing lithium carbonate is obtained;
the specific operation of separating lithium carbonate solids from a slurry containing lithium carbonate is:
filtering the slurry containing lithium carbonate, pulping and washing filter residues for 2-4 times, wherein the solid ratio of the slurry is 2:1 to 10:1, pulping water temperature is 50-99 ℃ and washing time is 0.5-3h;
after washing, the solid is dispersed into water, and is subjected to secondary stirring washing, then is filtered and is rinsed once by clean water, the temperature of the washing water is 50-99 ℃, and finally the lithium carbonate is prepared.
11. The lithium carbonate is characterized in that the grain size distribution is D10 more than or equal to 1 mu m, D50 more than or equal to 5 mu m less than or equal to 90 mu m, D90 more than or equal to 200 mu m, and the purity is battery grade.
12. The lithium carbonate according to claim 11, characterized in that it is prepared by a process according to any one of claims 1 to 10.
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