CN116692911A - Process for reducing magnetic substances in battery-grade lithium carbonate - Google Patents
Process for reducing magnetic substances in battery-grade lithium carbonate Download PDFInfo
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- CN116692911A CN116692911A CN202310985074.4A CN202310985074A CN116692911A CN 116692911 A CN116692911 A CN 116692911A CN 202310985074 A CN202310985074 A CN 202310985074A CN 116692911 A CN116692911 A CN 116692911A
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- lithium carbonate
- battery
- grade lithium
- roasting furnace
- ethanol solution
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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 88
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 50
- 239000000126 substance Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 142
- 239000000463 material Substances 0.000 claims abstract description 64
- 238000001035 drying Methods 0.000 claims abstract description 55
- 239000000725 suspension Substances 0.000 claims abstract description 38
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000460 chlorine Substances 0.000 claims abstract description 22
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000007599 discharging Methods 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 23
- 239000003595 mist Substances 0.000 claims description 19
- 238000005507 spraying Methods 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000005086 pumping Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 11
- 230000005347 demagnetization Effects 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000011010 flushing procedure Methods 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 230000005389 magnetism Effects 0.000 abstract description 9
- 238000004090 dissolution Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 4
- 238000004321 preservation Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910001416 lithium ion 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
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
- B03C1/30—Combinations with other devices, not otherwise provided for
-
- 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
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- 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 invention provides a process for reducing magnetic substances in battery-grade lithium carbonate. A process for reducing magnetic substances in battery-grade lithium carbonate comprises the following steps: pretreating a battery-grade lithium carbonate material, introducing chlorine, roasting, dissolving with an ethanol solution, filtering, atomizing the suspension, and drying. According to the invention, the battery grade lithium carbonate material containing the magnetic substance is roasted in a chlorine environment, so that a metal simple substance is converted into a metal chloride, and then the chloride is removed through dissolution, so that the effect of deeply reducing the magnetism of the battery grade lithium carbonate is achieved, and the safety, durability and environmental protection of the prepared battery are improved.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a process for reducing magnetic substances in battery-grade lithium carbonate.
Background
The battery grade lithium carbonate is one of the raw materials for producing lithium batteries and is mainly used for preparing lithium cobalt oxide, lithium manganate, ternary materials, lithium iron phosphate and other lithium ion battery anode materials, when magnetic substances such as Fe, cr, zn and the like exist in the anode materials, the battery can be self-discharged and bulge, even short circuit and explosion are caused, the higher the content of the magnetic substances in the lithium battery is, the larger the self-discharge rate is, the battery grade lithium carbonate material is usually subjected to magnetism reduction by adopting a physical adsorption method at present, but the effect of deep magnetism reduction is difficult to achieve only through physical adsorption, so that the battery prepared by utilizing the battery grade lithium carbonate material is low in safety, durability and environmental protection.
The foregoing is provided merely for the purpose of facilitating understanding of the technical solutions of the present invention and is not intended to represent an admission that the foregoing is prior art.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a process for reducing magnetic substances in battery-grade lithium carbonate.
A process for reducing magnetic substances in battery grade lithium carbonate, comprising the steps of:
s1: pretreatment of battery grade lithium carbonate material
Grinding a battery-grade lithium carbonate material containing magnetic substances, and performing primary demagnetization by an electromagnetic iron removing machine;
s2: introducing chlorine gas and calcining
Uniformly spraying the preliminary demagnetizing material in a roasting furnace in a chlorine environment, and roasting to obtain a mixed material;
s3: dissolving in ethanol solution and filtering
Adding the mixed materials into an ethanol solution, stirring and dissolving, and washing and centrifugally filtering the mixed materials by the ethanol solution to obtain a demagnetized product;
s4: atomizing the suspension and drying
And (3) homogenizing and mixing the ethanol solution and the demagnetizing product, and then performing spray drying to remove water and ethanol to obtain the demagnetizing lithium carbonate powder.
Further, the pretreatment of the battery-grade lithium carbonate material in the step S1 specifically comprises the following steps:
s1.1: putting the battery grade lithium carbonate material containing the magnetic substance into a grinder, and fully grinding and crushing to obtain battery grade lithium carbonate powder;
s1.2: and carrying out preliminary demagnetization on the battery-level lithium carbonate powder by using an electromagnetic iron removing machine to obtain a preliminary magnetism-reducing material.
Further, the step S2 of introducing chlorine and roasting specifically comprises the following steps:
s2.1: preheating a roasting furnace to 200-300 ℃, then introducing chlorine gas into the roasting furnace from the bottom of the roasting furnace, discharging hot air in the furnace from the top of the roasting furnace by the chlorine gas until a detector in the roasting furnace detects that the concentration of the chlorine gas is 95-100%, and stopping introducing the chlorine gas;
s2.2: adjusting the temperature in the roasting furnace to 500-700 ℃, and preserving heat for 0.5-1h until a temperature sensor in the roasting furnace detects that the temperature in the furnace is kept constant;
s2.3: and loading the preliminary demagnetizing materials into a sprayer in a roasting furnace, uniformly spraying the preliminary demagnetizing powder into the roasting furnace through the sprayer, and roasting for 3-5 hours to obtain a mixed material.
Further, the step S3 of dissolving and filtering by ethanol solution specifically comprises the following steps:
s3.1: adding ethanol solution into a centrifugal zone of a closed reactor, and heating to 40-50 ℃;
s3.2: adding the mixed material into ethanol solution, stirring by using a stirrer, and fully dissolving to obtain a solid-liquid mixture;
s3.3: centrifuging the solid-liquid mixture at a speed of 5000-8000r/min for 40-50min, and discharging filtrate to obtain demagnetizing filter residues;
s3.4: introducing ethanol solution into the demagnetizing filter residue, centrifuging at a speed of 3000-5000r/min for 20-30min, discharging filtrate, and repeating for 2-3 times to obtain the demagnetizing product.
Further, the step S4 of atomizing the suspension and drying the suspension specifically includes the following steps:
s4.1: pumping an ethanol solution into a closed reactor through a water pump, flushing a demagnetized product in the closed reactor into a homogenizing region by the ethanol solution, homogenizing for 20-45min, and obtaining a suspension;
s4.2: measuring the suspension by a measuring pump, pumping the suspension into a sprayer, and heating a drying area of the closed reactor by hot air;
s4.3: spraying the suspension into a drying area in the form of mist droplets by a sprayer, evaporating and removing water and ethanol in the mist droplets in the drying area, and collecting the obtained dry and demagnetized lithium carbonate powder after falling into a collector at the bottom of the drying area.
Further, in the step S2.1, the roasting furnace is preheated to obtain hot air, then chlorine is introduced to discharge the hot air, the hot air is collected and insulated through the insulation collecting box, then a valve between the insulation collecting box and a drying zone of the closed reactor is opened, the hot air is pressed into a heating layer of the drying zone of the closed reactor in the step S4.2 through a booster pump, and the drying zone is heated, so that water and ethanol in sprayed mist droplets are evaporated and removed.
Further, the ethanol solution is prepared from absolute ethanol and deionized water according to the volume ratio of (5-10) to (3-5).
Further, the stirring speed of the stirrer is 500-1000r/min, and the stirring time is 1-2h.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, the battery grade lithium carbonate material containing the magnetic substance is roasted in a chlorine environment, so that a metal simple substance is converted into a metal chloride, and then the chloride is removed through dissolution, so that the effect of deeply reducing the magnetism of the battery grade lithium carbonate is achieved, and the safety, durability and environmental protection of the prepared battery are improved.
2. According to the invention, the ethanol solution is used for dissolving the mixed materials and washing the demagnetized products, so that the dissolution of lithium carbonate can be reduced, and the aim of reducing the waste of lithium carbonate is fulfilled.
3. According to the invention, the heat-preserving collecting box is used for collecting hot air obtained by preheating the roasting furnace, and the hot air is used for heating the drying area of the closed reactor so as to evaporate and remove water and ethanol in mist droplets, thereby achieving the effect of fully and effectively utilizing resources and improving the preparation efficiency.
Drawings
Fig. 1 is a flow chart of a process for reducing magnetic substances in battery grade lithium carbonate according to an embodiment of the present invention.
FIG. 2 is a summary of test results for examples 1, 2, 3 and 4 of the present invention.
FIG. 3 is a summary of test results for example 1 and comparative example 1 of the present invention.
FIG. 4 is a summary of test results for example 1 and comparative example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A process for reducing magnetic substances in battery grade lithium carbonate, as shown in fig. 1, comprising the steps of:
s1: putting a battery grade lithium carbonate material containing 0.0001% of magnetic substances into a grinder, fully grinding and crushing to obtain battery grade lithium carbonate powder, and then performing primary demagnetization on the battery grade lithium carbonate powder by using an electromagnetic iron removing machine to obtain a primary demagnetizing material;
s2: preheating a roasting furnace to 200 ℃, then introducing chlorine from the bottom of the roasting furnace into the roasting furnace, discharging hot air in the furnace from the top of the roasting furnace, collecting and preserving heat through a heat preservation collecting box until a detector in the roasting furnace detects that the chlorine concentration is 95%, stopping introducing the chlorine, then adjusting the temperature in the roasting furnace to 500 ℃, preserving heat for 0.5h until a temperature sensor in the roasting furnace detects that the temperature in the furnace is kept constant, loading the primary demagnetizing material into a sprayer in the roasting furnace, uniformly spraying primary demagnetizing powder into the roasting furnace through the sprayer, and roasting for 3h to obtain a mixed material;
s3: adding an ethanol solution prepared by anhydrous ethanol and deionized water according to a volume ratio of 5:3 into a centrifugal area of a closed reactor, heating to 40 ℃, adding the mixed material into the ethanol solution, stirring for 1h at a speed of 500r/min by using a stirrer, fully dissolving to obtain a solid-liquid mixture, centrifuging the solid-liquid mixture at a speed of 5000r/min for 40min, discharging filtrate to obtain a demagnetized filter residue, introducing the ethanol solution into the demagnetized filter residue, centrifuging for 20min at a speed of 3000r/min, discharging the filtrate, and repeating for 2 times to obtain a demagnetized product;
s4: pumping an ethanol solution into a closed reactor through a water pump, flushing a magnetism-reducing product in the closed reactor into a homogenizing area by the ethanol solution, homogenizing for 20min to obtain a suspension, measuring the suspension by a metering pump, pumping the suspension into a sprayer, simultaneously opening a valve between a heat preservation collecting box and a drying area of the closed reactor, pressing hot air in the step S2 into a heating layer of the drying area of the closed reactor through a pressurizing pump, heating the drying area of the closed reactor by the hot air, spraying the suspension into the drying area in a mist droplet form by the sprayer, evaporating and removing water and ethanol in the mist droplet in the drying area, and collecting the obtained dry magnetism-reducing lithium carbonate powder in a collector at the bottom of the drying area to achieve the effect of fully and effectively utilizing resources, thereby improving the preparation efficiency.
After the dry reduced magnetic lithium carbonate powder is prepared, the product is subjected to test:
100g of the obtained dry reduced magnetic lithium carbonate powder was taken as a sample, and placed on a metal detector to detect the concentrations of Fe, cr, zn and the like, and as a result, as shown in FIG. 2, the concentrations of Fe, cr, zn were 48.2ppb, 1.2ppb, and 12.6ppb, respectively, and the total thereof was 62ppb.
Example 2
A process for reducing magnetic substances in battery grade lithium carbonate, as shown in fig. 1, comprising the steps of:
s1: putting a battery grade lithium carbonate material containing 0.0001% of magnetic substances into a grinder, fully grinding and crushing to obtain battery grade lithium carbonate powder, and then performing primary demagnetization on the battery grade lithium carbonate powder by using an electromagnetic iron removing machine to obtain a primary demagnetizing material;
s2: preheating a roasting furnace to 250 ℃, then introducing chlorine from the bottom of the roasting furnace into the roasting furnace, discharging hot air in the furnace from the top of the roasting furnace, collecting and preserving heat through a heat preservation collecting box until a detector in the roasting furnace detects that the chlorine concentration is 98%, stopping introducing the chlorine, then adjusting the temperature in the roasting furnace to 600 ℃, preserving heat for 0.75h until a temperature sensor in the roasting furnace detects that the temperature in the furnace is kept constant, loading the primary demagnetizing material into a sprayer in the roasting furnace, uniformly spraying primary demagnetizing powder into the roasting furnace through the sprayer, and roasting for 4h to obtain a mixed material;
s3: adding an ethanol solution prepared by anhydrous ethanol and deionized water according to a volume ratio of 7:4 into a centrifugal area of a closed reactor, heating to 45 ℃, adding the mixed material into the ethanol solution, stirring for 1.5h at a speed of 750r/min by using a stirrer, fully dissolving to obtain a solid-liquid mixture, centrifuging the solid-liquid mixture at a speed of 6500r/min for 45min, discharging filtrate to obtain a magnetism reduction filter residue, introducing the ethanol solution into the magnetism reduction filter residue, centrifuging for 25min at a speed of 4000r/min, discharging the filtrate, and repeating for 2 times to obtain a magnetism reduction product;
s4: pumping an ethanol solution into a closed reactor through a water pump, flushing a magnetism-reducing product in the closed reactor into a homogenizing area by the ethanol solution, homogenizing for 30min to obtain a suspension, measuring the suspension by a metering pump, pumping the suspension into a sprayer, simultaneously opening a valve between a heat preservation collecting box and a drying area of the closed reactor, pressing hot air in the step S2 into a heating layer of the drying area of the closed reactor through a pressurizing pump, heating the drying area of the closed reactor by the hot air, spraying the suspension into the drying area in a mist droplet form by the sprayer, evaporating and removing water and ethanol in the mist droplet in the drying area, and collecting the obtained dry magnetism-reducing lithium carbonate powder in a collector at the bottom of the drying area to achieve the effect of fully and effectively utilizing resources, thereby improving the preparation efficiency.
After the dry reduced magnetic lithium carbonate powder is prepared, the product is subjected to test:
100g of the obtained dry reduced magnetic lithium carbonate powder was taken as a sample, and placed on a metal detector to detect the concentrations of Fe, cr, zn and the like, and as a result, as shown in FIG. 2, the concentrations of Fe, cr, zn were 50.6ppb, 2.5ppb, and 10.8ppb, respectively, and the total thereof was 63.9ppb.
Example 3
A process for reducing magnetic substances in battery grade lithium carbonate, as shown in fig. 1, comprising the steps of:
s1: putting a battery grade lithium carbonate material containing 0.0001% of magnetic substances into a grinder, fully grinding and crushing to obtain battery grade lithium carbonate powder, and then performing primary demagnetization on the battery grade lithium carbonate powder by using an electromagnetic iron removing machine to obtain a primary demagnetizing material;
s2: preheating a roasting furnace to 300 ℃, then introducing chlorine from the bottom of the roasting furnace into the roasting furnace, discharging hot air in the furnace from the top of the roasting furnace, collecting and preserving heat through a heat preservation collecting box until a detector in the roasting furnace detects that the chlorine concentration is 100%, stopping introducing the chlorine, then adjusting the temperature in the roasting furnace to 700 ℃, preserving heat for 1h until a temperature sensor in the roasting furnace detects that the temperature in the roasting furnace is kept constant, then loading the primary demagnetizing material into a sprayer in the roasting furnace, uniformly spraying primary demagnetizing powder into the roasting furnace through the sprayer, and roasting for 5h to obtain a mixed material;
s3: adding an ethanol solution prepared by anhydrous ethanol and deionized water according to a volume ratio of 5:3 into a centrifugal area of a closed reactor, heating to 50 ℃, adding the mixed material into the ethanol solution, stirring for 2 hours at a speed of 1000r/min by using a stirrer, fully dissolving to obtain a solid-liquid mixture, centrifuging the solid-liquid mixture at a speed of 8000r/min for 50min, discharging filtrate to obtain a demagnetized filter residue, introducing the ethanol solution into the demagnetized filter residue, centrifuging at a speed of 5000r/min for 30min, discharging the filtrate, and repeating for 3 times to obtain a demagnetized product;
s4: pumping an ethanol solution into a closed reactor through a water pump, flushing a magnetism-reducing product in the closed reactor into a homogenizing area by the ethanol solution, homogenizing for 45min to obtain a suspension, measuring the suspension by a metering pump, pumping the suspension into a sprayer, simultaneously opening a valve between a heat-preserving collecting box and a drying area of the closed reactor, pressing hot air in the step S2 into a heating layer of the drying area of the closed reactor through a pressurizing pump, heating the drying area of the closed reactor by the hot air, spraying the suspension into the drying area in a form of mist droplets by the sprayer, evaporating and removing water and ethanol in the mist droplets in the drying area, and collecting the obtained dry magnetism-reducing lithium carbonate powder in a collector at the bottom of the drying area to achieve the effect of fully and effectively utilizing resources and improve the preparation efficiency.
After the dry reduced magnetic lithium carbonate powder is prepared, the product is subjected to test:
100g of the obtained dry reduced magnetic lithium carbonate powder was taken as a sample, and the sample was placed on a metal detector to detect the concentrations of elements such as Fe, cr and Zn, and the total of the concentrations of Fe, cr and Zn was 45.8ppb, 3.6ppb and 9.6ppb, respectively, as shown in FIG. 2.
Example 4
A process for reducing magnetic substances in battery grade lithium carbonate, as shown in fig. 1, comprising the steps of:
s1: putting a battery grade lithium carbonate material containing 0.0003% of magnetic substances into a grinder, fully grinding and crushing to obtain battery grade lithium carbonate powder, and then performing primary demagnetization on the battery grade lithium carbonate powder by using an electromagnetic iron removing machine to obtain a primary demagnetizing material;
s2: preheating a roasting furnace to 200 ℃, then introducing chlorine from the bottom of the roasting furnace into the roasting furnace, discharging hot air in the furnace from the top of the roasting furnace, collecting and preserving heat through a heat preservation collecting box until a detector in the roasting furnace detects that the chlorine concentration is 95%, stopping introducing the chlorine, then adjusting the temperature in the roasting furnace to 500 ℃, preserving heat for 0.5h until a temperature sensor in the roasting furnace detects that the temperature in the furnace is kept constant, loading the primary demagnetizing material into a sprayer in the roasting furnace, uniformly spraying primary demagnetizing powder into the roasting furnace through the sprayer, and roasting for 3h to obtain a mixed material;
s3: adding an ethanol solution prepared by anhydrous ethanol and deionized water according to a volume ratio of 5:3 into a centrifugal area of a closed reactor, heating to 40 ℃, adding the mixed material into the ethanol solution, stirring for 1h at a speed of 500r/min by using a stirrer, fully dissolving to obtain a solid-liquid mixture, centrifuging the solid-liquid mixture at a speed of 5000r/min for 40min, discharging filtrate to obtain a demagnetized filter residue, introducing the ethanol solution into the demagnetized filter residue, centrifuging for 20min at a speed of 3000r/min, discharging the filtrate, and repeating for 2 times to obtain a demagnetized product;
s4: pumping an ethanol solution into a closed reactor through a water pump, flushing a magnetism-reducing product in the closed reactor into a homogenizing area by the ethanol solution, homogenizing for 20min to obtain a suspension, measuring the suspension by a metering pump, pumping the suspension into a sprayer, simultaneously opening a valve between a heat preservation collecting box and a drying area of the closed reactor, pressing hot air in the step S2 into a heating layer of the drying area of the closed reactor through a pressurizing pump, heating the drying area of the closed reactor by the hot air, spraying the suspension into the drying area in a mist droplet form by the sprayer, evaporating and removing water and ethanol in the mist droplet in the drying area, and collecting the obtained dry magnetism-reducing lithium carbonate powder in a collector at the bottom of the drying area to achieve the effect of fully and effectively utilizing resources, thereby improving the preparation efficiency.
After the dry reduced magnetic lithium carbonate powder is prepared, the product is subjected to test:
100g of the obtained dry reduced magnetic lithium carbonate powder was taken as a sample, and placed on a metal detector to detect the concentrations of elements such as Fe, cr and Zn, and as a result, as shown in FIG. 2, the concentrations of Fe, cr and Zn were 56.6ppb, 2.9ppb and 25.9ppb, respectively, and the total thereof was 85.4ppb.
Comparative example 1
A process for reducing magnetic substances in battery grade lithium carbonate, comprising the steps of:
s1: putting a battery grade lithium carbonate material containing 0.0001% of magnetic substances into a grinder, fully grinding and crushing to obtain battery grade lithium carbonate powder, and then performing primary demagnetization on the battery grade lithium carbonate powder by using an electromagnetic iron removing machine to obtain a primary demagnetizing material;
s2: preheating a roasting furnace to 200 ℃, then introducing argon into the roasting furnace from the bottom of the roasting furnace, discharging hot air in the furnace from the top of the roasting furnace, collecting and preserving heat through a heat preservation collecting box until a detector in the roasting furnace detects that the concentration of the argon is 95%, stopping introducing the argon, then adjusting the temperature in the roasting furnace to 500 ℃, preserving heat for 0.5h until a temperature sensor in the roasting furnace detects that the temperature in the furnace is kept constant, loading the primary demagnetizing material into a sprayer in the roasting furnace, uniformly spraying primary demagnetizing powder into the roasting furnace through the sprayer, and roasting for 3h to obtain a mixed material;
s3: adding an ethanol solution prepared by anhydrous ethanol and deionized water according to a volume ratio of 5:3 into a centrifugal area of a closed reactor, heating to 40 ℃, adding the mixed material into the ethanol solution, stirring for 1h at a speed of 500r/min by using a stirrer, fully dissolving to obtain a solid-liquid mixture, centrifuging the solid-liquid mixture at a speed of 5000r/min for 40min, discharging filtrate to obtain a demagnetized filter residue, introducing the ethanol solution into the demagnetized filter residue, centrifuging for 20min at a speed of 3000r/min, discharging the filtrate, and repeating for 2 times to obtain a demagnetized product;
s4: pumping an ethanol solution into a closed reactor through a water pump, flushing a magnetism-reducing product in the closed reactor into a homogenizing area by the ethanol solution, homogenizing for 20min to obtain a suspension, measuring the suspension by a metering pump, pumping the suspension into a sprayer, simultaneously opening a valve between a heat preservation collecting box and a drying area of the closed reactor, pressing hot air in the step S2 into a heating layer of the drying area of the closed reactor through a pressurizing pump, heating the drying area of the closed reactor by the hot air, spraying the suspension into the drying area in a mist droplet form by the sprayer, evaporating and removing water and ethanol in the mist droplet in the drying area, and collecting the obtained dry magnetism-reducing lithium carbonate powder in a collector at the bottom of the drying area to achieve the effect of fully and effectively utilizing resources, thereby improving the preparation efficiency.
After the dry reduced magnetic lithium carbonate powder is prepared, the product is subjected to test:
100g of the obtained dry and demagnetized lithium carbonate powder was taken as a sample, and the sample was placed on a metal detector to detect the concentrations of elements such as Fe, cr and Zn, and the concentrations of Fe, cr and Zn were 312.3ppb, 125.7ppb and 228.8ppb, respectively, as shown in FIG. 3, and the total thereof was 666.8ppb.
As is apparent from comparison of the test results of the above example 1, the battery grade lithium carbonate material containing the magnetic substance is baked in a chlorine atmosphere to convert the metal simple substance into metal chloride, and then the chloride is removed by dissolution, so as to achieve the effect of deeply reducing the magnetism of the battery grade lithium carbonate, thereby improving the safety, durability and environmental protection of the prepared battery.
Comparative example 2
A process for reducing magnetic substances in battery grade lithium carbonate, comprising the steps of:
s1: putting a battery grade lithium carbonate material containing 0.0001% of magnetic substances into a grinder, fully grinding and crushing to obtain battery grade lithium carbonate powder, and then performing primary demagnetization on the battery grade lithium carbonate powder by using an electromagnetic iron removing machine to obtain a primary demagnetizing material;
s2: preheating a roasting furnace to 200 ℃, then introducing nitrogen into the roasting furnace from the bottom of the roasting furnace, discharging hot air in the furnace from the top of the roasting furnace, collecting and preserving heat through a heat preservation collecting box until a detector in the roasting furnace detects that the nitrogen concentration is 95%, stopping introducing nitrogen, then adjusting the temperature in the roasting furnace to 500 ℃, preserving heat for 0.5h until a temperature sensor in the roasting furnace detects that the temperature in the furnace is kept constant, then loading the primary demagnetizing material into a sprayer in the roasting furnace, uniformly spraying primary demagnetizing powder into the roasting furnace through the sprayer, and roasting for 3h to obtain a mixed material;
s3: adding an ethanol solution prepared by anhydrous ethanol and deionized water according to a volume ratio of 5:3 into a centrifugal area of a closed reactor, heating to 40 ℃, adding the mixed material into the ethanol solution, stirring for 1h at a speed of 500r/min by using a stirrer, fully dissolving to obtain a solid-liquid mixture, centrifuging the solid-liquid mixture at a speed of 5000r/min for 40min, discharging filtrate to obtain a demagnetized filter residue, introducing the ethanol solution into the demagnetized filter residue, centrifuging for 20min at a speed of 3000r/min, discharging the filtrate, and repeating for 2 times to obtain a demagnetized product;
s4: pumping an ethanol solution into a closed reactor through a water pump, flushing a magnetism-reducing product in the closed reactor into a homogenizing area by the ethanol solution, homogenizing for 20min to obtain a suspension, measuring the suspension by a metering pump, pumping the suspension into a sprayer, simultaneously opening a valve between a heat preservation collecting box and a drying area of the closed reactor, pressing hot air in the step S2 into a heating layer of the drying area of the closed reactor through a pressurizing pump, heating the drying area of the closed reactor by the hot air, spraying the suspension into the drying area in a mist droplet form by the sprayer, evaporating and removing water and ethanol in the mist droplet in the drying area, and collecting the obtained dry magnetism-reducing lithium carbonate powder in a collector at the bottom of the drying area to achieve the effect of fully and effectively utilizing resources, thereby improving the preparation efficiency.
After the dry reduced magnetic lithium carbonate powder is prepared, the product is subjected to test:
100g of the obtained dry reduced magnetic lithium carbonate powder was taken as a sample, and placed on a metal detector to detect the concentrations of Fe, cr, zn and the like, and as a result, as shown in FIG. 4, the concentrations of Fe, cr, zn were 252.1ppb, 146.1ppb, and 314.5ppb, respectively, and the total thereof was 712.7ppb.
As is apparent from comparison of the test results of the above example 1, the battery grade lithium carbonate material containing the magnetic substance is baked in a chlorine atmosphere to convert the metal simple substance into metal chloride, and then the chloride is removed by dissolution, so as to achieve the effect of deeply reducing the magnetism of the battery grade lithium carbonate, thereby improving the safety, durability and environmental protection of the prepared battery.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (8)
1. A process for reducing magnetic substances in battery grade lithium carbonate, comprising the steps of:
s1: pretreatment of battery grade lithium carbonate material
Grinding a battery-grade lithium carbonate material containing magnetic substances, and performing primary demagnetization by an electromagnetic iron removing machine;
s2: introducing chlorine gas and calcining
Uniformly spraying the preliminary demagnetizing material in a roasting furnace in a chlorine environment, and roasting to obtain a mixed material;
s3: dissolving in ethanol solution and filtering
Adding the mixed materials into an ethanol solution, stirring and dissolving, and washing and centrifugally filtering the mixed materials by the ethanol solution to obtain a demagnetized product;
s4: atomizing the suspension and drying
And (3) homogenizing and mixing the ethanol solution and the demagnetizing product, and then performing spray drying to remove water and ethanol to obtain the demagnetizing lithium carbonate powder.
2. The process for reducing magnetic substances in battery grade lithium carbonate according to claim 1, wherein the battery grade lithium carbonate material pretreatment of step S1 specifically comprises the following steps:
s1.1: putting the battery grade lithium carbonate material containing the magnetic substance into a grinder, and fully grinding and crushing to obtain battery grade lithium carbonate powder;
s1.2: and carrying out preliminary demagnetization on the battery-level lithium carbonate powder by using an electromagnetic iron removing machine to obtain a preliminary magnetism-reducing material.
3. The process for reducing magnetic substances in battery-grade lithium carbonate according to claim 1, wherein the step S2 of introducing chlorine gas and roasting comprises the following steps:
s2.1: preheating a roasting furnace to 200-300 ℃, then introducing chlorine gas into the roasting furnace from the bottom of the roasting furnace, discharging hot air in the furnace from the top of the roasting furnace by the chlorine gas until a detector in the roasting furnace detects that the concentration of the chlorine gas is 95-100%, and stopping introducing the chlorine gas;
s2.2: adjusting the temperature in the roasting furnace to 500-700 ℃, and preserving heat for 0.5-1h until a temperature sensor in the roasting furnace detects that the temperature in the furnace is kept constant;
s2.3: and loading the preliminary demagnetizing materials into a sprayer in a roasting furnace, uniformly spraying the preliminary demagnetizing powder into the roasting furnace through the sprayer, and roasting for 3-5 hours to obtain a mixed material.
4. The process for reducing magnetic substances in battery grade lithium carbonate according to claim 1, wherein the step S3 of dissolving and filtering with an ethanol solution comprises the steps of:
s3.1: adding ethanol solution into a centrifugal zone of a closed reactor, and heating to 40-50 ℃;
s3.2: adding the mixed material into ethanol solution, stirring by using a stirrer, and fully dissolving to obtain a solid-liquid mixture;
s3.3: centrifuging the solid-liquid mixture at a speed of 5000-8000r/min for 40-50min, and discharging filtrate to obtain demagnetizing filter residues;
s3.4: introducing ethanol solution into the demagnetizing filter residue, centrifuging at a speed of 3000-5000r/min for 20-30min, discharging filtrate, and repeating for 2-3 times to obtain the demagnetizing product.
5. A process for reducing magnetic substances in battery grade lithium carbonate according to claim 3, wherein said atomizing suspension of step S4 is dried, specifically comprising the steps of:
s4.1: pumping an ethanol solution into a closed reactor through a water pump, flushing a demagnetized product in the closed reactor into a homogenizing region by the ethanol solution, homogenizing for 20-45min, and obtaining a suspension;
s4.2: measuring the suspension by a measuring pump, pumping the suspension into a sprayer, and heating a drying area of the closed reactor by hot air;
s4.3: spraying the suspension into a drying area in the form of mist droplets by a sprayer, evaporating and removing water and ethanol in the mist droplets in the drying area, and collecting the obtained dry and demagnetized lithium carbonate powder after falling into a collector at the bottom of the drying area.
6. The process for reducing magnetic substances in battery-grade lithium carbonate according to claim 5, wherein in step S2.1, a roasting furnace is preheated to obtain hot air, then chlorine is introduced to discharge the hot air, the hot air is collected and insulated through an insulation collecting box, a valve between the insulation collecting box and a drying zone of a closed reactor is opened, the hot air is pressed into a heating layer of the drying zone of the closed reactor in step S4.2 through a booster pump, and the drying zone is heated, so that water and ethanol in sprayed mist droplets are evaporated and removed.
7. The process for reducing magnetic substances in battery grade lithium carbonate according to claim 4, wherein the ethanol solution is prepared from absolute ethanol and deionized water according to a volume ratio of (5-10) to (3-5).
8. The process for reducing magnetic substances in battery grade lithium carbonate according to claim 4, wherein the stirring speed of the stirrer is 500-1000r/min and the stirring time is 1-2h.
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