CN116282086B - Impurity removing method for industrial grade lithium carbonate - Google Patents
Impurity removing method for industrial grade lithium carbonate Download PDFInfo
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- CN116282086B CN116282086B CN202211654286.6A CN202211654286A CN116282086B CN 116282086 B CN116282086 B CN 116282086B CN 202211654286 A CN202211654286 A CN 202211654286A CN 116282086 B CN116282086 B CN 116282086B
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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 145
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 145
- 239000012535 impurity Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 46
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 39
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 39
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 39
- 239000002002 slurry Substances 0.000 claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001301 oxygen Substances 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 230000004913 activation Effects 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 238000007885 magnetic separation Methods 0.000 claims description 27
- 230000006698 induction Effects 0.000 claims description 17
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 82
- 229910052742 iron Inorganic materials 0.000 abstract description 40
- 239000000243 solution Substances 0.000 abstract description 33
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 239000011259 mixed solution Substances 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000013078 crystal Substances 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000006148 magnetic separator Substances 0.000 description 11
- 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 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 239000011591 potassium Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000004321 preservation Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000010926 purge Methods 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 230000003213 activating effect Effects 0.000 description 6
- 230000005496 eutectics Effects 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- -1 aluminum ions Chemical class 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052629 lepidolite Inorganic materials 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
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229910052642 spodumene Inorganic materials 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
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to a method for removing impurities from industrial grade lithium carbonate. The method comprises the following steps: preparing industrial lithium carbonate and ammonium carbonate solution into a mixed phase, and then introducing oxygen-containing gas into the mixed solution for activation; filtering the activated mixed phase to obtain filter residues, and adding a reducing agent into the filter residues to pulp to obtain slurry; calcining the slurry in a reducing gas atmosphere to obtain a preform; the preform is screened. The method for removing impurities from the industrial grade lithium carbonate can prepare the battery grade lithium carbonate with lower iron residual quantity and lower content of other metal impurities.
Description
Technical Field
The application relates to the technical field of lithium ion battery anode materials, in particular to a method for removing impurities from industrial grade lithium carbonate.
Background
As a new type of secondary energy battery, the market demand of lithium ion batteries is increasing. The lithium carbonate is one of the main raw materials of the positive electrode material of the lithium ion battery, can be used for preparing the positive electrode material of the lithium ion battery such as lithium iron phosphate, lithium manganese phosphate and the like, the demand of the lithium carbonate is gradually increased, and the demand of the lithium carbonate on the purity is also gradually increased. The existing preparation process of lithium carbonate mainly comprises the steps of preparing industrial grade lithium carbonate by using spodumene, lepidolite and other lithium ores and lithium-containing brine as raw materials, wherein the iron residual quantity of the industrial grade lithium carbonate is about 20ppm, the iron residual quantity of the battery grade lithium carbonate needs to be controlled within 10ppm, the residual forms of impurity iron in the lithium carbonate exist in the forms of Fe (III), fe (II) and elemental iron, and the content of the impurity iron needs to be reduced during the preparation of the battery grade lithium carbonate.
Disclosure of Invention
Based on the above, it is necessary to provide a method for removing impurities from industrial lithium carbonate, which can reduce the content of impurity iron in industrial lithium carbonate and prepare battery grade lithium carbonate with low iron residue.
The application provides a method for removing impurities from industrial grade lithium carbonate, which comprises the following steps:
preparing industrial lithium carbonate and ammonium carbonate solution into a mixed phase, and then introducing oxygen-containing gas into the mixed phase for activation;
Filtering the activated mixed phase to obtain filter residues, and adding a reducing agent into the filter residues to pulp to obtain slurry;
Calcining the slurry in a reducing gas atmosphere to obtain a preform;
sieving the preform.
In some embodiments, the ammonium carbonate solution has a solute mass fraction of 4.5% to 22%.
In some embodiments, the mass ratio of the ammonium carbonate solution to the technical grade lithium carbonate is 3 to 5.3.
In some embodiments, when the oxygen-containing gas is introduced into the mixed phase for activation, the flow rate of the oxygen-containing gas is 45 to 650 liters/hour.
In some embodiments, when the oxygen-containing gas is introduced into the mixed phase for activation, the time for introducing the oxygen-containing gas is 3-5 h.
In some embodiments, the reducing agent comprises one or more of lithium formate, formaldehyde, hydrazine hydrate, hydroxylamine.
In some embodiments, the mass ratio of the reducing agent to the technical grade lithium carbonate is 7% to 25%.
In some embodiments, the reducing gas comprises one or more of hydrogen, methane, ethane, acetylene, and propane.
In some embodiments, the reducing gas is introduced at a flow rate of 35 liters/hr to 80 liters/hr.
In some embodiments, the temperature of the calcination is 700 ℃ to 800 ℃.
In some embodiments, the calcination is for a period of 3 to 5 hours.
In some embodiments, the calcining further comprises cooling the calcined product to a temperature of 50 ℃ to 80 ℃.
In some embodiments, the step of configuring the technical grade lithium carbonate and ammonium carbonate solution into a mixed phase further comprises stirring.
In some embodiments, the agitation is at a speed of 2500 rpm to 10500 rpm.
In some embodiments, the screened mesh number is 60 mesh to 320 mesh.
In some embodiments, further comprising magnetically separating the sieved preform.
In some embodiments, the magnetic concentration of the magnetic separation is 1600 gauss to 12000 gauss.
In the industrial lithium carbonate crystal, metal impurities such as iron and the like can form eutectic crystals with lithium carbonate or are mixed by the lithium carbonate crystal, and the impurity removing method of the industrial lithium carbonate can change the crystal structure of the lithium carbonate by utilizing the dissolution balance in the dispersing process through mixing an ammonium carbonate solution and the industrial lithium carbonate, and discharge the metal impurities which form eutectic crystals with the lithium carbonate or are clamped by the lithium carbonate from the crystal to enter the ammonium carbonate solution or form solid which does not clamp and eutectic with the lithium carbonate crystal. Meanwhile, oxygen-containing gas is introduced to strengthen dispersion, increase specific surface area of lithium carbonate and enable the reducing agent to fully contact with the lithium carbonate. The filter residue and the reducing agent are mixed and then calcined in the reducing gas atmosphere, so that ferric iron can be reduced, and the separation of the ferric iron and lithium carbonate crystals is realized. Because the reduced impurity particles are larger, the impurity particles can be separated from lithium carbonate by sieving with a screen. The method for removing impurities from the industrial grade lithium carbonate can prepare the battery grade lithium carbonate with lower iron residual quantity and lower content of other metal impurities.
Drawings
Fig. 1 is a schematic flow chart of a method for removing impurities from industrial lithium carbonate according to an embodiment of the application.
Detailed Description
In order that the above objects, features and advantages of the application will be readily understood, a more particular description of the application will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. The present application may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the application, whereby the application is not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, an embodiment of the present application provides a method for removing impurities from industrial grade lithium carbonate, comprising:
s101: preparing industrial lithium carbonate and ammonium carbonate solution into a mixed phase, and then introducing oxygen-containing gas into the mixed phase for activation;
S102: filtering the activated mixed phase to obtain filter residues, and adding a reducing agent into the filter residues to pulp to obtain slurry;
S103: calcining the slurry in a reducing gas atmosphere to obtain a preform;
S104: the preform is screened.
In the industrial lithium carbonate crystal, metal impurities can form eutectic crystals with lithium carbonate or are intercalated by the lithium carbonate crystal, and the impurity removing method of the industrial lithium carbonate can change the crystal structure of the lithium carbonate by utilizing the dissolution balance in the dispersion process through mixing an ammonium carbonate solution and the industrial lithium carbonate, so that the impurities which form eutectic crystals with the lithium carbonate or are intercalated by the lithium carbonate are discharged from the crystal and enter the ammonium carbonate solution or form solid which does not intercalate and eutectic with the lithium carbonate crystal. Meanwhile, oxygen-containing gas is introduced to strengthen dispersion, increase the specific surface area of lithium carbonate, enable the reducing agent to fully contact with the lithium carbonate, strip impurity sites of sodium, potassium and aluminum ions in the lithium carbonate, activate the sodium, potassium and aluminum ions and promote the separation efficiency of the sodium, potassium and aluminum ions in the filtering step. The oxygen-containing gas is introduced to promote the heavy metal impurities such as nickel, cobalt and the like to be dissolved in the ammonium carbonate solution from the lithium carbonate, the activation is carried out, the valence state change of the metal occurs, and the nickel and cobalt heavy metals with the valence state change can catalyze the removal of other metal impurities from the lithium carbonate. The filter residue and the reducing agent are mixed and then calcined in a reducing gas atmosphere, so that ferric iron can be reduced, the separation of the ferric iron and lithium carbonate crystals is realized, and metals such as copper, zinc, nickel, cobalt, manganese, lead and the like can be reduced. Because the reduced impurity particles are larger, the impurity particles can be separated from lithium carbonate by sieving with a screen. The method for removing impurities from the industrial grade lithium carbonate can prepare the battery grade lithium carbonate with lower iron residue and lower other metal impurity content.
In one embodiment, the residual iron content of the technical grade lithium carbonate is greater than or equal to 20ppm.
In some embodiments, the oxygen-containing gas comprises one of oxygen, air.
In some embodiments, the mass fraction of ammonium carbonate solution is 4.5% to 22%. When the mass fraction of the ammonium carbonate solution is too low, the activation effect is poor, so that heavy metal impurities cannot be removed, and when the mass fraction of the ammonium carbonate solution is too high, the iron removal rate is reduced. Alternatively, the mass fraction of the ammonium carbonate solution is 4.5%, 5%, 6%, 8%, 10%, 12%, 14%, 15%, 17%, 18%, 20% or 22%.
In some embodiments, the mass ratio of the ammonium carbonate solution to the technical grade lithium carbonate is 3 to 5.3. When the amount of the ammonium carbonate solution is too low, the activation effect is poor, so that heavy metal impurities cannot be removed, and when the amount of the ammonium carbonate solution is too high, the iron removal rate is reduced. Alternatively, the mass ratio of ammonium carbonate solution to technical grade lithium carbonate is 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2 or 5.3.
In one embodiment, the mass fraction of the ammonium carbonate solution is 4.5% -22%; and the mass ratio of the ammonium carbonate solution to the industrial grade lithium carbonate is 3-5.3.
In some embodiments, the oxygen-containing gas is introduced into the mixed phase at a flow rate of 45 liters/hr to 650 liters/hr for activation. When the flow rate of the oxygen-containing gas is too low, the removal rate of impurities such as sodium, potassium, aluminum and the like and iron can be influenced, sulfate and chloride ions possibly remain in the raw materials, and when the flow rate of the oxygen-containing gas is too high, the iron can be oxidized, and the removal rate of the iron can be influenced. Optionally, the oxygen-containing gas is introduced into the mixed solution at a flow rate of 45 liters/hr, 50 liters/hr, 70 liters/hr, 100 liters/hr, 150 liters/hr, 200 liters/hr, 250 liters/hr, 300 liters/hr, 350 liters/hr, 400 liters/hr, 450 liters/hr, 500 liters/hr, 550 liters/hr, 600 liters/hr or 650 liters/hr.
In some embodiments, the oxygen-containing gas is introduced into the mixed phase for activation for a period of time ranging from 3 hours to 5 hours. When the oxygen-containing gas is excessively short in the time, the removal rate of impurities such as sodium, potassium and aluminum and iron can be affected, sulfate and chloride ions possibly remain in the raw materials, and when the oxygen-containing gas is excessively long in the time, the iron can be oxidized, and the removal rate of the iron can be affected. Optionally, the oxygen-containing gas is introduced for 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours or 5 hours.
In one embodiment, the flow rate of the oxygen-containing gas is 45 to 650 liters/hour; and the oxygen-containing gas is introduced for 3 to 5 hours.
In some embodiments, the reducing agent includes one or more of lithium formate, formaldehyde, hydrazine hydrate, hydroxylamine.
In some embodiments, the mass ratio of reducing agent to technical grade lithium carbonate is 7% to 25%. When the amount of the reducing agent is too low, the iron removal rate is affected, and when the amount of the reducing agent is too high, the copper removal rate is affected. Alternatively, the mass ratio of the reducing agent to the technical grade lithium carbonate is 7%, 8%, 10%, 12%, 15%, 18%, 20%, 22% or 25%.
In one embodiment, the reducing agent comprises one or more of lithium formate, formaldehyde, hydrazine hydrate, hydroxylamine; and the mass ratio of the reducing agent to the industrial grade lithium carbonate is 7-25%.
In some embodiments, the reducing gas comprises one or more of hydrogen, methane, ethane, acetylene, and propane.
In some embodiments, the reducing gas is introduced at a flow rate of 35 liters/hr to 80 liters/hr. When the flow rate of the reducing gas is too low, the removal rate of iron is low, and when the flow rate of the reducing gas is too high, the residual amount of sodium, potassium and aluminum impurities is high. Alternatively, the flow rate of the reducing gas is 35 liters/hr, 40 liters/hr, 45 liters/hr, 50 liters/hr, 55 liters/hr, 60 liters/hr, 65 liters/hr, 70 liters/hr, 75 liters/hr, or 80 liters/hr.
In some embodiments, the temperature of calcination is 700 ℃ to 800 ℃. When the temperature of calcination is too low, the removal rate of iron is low, and when the temperature of calcination is too high, the removal rate of copper is low. Alternatively, the temperature of calcination is 700 ℃, 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃, or 800 ℃.
In some embodiments, the calcination time is 3 to 5 hours. Too short a calcination time results in a low iron removal rate, and too long a calcination time results in a low copper removal rate. Alternatively, the calcination time is 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h, or 5h.
In some embodiments, calcining further comprises cooling the calcined product to a temperature of 50 ℃ to 80 ℃. When the temperature of the calcined product is too low or too high, the residual amount of iron is high. Optionally, the calcining further comprises cooling the calcined product to 50 ℃, 55 ℃,60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃.
In some embodiments, the step of configuring the technical grade lithium carbonate and ammonium carbonate solution into a mixed phase further comprises stirring.
In some embodiments, the rotational speed of the agitation is 2500 rpm to 10500 rpm. When the stirring speed is too low, the impurity removal rate of sodium, potassium, aluminum and the like is low, and when the stirring speed is too high, the lithium carbonate is doped with metal impurities such as copper, nickel and the like. Alternatively, the rotational speed of the agitation is 2500 rpm, 3000 rpm, 3500 rpm, 4000 rpm, 4500 rpm, 5000 rpm, 5500 rpm, 6000 rpm, 6500 rpm, 7000 rpm, 7500 rpm, 8000 rpm, 8500 rpm, 9000 rpm, 9500 rpm, 10000 rpm, or 10500 rpm.
In some embodiments, the number of screen meshes of the screen is 60 mesh to 320 mesh. When the screen mesh number is too low, the content of lithium carbonate metal impurities is high, and when the screen mesh number is too high, the yield of lithium carbonate is reduced. Alternatively, the number of screen meshes of the screen is 60 mesh, 80 mesh, 100 mesh, 120 mesh, 140 mesh, 160 mesh, 180 mesh, 200 mesh, 220 mesh, 240 mesh, 260 mesh, 280 mesh, 300 mesh or 320 mesh.
In some embodiments, further comprising magnetically separating the sieved preform.
In some embodiments, the magnetic induction of the magnetic separation is 1600 gauss to 12000 gauss. When the magnetic induction intensity of magnetic separation is too low, the removal rate of nickel and zinc is lower, and when the magnetic induction intensity of magnetic separation is too high, the removal rate of iron is lower. Optionally, the magnetic induction intensity of the magnetic separation is 2000 gauss to 10000 gauss. Further alternatively, the magnetic induction of the magnetic separation is 2000 gauss, 3000 gauss, 4000 gauss, 5000 gauss, 6000 gauss, 7000 gauss, 8000 gauss, 9000 gauss, or 10000 gauss.
In one embodiment, the method for removing impurities from technical grade lithium carbonate comprises the following steps:
(1) The technical grade lithium carbonate and the ammonium carbonate solution are prepared into a mixed phase, and then oxygen-containing gas is introduced into the mixed phase for activation.
(2) Filtering the activated mixed phase to obtain filter residues, and adding a reducing agent into the filter residues to pulp to obtain slurry.
(3) Calcining the slurry in a reducing gas atmosphere to obtain a preform.
(4) The preform is screened.
(5) And carrying out magnetic separation on the screened preform.
In one embodiment, the method for removing impurities from technical grade lithium carbonate comprises the following steps:
(1) The technical grade lithium carbonate and the ammonium carbonate solution are prepared into a mixed phase, and then oxygen-containing gas is introduced into the mixed phase for activation.
(2) Filtering the activated mixed phase to obtain filter residues, and adding a reducing agent into the filter residues to pulp to obtain slurry.
(3) Calcining the slurry in a reducing gas atmosphere to obtain a preform.
(4) The preform is screened.
(5) And carrying out magnetic separation on the screened preform.
The following are specific examples
Example 1
Removing impurities from the industrial grade lithium carbonate to prepare battery grade lithium carbonate:
(1) And (3) taking 10kg of ammonium carbonate solution with the mass fraction of 10% in a dispersing machine, adding 2kg of industrial grade lithium carbonate containing 300ppm of iron, dispersing at the rotating speed of 4000 rpm, introducing air at the flow rate of 55 liters/hour, activating for 3 hours, filtering, and adding 0.5kg of hydrazine hydrate into the obtained filter cake to pulp to obtain lithium carbonate slurry.
(2) And (3) loading the lithium carbonate slurry obtained in the step (1) into a crucible, then placing the crucible into a tubular furnace, introducing hydrogen to purge, introducing hydrogen at a flow rate of 70 liters/hour, heating to 750 ℃, reducing in a hydrogen protection atmosphere for 4 hours at the temperature of 750 ℃, stopping heat preservation, and continuing introducing hydrogen until the temperature of the material is reduced to 50 ℃.
(3) And (3) transferring the cooled lithium carbonate into a magnetic separator after passing through a 100-mesh screen, and carrying out magnetic separation with the magnetic induction intensity of 6000 gauss to obtain the battery-grade lithium carbonate after magnetic separation.
Example 2
Removing impurities from the industrial grade lithium carbonate to prepare battery grade lithium carbonate:
(1) Taking 12kg of ammonium carbonate solution with the mass fraction of 20% in a dispersing machine, adding 2.5kg of industrial grade lithium carbonate containing 650ppm of iron, dispersing at a rotating speed of 10000 revolutions per minute, introducing air at a flow rate of 60 liters per hour, activating for 4.5 hours, filtering, adding 0.25kg of formaldehyde into the obtained filter cake, and pulping to obtain lithium carbonate slurry.
(2) And (3) loading the lithium carbonate slurry obtained in the step (1) into a crucible, then placing the crucible into a tubular furnace, introducing methane into the tubular furnace at a flow rate of 75 liters/hour after purging, heating to 800 ℃, reducing in a methane protection atmosphere at 800 ℃ for 5 hours, stopping heat preservation, and continuing introducing hydrogen until the temperature of the material is reduced to 80 ℃.
(3) And (3) transferring the cooled lithium carbonate into a magnetic separator after passing through a 300-mesh screen, and carrying out magnetic separation with 10000 Gaussian magnetic induction intensity to obtain the battery-grade lithium carbonate after magnetic separation.
Example 3
Removing impurities from the industrial grade lithium carbonate to prepare battery grade lithium carbonate:
(1) 15kg of ammonium carbonate solution with the mass fraction of 10% is taken and put into a dispersing machine, 5kg of industrial grade lithium carbonate containing 400ppm of iron is put into the dispersing machine to be dispersed at the rotating speed of 6000 rpm, air is introduced at the flow rate of 50 liters/hour, the mixture is activated for 3 hours and then filtered, and the obtained filter cake is added with 0.35kg of lithium formate to be pulped, so as to obtain lithium carbonate slurry.
(2) And (3) loading the lithium carbonate slurry obtained in the step (1) into a crucible, then placing the crucible into a tubular furnace, introducing propane at a flow rate of 40 liters/hour after purging, heating to 720 ℃, reducing in a propane protective atmosphere at the temperature of 720 ℃ for 5 hours, stopping heat preservation, and continuing introducing hydrogen until the temperature of the material is reduced to 60 ℃.
(3) And (3) transferring the cooled lithium carbonate into a magnetic separator after passing through a 150-mesh screen, and carrying out magnetic separation with a magnetic induction intensity of 7000 gauss to obtain the battery-grade lithium carbonate after magnetic separation.
Example 4
Removing impurities from the industrial grade lithium carbonate to prepare battery grade lithium carbonate:
(1) 7.95kg of ammonium carbonate solution with the mass fraction of 20% is taken and put into a dispersing machine, 1.5kg of industrial grade lithium carbonate containing 50ppm of iron is put into the dispersing machine to be dispersed at the rotating speed of 3000 r/min, air is introduced at the flow rate of 60L/h, the mixture is activated for 3.5 hours and then filtered, and the obtained filter cake is added with 0.15kg of hydroxylamine to be pulped, so as to obtain lithium carbonate slurry.
(2) And (3) loading the lithium carbonate slurry obtained in the step (1) into a crucible, then placing the crucible into a tubular furnace, introducing acetylene into the tubular furnace at a flow rate of 60L/h after purging, heating to 780 ℃, reducing in an acetylene protection atmosphere at 780 ℃ for 5 hours, stopping heat preservation, and continuing introducing hydrogen until the temperature of the material is reduced to 60 ℃.
(3) And (3) transferring the cooled lithium carbonate into a magnetic separator after passing through a 150-mesh screen, and carrying out magnetic separation with a magnetic induction intensity of 7000 gauss to obtain the battery-grade lithium carbonate after magnetic separation.
Comparative example 1
(1) 6Kg of ammonium carbonate solution with the mass fraction of 10% is taken and put into a dispersing machine, 3.5kg of industrial grade lithium carbonate containing 150ppm of iron is put into the dispersing machine to be dispersed at the rotating speed of 3000 r/min, air is introduced at the flow rate of 10L/h, the mixture is activated for 2 hours and then filtered, and the obtained filter cake is added with 0.05kg of hydrazine hydrate to pulp, thus obtaining lithium carbonate slurry.
(2) And (3) loading the lithium carbonate slurry obtained in the step (1) into a crucible, then placing the crucible into a tubular furnace, introducing hydrogen to purge, introducing hydrogen at a flow rate of 50 liters/hour, heating to 750 ℃, reducing in a hydrogen protection atmosphere for 3 hours at the temperature of 750 ℃, stopping heat preservation, and continuing introducing hydrogen until the temperature of the material is reduced to 80 ℃.
(3) And (3) transferring the cooled lithium carbonate into a magnetic separator after passing through a 300-mesh screen, and carrying out magnetic separation with magnetic induction intensity of 3000 gauss to obtain the lithium carbonate after magnetic separation.
Comparative example 2
(1) Taking 11kg of ammonium carbonate solution with the mass fraction of 10% in a dispersing machine, adding 3.5kg of industrial grade lithium carbonate containing 120ppm of iron, dispersing at the rotating speed of 1000 rpm, introducing air at the flow rate of 30 liters/hour, activating for 3 hours, filtering, adding 0.05kg of hydrazine hydrate into the obtained filter cake, and pulping to obtain lithium carbonate slurry.
(2) And (3) loading the lithium carbonate slurry obtained in the step (1) into a crucible, then placing the crucible into a tubular furnace, introducing hydrogen to purge, introducing hydrogen at a flow rate of 50 liters/hour, heating to 600 ℃, reducing in a hydrogen protection atmosphere at 600 ℃ for 3 hours, stopping heat preservation, and continuing introducing hydrogen until the temperature of the material is reduced to 30 ℃.
(3) And (3) transferring the cooled lithium carbonate into a magnetic separator after passing through a 300-mesh screen, and carrying out magnetic separation with magnetic induction intensity of 3000 gauss to obtain the lithium carbonate after magnetic separation.
Comparative example 3
(1) Taking 13.5kg of ammonium carbonate solution with the mass fraction of 25% in a dispersing machine, adding 4.5kg of industrial grade lithium carbonate containing 100ppm of iron, dispersing at the rotating speed of 13000 r/min, introducing air at the flow rate of 60L/h, activating for 3 h, filtering, adding 0.35kg of hydrazine hydrate into the obtained filter cake, and pulping to obtain lithium carbonate slurry.
(2) And (3) loading the lithium carbonate slurry obtained in the step (1) into a crucible, then placing the crucible into a tubular furnace, introducing hydrogen to purge, introducing hydrogen at a flow rate of 50 liters/hour, heating to 900 ℃, reducing in a hydrogen protection atmosphere at 900 ℃ for 3 hours, stopping heat preservation, and continuing introducing hydrogen until the temperature of the material is reduced to 50 ℃.
(3) And (3) transferring the cooled lithium carbonate into a magnetic separator after passing through a 100-mesh screen, and carrying out magnetic separation with magnetic induction intensity of 3000 gauss to obtain the lithium carbonate after magnetic separation.
Comparative example 4
(1) 18Kg of ammonium carbonate solution with the mass fraction of 10% is taken and put into a dispersing machine, 4.5kg of industrial grade lithium carbonate containing 180ppm of iron is put into the dispersing machine to be dispersed at the speed of 14000 r/min, air is introduced at the flow rate of 700L/h, the mixture is activated for 3 hours and then filtered, and the obtained filter cake is added with 0.40kg of lithium formate to be pulped, so as to obtain lithium carbonate slurry.
(2) And (3) loading the lithium carbonate slurry obtained in the step (1) into a crucible, then placing the crucible into a tubular furnace, introducing hydrogen to purge, introducing hydrogen at a flow rate of 30 liters/hour, heating to 750 ℃, reducing in a hydrogen protection atmosphere for 3 hours at the temperature of 750 ℃, stopping heat preservation, and continuing introducing hydrogen until the temperature of the material is reduced to 60 ℃.
(3) And (3) transferring the cooled lithium carbonate into a magnetic separator after passing through a 350-mesh screen, and carrying out magnetic separation with magnetic induction intensity of 1000 gauss to obtain the lithium carbonate after magnetic separation.
Comparative example 5
(1) Taking 4.6kg of ammonium carbonate solution with the mass fraction of 20% in a dispersing machine, adding 1.5kg of industrial grade lithium carbonate containing 130ppm of iron, dispersing at the rotating speed of 4000 rpm, introducing air at the flow rate of 15 liters/hour, activating for 3 hours, filtering, adding 0.23kg of hydrazine hydrate into the obtained filter cake, and pulping to obtain lithium carbonate slurry.
(2) And (3) loading the lithium carbonate slurry obtained in the step (1) into a crucible, then placing the crucible into a tubular furnace, introducing hydrogen to purge, introducing hydrogen at a flow rate of 50 liters/hour, heating to 850 ℃, reducing in a hydrogen protection atmosphere at a temperature of 850 ℃ for 3 hours, stopping heat preservation, and continuing introducing hydrogen until the temperature of the material is reduced to 30 ℃.
(3) And (3) transferring the cooled lithium carbonate into a magnetic separator after passing through a 40-mesh screen, and carrying out magnetic separation with the magnetic induction intensity of 15000 gauss to obtain the lithium carbonate after magnetic separation.
The impurity contents in the lithium carbonate products obtained in examples 1 to 4 and comparative examples 1 to 5 were measured, and the measurement results are shown in table 1 below:
TABLE 1
In addition, the lithium carbonate product prepared in comparative example 1 also included 27ppm of aluminum, 820ppm of sulfate ion, and 55ppm of chloride ion. The lithium carbonate product prepared in comparative example 3 also included 15ppm copper. The lithium carbonate product prepared in comparative example 4 also included 17ppm zinc and 15ppm nickel.
Analysis of results
The impurity contents in the lithium carbonate products obtained in comparative examples 1 to 4 and comparative examples 1 to 5 were found to be: when the amount of ammonium carbonate is too low, the effect of activating the gas containing oxygen is poor, heavy metal impurities cannot be removed, and when the amount of ammonium carbonate is too high, the iron removal rate is reduced. When the rotation speed of the disperser is too low, the impurity removal rate of sodium, potassium, aluminum and the like is reduced, and when the rotation speed of the disperser is too high, metal impurities such as copper, nickel and the like are clamped in lithium carbonate. When the air flow rate in the step (1) is too low, the removal rate of impurities such as sodium, potassium, aluminum and the like and iron can be influenced, and sulfate and chloride ions possibly remained in the raw materials can not be removed. When the addition amount of the reducing agent in the step (1) is too low, the iron removal rate is affected, and when the addition amount of the reducing agent is too high, the copper removal rate is affected. In the step (2), if the temperature is lower than 700 ℃, the iron removal rate is low, and if the temperature is higher than 800 ℃, the copper removal rate is low; the reduced temperature of less than 50 ℃ or more than 80 ℃ can lead to the reduction of the iron removal rate; too low flow of the introduced shielding gas can lead to low iron removal rate, and too high flow of the introduced shielding gas can lead to residues of impurities such as sodium, potassium and aluminum. In the step (3), when the screen mesh number is too low, the metal impurity content of the obtained lithium carbonate is increased, and when the screen mesh number is too high, the yield of the obtained lithium carbonate is reduced; when the magnetic induction intensity of the magnetic separator is too low, the nickel and zinc removal rate is low, and when the magnetic induction intensity of the magnetic separator is too high, the iron removal rate is low.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. The scope of the application is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted in accordance with the contents of the claims.
Claims (6)
1. The method for removing impurities from the industrial grade lithium carbonate is characterized by comprising the following steps:
Preparing industrial lithium carbonate and ammonium carbonate solution into a mixed phase, and then introducing oxygen-containing gas into the mixed phase for activation; the mass fraction of the solute of the ammonium carbonate solution is 4.5% -22%; the mass ratio of the ammonium carbonate solution to the industrial grade lithium carbonate is 3-5.3; the flow rate of the oxygen-containing gas is 45-650L/h;
Filtering the activated mixed phase to obtain filter residues, and adding a reducing agent into the filter residues to pulp to obtain slurry; the mass ratio of the reducing agent to the industrial grade lithium carbonate is 7% -25%;
calcining the slurry in a reducing gas atmosphere, and cooling the calcined product to 50-80 ℃ to obtain a preform; the calcining temperature is 700-800 ℃; the flow rate of the reducing gas is 35-80L/h;
Sieving the preform; the number of the screened screen meshes is 60-320 meshes;
Magnetically separating the screened preform; the magnetic induction intensity of the magnetic separation is 1600-12000 gauss.
2. The method for removing impurities from industrial grade lithium carbonate according to claim 1, wherein the oxygen-containing gas is introduced for 3-5 hours.
3. The method for removing impurities from technical grade lithium carbonate according to claim 1, wherein the reducing agent comprises one or more of lithium formate, formaldehyde, hydrazine hydrate, and hydroxylamine.
4. The method of claim 1, wherein the reducing gas comprises one or more of hydrogen, methane, ethane, acetylene, and propane.
5. The method for removing impurities from technical grade lithium carbonate according to claim 1, wherein the calcination time is 3-5 h.
6. The method for removing impurities from technical grade lithium carbonate according to claim 1, wherein the step of preparing the technical grade lithium carbonate and the ammonium carbonate solution into a mixed phase further comprises stirring; the stirring speed is 2500-10500 rpm.
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