CN107857283B - A method of isolation technics is consolidated based on selectivity and prepares battery-level lithium carbonate - Google Patents
A method of isolation technics is consolidated based on selectivity and prepares battery-level lithium carbonate Download PDFInfo
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- CN107857283B CN107857283B CN201711330275.1A CN201711330275A CN107857283B CN 107857283 B CN107857283 B CN 107857283B CN 201711330275 A CN201711330275 A CN 201711330275A CN 107857283 B CN107857283 B CN 107857283B
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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 68
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000002955 isolation Methods 0.000 title claims abstract description 13
- 238000004062 sedimentation Methods 0.000 claims abstract description 68
- 238000005360 mashing Methods 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000012216 screening Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 229920002472 Starch Polymers 0.000 claims abstract description 6
- 235000019698 starch Nutrition 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 41
- 239000012065 filter cake Substances 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 26
- 239000000706 filtrate Substances 0.000 claims description 20
- 239000010882 bottom ash Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000010009 beating Methods 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- ZCJHFOLNXNSZJG-UHFFFAOYSA-N [Na].NS(O)(=O)=O Chemical compound [Na].NS(O)(=O)=O ZCJHFOLNXNSZJG-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 238000009955 starching Methods 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 22
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000013043 chemical agent Substances 0.000 abstract description 2
- 229910052596 spinel Inorganic materials 0.000 abstract description 2
- 239000011029 spinel Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229910017053 inorganic salt Inorganic materials 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 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 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000000203 Salix gracilistyla Species 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
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical group [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 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
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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
A method of isolation technics is consolidated using selectivity and prepares battery-level lithium carbonate, belongs to chemical materials preparation field.So-called selectivity separates the technology for referring to and separating wherein certain or several compounds with other components when not changing powder mixture phase admittedly.This method includes mashing screening, level-one sedimentation separation, second level sedimentation separation and the processing steps such as washes and starches.Its main feature is that not changing powder phase, does not grind, calcines contour energy consumption process, consumption of chemical agent is few；Gently, heavy seeds step-by-step processing；Impurity substantially increases oxide spinel lithium utilization rate using partial discharge, the processing mode largely returned simultaneously；Level-one sedimentation separation, second level sedimentation separation liquid closed circulating, non-wastewater discharge, water consumption are few；The present invention has the characteristics that the lithium carbonate rate of recovery is high, production cost is low, production capacity is big, is convenient for automatic operating, opens up a new way for the purification of high-purity inorganic salt.
Description
Technical field
Isolation technics preparation LITHIUM BATTERY pure Lithium Carbonate method is consolidated using selectivity the present invention relates to a kind of, belongs to chemical industry
Field of material preparation.
Background technique
After many decades research and development, domestic and international experts and scholars have had developed a series of from the extraction of salt lake brine containing lithium
The technology of lithium carbonate.Wherein, the heavy method of sour molten-alkali and hydrogenation-pyrolysismethod are Typical Representative.
The heavy process flow of the molten-alkali of typical acid are as follows: raw material → ore grinding → high-temperature calcination → acidleach → filtering → removal of impurities → alkali
Heavy → filtering → essence removal of impurities → drying → packaging.The part such as CN106636615A, CN201610023541.5 uses this technique.
The process characteristic is that the lithium salts in raw material is converted to soluble lithium salt by high-temperature calcination and acidleach cooperation, and it is insoluble to filter off deacidification
Then impurity reacts to obtain lithium carbonate with sodium carbonate, essence cleans after removal trace impurity, obtains product.The technique is suitable to raw material
Answering property is preferable, can be used for middle-low grade lithium salts raw material, such as spodumene.Be disadvantageous in that: high-temperature calcination energy consumption is larger, acidleach
The process lithium rate of recovery is relatively low, generally 80-90%；Abraum salt water circulation use difficulty is big, and processing cost is high.
Typical hydrogenation-pyrolytic process process are as follows: raw material → ore grinding → washup → carbonic acid hydrogenation → filtering → removal of impurities → heat
Solution → filtering → essence removal of impurities → drying → packaging.CN105540619B, CN106745100A etc. are exactly part using the technique.It should
Process characteristic is that hydrogenating mode with carbonic acid dissolves lithium carbonate, and filtering removes undissolved impurity, and precipitating reagent is added and goes deliming
The impurity such as magnesium, then pyrolysis generates lithium carbonate, essence removal of impurities removal trace impurity.The technological advantage is whole process almost without forging
The operations such as burning, evaporation, low energy consumption；It is most of after process water processing to be recycled.Deficiency is lithium bicarbonate solubility
Very little, and it is unstable, general carbonic acid hydrogenation solution lithium content is (with Li2O meter) only have 1-1.2%, thus water consumption is larger.Even if
Most of process water is recycled, and the water consumption of ton product is still up to 8-10 tons.Lithium carbonate is also sl. sol. in water simultaneously, is caused
Production efficiency is low.Importantly, impurity calcium and magnesium also has carbonic acid to hydrogenate-be pyrolyzed similar procedure, therefore, the removal of calcium and magnesium impurity is difficult
It spends larger.
In conclusion existing lithium carbonate technique is reducing energy consumption, water consumption, reduction " three wastes " discharge, individual impurities removal
Etc., still there is larger room for improvement.
Summary of the invention
Consolidate the method that isolation technics prepares battery-level lithium carbonate based on selectivity the object of the present invention is to provide a kind of, with
The insufficient and defects such as high energy consumption in the presence of the prior art, high water volume, raw material availability be low are solved, " three wastes " are made it have
Discharge less, at low cost and continuous operation the advantages that.
Technical scheme is as follows:
It is a kind of that isolation technics preparation LITHIUM BATTERY pure Lithium Carbonate method is consolidated using selectivity, which is characterized in that the side
Method includes the following steps:
1) mashing screening: mixing Crude lithium Carbonate, water and low temperature cleaner mashing kettle is added at room temperature, stirring to pulp,
Slurries are after vibrating screen sieves, slag discharge, and slurries are stand-by；
2) level-one sedimentation separation: slurries after screening enter level-one sedimentation, after the sedimentation of level-one overflow subsider, bottom ash
Discharge, overflowing liquid filtering, filtrate return step 1) in mashing kettle, filter cake is stand-by；
3) second level sedimentation separation: entering second level sedimentation through level-one sedimentation, filtered filter cake, will filter in second level sedimentation
Cake, deionized water and high temperature cleaner are mixed, and are beaten at being 60-90 DEG C in temperature, and slurries enter second level overflow subsider,
Obtain overflowing liquid and bottom ash；Filtrate returns to the mashing kettle in second level sedimentation, filter cake discharge after overflowing liquid filtering；It is filtered after bottom ash filtering
Liquid returns to the mashing kettle in second level sedimentation, and filter cake is stand-by；
4) wash and starch: by second level settle obtained in filter cake mix with deionized water, stirring is warming up to 80-95 DEG C, and mashing is washed
It washs, filtering, drying obtain the product.
In above-mentioned technical proposal, which is characterized in that the solid holdup of slurries described in mashing screening is 5-20%, low temperature removal of impurities
Agent additive amount is the 0.1-10% of lithium carbonate weight in raw material.Slurries solid holdup described in second level sedimentation is 5-20%, and high temperature removes
Miscellaneous dose of additive amount is the 0.1-10% of lithium carbonate weight in raw material.
Low temperature cleaner of the present invention is sodium carbonate, sodium citrate, sodium hydroxide, ammonium hydrogen carbonate, Tween-80, three
One or more of ethanol amine, cetyl ammonium bromide, tributyl phosphate and sodium hexadecyl sulfate mixture.The height
Warm cleaner is one or more of ammonium chloride, sodium hydroxide, EDTA, salicylic acid, sulfamic acid sodium and quinoline mixture.
Preferably, being beaten mixing speed in screening process is 300-1000 revs/min, beating time 30-60 minutes；Vibrating screen
Sieve pore is 100-400 mesh.Mixing speed is 80-200 revs/min, beating time 30-60 minutes in second level sedimentation.
Preferably, during the washing and starching of step 4), drying temperature is 100-250 DEG C, and drying time is 1-4 hours.
Compared with prior art, the present invention having the following advantages that and the technical effect of high-lighting: 1. do not change powder phase,
It does not grind, calcine contour energy consumption process, low energy consumption, and consumption of chemical agent is few；2. light, heavy seeds step-by-step processing, ion exchange resin
Clean trace impurity of checking on, and ensures product quality；3. impurity is using partial discharge, most of return processing mode simultaneously, significantly
Oxide spinel lithium utilization rate is improved, and can flexibly change discharge ratio according to material composition variation, impurity removal situation etc..4. low
Temperature, separating at high temperature liquid closed circulating, non-wastewater discharge, water consumption are few；Continuous operation, compact layout, land occupation is few, produces energy
Power is big, is convenient for automatic operating.
Detailed description of the invention
Fig. 1 is the process flow chart of the method for the present invention.
Specific embodiment
The present invention is described further with reference to the accompanying drawings and examples.
So-called selectivity separates that refer to when not changing powder mixture phase will wherein certain or severalization admittedly
Close the technology that object is separated with other components.The present invention bases oneself upon carbonic acid powder for lithium microstructure, from variable grain micro interface difference
Start with, first uses the highly selective low temperature cleaner filtered out through test of many times, adhesion object between selective dissolution crystalline particle
Matter realizes the dissociation of powder each component microscopic particles space by high-speed stirred, while inhibiting carbonic acid well using low temperature medicament
Lithium particle growth causes different component crystalline particle difference in size, to settle removal without influencing other component crystalline growths
Heavy seeds.Then in a heated condition, high temperature cleaner is added, selectivity accelerates the growth of crystallization of lithium carbonate particle, causes difference
Component particles difference in size, overflow remove light impurity, most obtain pure lithium carbonate product after washing and starching afterwards.Its specific process step is such as
Under:
The present invention was spat a kind of using the selective preparation LITHIUM BATTERY pure Lithium Carbonate method of isolation technics admittedly, this method
Specifically comprise the following steps:
1) mashing screening: mixing Crude lithium Carbonate, water and low temperature cleaner mashing kettle is added at room temperature, stirring to pulp,
Slurries are after vibrating screen sieves, slag discharge, and slurries are stand-by；The low temperature cleaner be sodium carbonate, sodium citrate, sodium hydroxide,
One of ammonium hydrogen carbonate, Tween-80, triethanolamine, cetyl ammonium bromide, tributyl phosphate and sodium hexadecyl sulfate or
Several mixtures.The solid holdup of slurries described in mashing screening is 5-20%, and low temperature cleaner additive amount is lithium carbonate in raw material
The 0.1-10% of weight.Being beaten mixing speed in screening process is preferably 300-1000 revs/min, and beating time 30-60 minutes；Vibration
Dynamic sieve sieve pore is 100-400 mesh.
2) level-one sedimentation separation: slurries after screening enter level-one sedimentation, after the sedimentation of level-one overflow subsider, bottom ash
Discharge, overflowing liquid filtering, filtrate return step 1) in mashing kettle, filter cake is stand-by；
3) second level sedimentation separation: entering second level sedimentation through level-one sedimentation, filtered filter cake, will filter in second level sedimentation
Cake, deionized water and high temperature cleaner are mixed, and are beaten at being 60-90 DEG C in temperature, and slurries enter second level overflow subsider,
Obtain overflowing liquid and bottom ash；Filtrate returns to the mashing kettle in second level sedimentation, filter cake discharge after overflowing liquid filtering；It is filtered after bottom ash filtering
Liquid returns to the mashing kettle in second level sedimentation, and filter cake is stand-by；The high temperature cleaner is ammonium chloride, sodium hydroxide, EDTA, bigcatkin willow
One or more of acid, sulfamic acid sodium and quinoline mixture.Slurries solid holdup described in second level sedimentation is 5-20%, high temperature
Cleaner additive amount is the 0.1-10% of lithium carbonate weight in raw material.Mixing speed is preferably 80-200 revs/min in second level sedimentation,
Beating time 30-60 minutes.
4) wash and starch: by second level settle obtained in filter cake mix with deionized water, stirring is warming up to 80-95 DEG C, and mashing is washed
It washs, filters, dries, drying temperature is generally 100-250 DEG C, and drying time is 1-4 hours, finally obtains the product.
Embodiment 1:
Raw material be Tibet salt lake Crude lithium Carbonate, carbonic acid lithium content 75.2%, moisture content 5.4%, major impurity be potassium,
Sodium, calcium, magnesium, silicon, chlorine, sulfate radical etc..
Saturated carbon is mixed and made into pure Lithium Carbonate or the lithium carbonate product prepared and deionized water at room temperature first
Sour lithium solution is used as level-one sedimentation separation, second level sedimentation separation circulation fluid.
1kg Crude lithium Carbonate is mixed with 9kg unsaturated carbonate lithium solution, sodium hydroxide 10g, triethanolamine 5ml, Tween 80 2g
Mashing kettle is added in (the practical solid holdup 9.4% of slurries), is stirred 1.5 hours with 400 revs/min.Slurries cross 300 mesh vibrating screens, and slag stays
Primary settler overflow slot is added in the standby inspection of sample, sieving slurries, and slurries are 2 minutes in the primary settler overflow slot residence time.After sedimentation
Bottom ash filtering, filtrate return to above-mentioned mashing kettle, and filter cake discards；Overflowing liquid filtering, filtrate return to mashing kettle, filter cake (actual measurement weight
989 grams, moisture content 14.5%) enter the mashing kettle of second level sedimentation separation.
The overflow filter cake and unsaturated carbonate lithium solution 8kg, salicylic acid 2g, EDTA 5g, ammonium chloride 10g of level-one sedimentation separation
The mashing kettle that second level sedimentation separation is added in (the practical solid holdup 9.4% of slurries) is mixed, 100 revs/min of mixing speed, is warming up to 60
DEG C, insulated and stirred 1.5 hours.Second level settler overflow slot is added in gained slurries, and slurries are 1 in the second level settler overflow slot residence time
Minute.Overflowing liquid filters after second level sedimentation separation, and filtrate returns to the mashing kettle of second level sedimentation, and filter cake discards；It is filtered after bottom ash filtering
Liquid returns to the mashing kettle of second level sedimentation separation, and filter cake (874 grams of weight of actual measurement, moisture content 14.6%), which enters, washes and starches kettle.
Kettle (the practical solid holdup of slurries is washed and starched in bottom ash filter cake and unsaturated carbonate lithium solution the 7.5kg addition of second level sedimentation separation
9.0%) 80 DEG C, are warming up under stirring, 100 revs/min of mixing speed, insulated and stirred 1.5 hours, filtering, filtrate was continued to employ, and filter cake exists
250 DEG C dry 3 hours, obtain product lithium carbonate.
The specific data of operating result such as following table.The lithium carbonate rate of recovery 93.5%, product index detected have reached electricity
The standard requirements of pond level lithium carbonate.
Sample analysis result: it is as follows:
Embodiment 2:
Raw material be Tibet salt lake Crude lithium Carbonate, carbonic acid lithium content 65.1%, moisture content 8.7%, major impurity be magnesium,
Sodium, calcium, silicon, chlorine, sulfate radical etc..
Saturated carbon is mixed and made into pure Lithium Carbonate or the lithium carbonate product prepared and deionized water at room temperature first
Sour lithium solution is used as level-one sedimentation separation, second level sedimentation separation circulation fluid.
1kg Crude lithium Carbonate and 9kg unsaturated carbonate lithium solution, sodium hydroxide 15g, triethanolamine 10ml, hexadecyl hydrosulfate
Sodium 1g mixes (the practical solid holdup 9.1% of slurries), is stirred 1.5 hours with 400 revs/min.Slurries cross 300 mesh vibrating screens, and slag discards,
Primary settler overflow slot is added in the slurries that are sieved, and slurries are 2 minutes in the primary settler overflow slot residence time.After level-one sedimentation separation
Bottom ash filtering, filtrate return to mashing kettle, and filter cake discards；Overflowing liquid filtering, filtrate return to mashing kettle, filter cake (actual measurement weight 975
Gram, moisture content 20%) enter second level sedimentation separation mashing kettle.
The overflow filter cake of level-one sedimentation separation is mixed with unsaturated carbonate lithium solution 7kg, tributyl phosphate 5g, EDTA 15g
The mashing kettle of second level sedimentation separation is added in (the practical solid holdup 9.8% of slurries), 100 revs/min of mixing speed, is warming up to 80 DEG C, protects
Temperature stirring 1.5 hours.Second level settler overflow slot is added in gained slurries, and slurries are 1 minute in the second level settler overflow slot residence time.
Overflowing liquid filters after second level sedimentation, and filtrate returns to the mashing kettle of second level sedimentation separation, and filter cake discards；Filtrate returns after bottom ash filtering
The mashing kettle of second level sedimentation separation, filter cake (737 grams of weight of actual measurement, moisture content 14.5%), which enters, washes and starches kettle.
The bottom ash filter cake and unsaturated carbonate lithium solution 6kg (the practical solid holdup 9.4% of slurries) of second level sedimentation separation, which are added, to be starched
Kettle is washed, 80 DEG C are warming up under stirring, 100 revs/min of mixing speed, insulated and stirred 1.5 hours, filtering, filtrate was continued to employ, and filter cake exists
250 DEG C dry 3 hours, obtain product lithium carbonate.
The specific data of operating result such as following table.The lithium carbonate rate of recovery 92.0%, product index detected have reached battery
The standard requirements of level lithium carbonate.
Sample analysis result: it is as follows:
Embodiment 3:
Raw material be Qinghai salt lake Crude lithium Carbonate, carbonic acid lithium content 55.1%, moisture content 9.5%, major impurity be magnesium,
Sodium, calcium, boron, chlorine, sulfate radical etc..
Saturated carbon is mixed and made into pure Lithium Carbonate or the lithium carbonate product prepared and deionized water at room temperature first
Sour lithium solution is used as level-one sedimentation separation, second level sedimentation separation circulation fluid.
1kg Crude lithium Carbonate and 9kg unsaturated carbonate lithium solution, sodium hydroxide 30g, triethanolamine 20ml, cetyl bromination
Ammonium 1g mixes (the practical solid holdup 9.0% of slurries), is stirred 2 hours with 400 revs/min.Slurries cross 400 mesh vibrating screens, and slag discards, mistake
Primary settler overflow slot is added in screening the pulp liquid, and slurries are 4 minutes in the primary settler overflow slot residence time.Bottom after level-one sedimentation separation
Slag discards；Overflowing liquid filtering, filtrate return to mashing kettle, and filter cake (886 grams of weight of actual measurement, moisture content 21%) enters second level sedimentation point
From mashing kettle.
The overflow filter cake and unsaturated carbonate lithium solution 7kg, tributyl phosphate 8g, sodium carbonate 10g, chlorination of level-one sedimentation separation
Ammonium 5g mixes the mashing kettle that second level sedimentation separation is added in (the practical solid holdup 8.9% of slurries), 150 revs/min of mixing speed, is warming up to
90 DEG C, insulated and stirred 1.5 hours.Second level settler overflow slot is added in gained slurries, and slurries are in the second level settler overflow slot residence time
It is 0.5 minute.Overflowing liquid filters after second level sedimentation separation, and filtrate returns to the mashing kettle of second level sedimentation separation, filter cake discharge；Bottom ash
Filtrate returns to the mashing kettle of second level sedimentation separation after filtering, and filter cake (608 grams of weight of actual measurement, moisture content 14.5%), which enters, to be washed and starched
Kettle.
The bottom ash filter cake and unsaturated carbonate lithium solution 5kg (the practical solid holdup 9.4% of slurries) of second level sedimentation separation, which are added, to be starched
Kettle is washed, 90 DEG C are warming up under stirring, 200 revs/min of mixing speed, insulated and stirred 2 hours, filtering, filtrate was continued to employ, and filter cake is 150
DEG C drying 4 hours, obtain product lithium carbonate.
The specific data of operating result such as following table.The lithium carbonate rate of recovery 92.1%, product index detected have reached battery
The standard requirements of level lithium carbonate.
Sample analysis result: such as following table.
Claims (6)
1. a kind of consolidate isolation technics preparation LITHIUM BATTERY pure Lithium Carbonate method using selectivity, which is characterized in that the method
Include the following steps:
1) it is mixed and made into unsaturated carbonate lithium solution with pure Lithium Carbonate or the lithium carbonate product prepared and deionized water, it is spare；
2) mashing screening: Crude lithium Carbonate, unsaturated carbonate lithium solution and low temperature cleaner are mixed mashing kettle is added at room temperature, stirred
Mashing is mixed, slurries are after vibrating screen sieves, slag discharge, and slurries are stand-by；
The low temperature cleaner is sodium carbonate, sodium citrate, sodium hydroxide, ammonium hydrogen carbonate, Tween-80, triethanolamine, hexadecane
One or more of base ammonium bromide, tributyl phosphate and sodium hexadecyl sulfate mixture；Low temperature cleaner additive amount is original
The 0.1-10% of lithium carbonate weight in material；
3) level-one sedimentation separation: slurries after screening enter level-one sedimentation, after the sedimentation of level-one overflow subsider, bottom ash row
Out, overflowing liquid filters, filtrate return step 2) in mashing kettle, filter cake is stand-by；
4) second level sedimentation separation: entering second level sedimentation through level-one sedimentation, filtered filter cake, by filter cake, full in second level sedimentation
It is mixed, is beaten at being 60-90 DEG C in temperature, slurries enter second level overflow sedimentation with Lithium carbonate solution and high temperature cleaner
Slot obtains overflowing liquid and bottom ash；Filtrate returns to the mashing kettle in second level sedimentation, filter cake discharge after overflowing liquid filtering；Bottom ash filtering
Filtrate returns to the mashing kettle in second level sedimentation afterwards, and filter cake is stand-by；The high temperature cleaner be ammonium chloride, sodium hydroxide, EDTA,
One or more of salicylic acid, sulfamic acid sodium and quinoline mixture；High temperature cleaner additive amount is lithium carbonate weight in raw material
The 0.1-10% of amount；
5) wash and starch: by second level settle obtained in filter cake mix with unsaturated carbonate lithium solution, stirring is warming up to 80-95 DEG C, mashing
Washing, filtering, drying obtain the LITHIUM BATTERY pure Lithium Carbonate.
2. a kind of as described in claim 1 consolidate isolation technics preparation LITHIUM BATTERY pure Lithium Carbonate method using selectivity,
It is characterized in that, in the mashing screening of step 2), the solid holdup of the slurries is 5-20%.
3. a kind of as described in claim 1 consolidate isolation technics preparation LITHIUM BATTERY pure Lithium Carbonate method using selectivity,
It is characterized in that, in the second level sedimentation separation of step 4), the slurries solid holdup is 5-20%.
4. a kind of use selectivity described in accordance with the claim 1 consolidates isolation technics and prepares LITHIUM BATTERY pure Lithium Carbonate method,
It is characterized in that, mixing speed is 300-1000 revs/min, beating time 30-60 minutes in mashing screening process；Vibrating screen sieve pore
For 100-400 mesh.
5. a kind of use selectivity described in accordance with the claim 1 consolidates isolation technics and prepares LITHIUM BATTERY pure Lithium Carbonate method,
It is characterized in that, mixing speed is 80-200 revs/min, beating time 30-60 minutes in second level sedimentation separation.
6. a kind of use selectivity described in accordance with the claim 1 consolidates isolation technics and prepares LITHIUM BATTERY pure Lithium Carbonate method,
It is characterized in that, drying temperature is 100-250 DEG C during the washing and starching of step 5), drying time is 1-4 hours.
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| CN108793204B (en) * | 2018-08-24 | 2020-09-04 | 中国科学院青海盐湖研究所 | Method and system for preparing lithium carbonate from lithium-containing feed liquid |
| CN109437331A (en) * | 2018-09-20 | 2019-03-08 | 广东佳纳能源科技有限公司 | A kind of method of precursor of lithium ionic cell positive material impurity removal |
| CN111453748B (en) * | 2020-06-06 | 2021-01-29 | 江西南氏锂电新材料有限公司 | Lithium precipitation crystallization method for preparing snowflake monocrystal high-purity lithium carbonate |
| CN116573656B (en) * | 2023-06-09 | 2023-11-24 | 广东盛祥新材料科技有限公司 | Lithium carbonate washing process based on high-lift hot water pump |
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