CN114589186B - Comprehensive treatment method of lithium-containing waste - Google Patents
Comprehensive treatment method of lithium-containing waste Download PDFInfo
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- CN114589186B CN114589186B CN202210189729.2A CN202210189729A CN114589186B CN 114589186 B CN114589186 B CN 114589186B CN 202210189729 A CN202210189729 A CN 202210189729A CN 114589186 B CN114589186 B CN 114589186B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 148
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000002699 waste material Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000012535 impurity Substances 0.000 claims abstract description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 238000001556 precipitation Methods 0.000 claims abstract description 26
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 230000001877 deodorizing effect Effects 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 19
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 229910001424 calcium ion Inorganic materials 0.000 claims description 7
- 238000004332 deodorization Methods 0.000 claims description 6
- 238000011084 recovery Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 organic matters Chemical compound 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention belongs to the technical field of lithium battery recovery, and discloses a comprehensive treatment method of lithium-containing waste, which comprises the following steps: s1: mixing and stirring lithium-containing waste with hydrochloric acid for reaction to obtain a mixed extracting solution; s2: deodorizing and removing impurities from the mixed extracting solution to obtain refined lithium-containing extracting solution; s3: and adding a precipitant into the refined lithium-containing extracting solution to perform lithium precipitation operation, so as to obtain a lithium carbonate product. The method provided by the invention not only can neutralize the acidic substances in the lithium ion battery to reduce the pollution to the environment, but also can recycle the lithium element in the lithium ion battery to generate great economic benefit. The method has the advantages of simple operation, safe process, high recovery efficiency of lithium resources, high comprehensive recovery rate up to more than 90%, and reduced resource waste.
Description
Technical Field
The invention relates to the technical field of lithium battery recovery, in particular to a comprehensive treatment method of lithium-containing waste.
Background
In the production process of lithium batteries, some waste (commonly called waste lithium strips) consisting of lithium metal sheet scraps, lithium sheet fragments, lithium aluminate, electrolyte and the like is generated. Because of the impurities including aluminum, organic matters, sulfurous acid and the like, the lithium-containing waste is generally treated as hazardous waste, not only is the environment polluted, but also high treatment cost is required, and the lithium-containing waste contains about 20% of lithium element by mass percent, so that if the lithium element in the lithium-containing waste can be recovered, a certain economic value can be generated.
Therefore, there is a need in the art for developing a comprehensive treatment method for lithium-containing waste, which can treat pollutants in lithium-containing waste and recycle resources.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a comprehensive treatment method of lithium-containing waste, which not only can neutralize acidic substances in the waste and reduce environmental pollution, but also can recycle lithium elements in the waste to generate great economic benefit. The method has the advantages of simple operation, safe process, high lithium resource recovery efficiency and the like.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a comprehensive treatment method of lithium-containing waste comprises the following steps:
s1: mixing and stirring lithium-containing waste with hydrochloric acid for reaction to obtain a mixed extracting solution;
s2: deodorizing and removing impurities from the mixed extracting solution to obtain refined lithium-containing extracting solution;
s3: and adding a precipitant into the refined lithium-containing extracting solution to perform lithium precipitation operation, so as to obtain a lithium carbonate product.
Further, the concentration of the hydrochloric acid in the step S1 is 20-30%.
Further, the step of mixing and stirring reaction in the step S1 is as follows: mixing the hydrochloric acid and the lithium-containing waste in a solid-liquid ratio of (2-4) to 1, and then reacting for 2-6 h under the stirring condition.
Further, the deodorizing and impurity removing operation in the step S2 includes the following steps:
s100: adding a certain amount of hydrogen peroxide into the mixed extracting solution to perform deodorization to obtain a first lithium-containing extracting solution;
s200: adding an alkali reagent into the first lithium-containing extracting solution to adjust the pH to 6.5-7.5, and obtaining a second lithium-containing extracting solution after precipitation and impurity removal;
s300: adding a certain amount of activated carbon into the second lithium-containing extracting solution, and adsorbing and removing impurities to obtain a third lithium-containing extracting solution;
s400: and adding a certain amount of barium carbonate into the third lithium-containing extracting solution, and precipitating and removing impurities to obtain the refined lithium-containing extracting solution.
Further, the addition amount of the hydrogen peroxide in the step S100 is 0.5-5 wt% of the mass of the lithium-containing waste.
Further, the alkaline agent in step S200 may be at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like.
Further, the addition amount of the activated carbon in the step S300 is 0.5-5 wt% of the mass of the lithium-containing waste, and the activated carbon is added and then stirred continuously for 6-12 h.
Further, the addition amount of the barium carbonate in the step S400 is 1.1 to 2.5 times of the total number of moles of calcium ions and sulfate ions in the reaction system.
Further, in the step S3, the precipitant is sodium carbonate, and the adding amount of the sodium carbonate is 1.05-1.5 times of the molar amount of lithium ions in the refined lithium-containing extracting solution.
Further, the conditions of the lithium precipitation operation in the step S3 are that the lithium precipitation is carried out for 0.5 to 2 hours at the temperature of 90 to 95 ℃, and the filtration is carried out at the temperature of 90 to 95 ℃ after the lithium precipitation.
Compared with the prior art, the invention has the following advantages:
the waste lithium belt contains about 20% of lithium element by mass, and the method provided by the invention not only can neutralize acidic substances in the waste lithium belt and reduce environmental pollution, but also can recycle the lithium element in the waste lithium belt, thereby generating great economic benefit. The method has the advantages of simple operation, safe process, high recovery efficiency of lithium resources, high comprehensive recovery rate up to more than 90%, and reduced resource waste.
Drawings
Fig. 1 is a process flow chart of the comprehensive treatment method of lithium-containing waste in example 1 of the present invention.
Detailed Description
The invention will be described in further detail with reference to specific embodiments and examples in the following, but embodiments of the invention are not limited thereto. All materials and reagents used in the present invention are commercially available conventional materials and reagents unless otherwise specified. The dosage of each component in the examples is g and mL in parts by mass and volume.
A comprehensive treatment method of lithium-containing waste comprises the following steps:
s1: mixing and stirring lithium-containing waste with hydrochloric acid for reaction to obtain a mixed extracting solution;
s2: deodorizing and removing impurities from the mixed extracting solution to obtain refined lithium-containing extracting solution;
s3: and adding a precipitant into the refined lithium-containing extracting solution to perform lithium precipitation operation, so as to obtain a lithium carbonate product.
In addition, conventionally, waste lithium strips are generally treated as hazardous waste, and after a certain weight is collected, the waste lithium strips are uniformly treated by a third party treatment mechanism, so that the treatment cost is low, and the applicant designs a method for comprehensively recovering and treating the lithium-containing waste, so that not only can the hazardous substances in the waste lithium strips be treated, but also lithium metal in the lithium-containing waste can be recovered.
S1: mixing and stirring lithium-containing waste and hydrochloric acid for reaction to obtain a mixed extracting solution.
Further, the concentration of hydrochloric acid in the step S1 is 20 to 30%, preferably 30%.
Further, the step of mixing and stirring reaction in the step S1 is as follows: mixing the hydrochloric acid and the lithium-containing waste in a solid-liquid ratio of (2-4) to 1, then reacting for 2-6 hours under stirring, preferably mixing the hydrochloric acid and the lithium-containing waste in a mass ratio of 2.5 to 1, and then reacting for 2 hours under stirring.
It should be noted that, the hydrochloric acid and the lithium-containing waste should be mixed in a proper mass ratio, when the amount of the hydrochloric acid is too small, the leaching of lithium element in the lithium-containing waste is not complete, and when the amount of the hydrochloric acid is too large, the next deodorizing and impurity removing operation is affected.
S2: and (3) deodorizing and removing impurities from the mixed extracting solution to obtain a refined lithium-containing extracting solution.
Further, the deodorizing and impurity removing operation in the step S2 includes the following steps:
s100: and adding a certain amount of hydrogen peroxide into the mixed extracting solution to perform deodorization, so as to obtain a first lithium-containing extracting solution.
The amount of hydrogen peroxide added is 0.5 to 5wt%, preferably 1wt%, based on the mass of the lithium-containing waste. The added hydrogen peroxide can oxidize sulfide (such as sulfurous acid and the like) in the mixed extracting solution, so that the mixed extracting solution is not easy to decompose to generate pungent gases such as sulfur dioxide and the like, and meanwhile, the hydrogen peroxide is used as a strong oxidant, so that the mixed extracting solution has the advantage of simple structure, and new impurity elements cannot be introduced into the mixed extracting solution.
S200: and adding an alkali reagent into the first lithium-containing extracting solution to adjust the pH to 6.5-7.5, and obtaining a second lithium-containing extracting solution after precipitation and impurity removal.
The purpose of adding the alkali reagent in this step is mainly to add Al 3+ Impurity ions are removed in a precipitation mode, and the reaction equation is Al 3+ +3OH - ＝Al(OH) 3 And ∈. In addition, the operation of adding the alkaline reagent can also add Fe 2+ 、Fe 3+ 、Mg 2+ 、Ca 2+ The plasma is removed, wherein the alkali agent can be at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. The alkali agent is preferably lithium hydroxide, so that no new impurity element is introduced into the reaction system. Further, the alkaline reagent is added under stirring, and after the precipitation is completed, the precipitate is removed by a conventional separation method, for example, filtration is adopted to remove the precipitate.
S300: and adding a certain amount of activated carbon into the second lithium-containing extracting solution, and adsorbing and removing impurities to obtain a third lithium-containing extracting solution.
The main purpose of adding activated carbon is to adsorb and remove organic substances, heavy metals, phosphorus and other impurities in the solution. The addition amount of the active carbon is 0.5-5 wt% of the mass of the lithium-containing waste, for example, 2wt%, 3wt% and 4wt% can be added; after adding the activated carbon, stirring continuously for 6-12 h to ensure that the activated carbon adsorbs organic matters more completely, wherein the stirring time can be 6h, 8h, 10h, 12h and the like; after the adsorption is completed, the active carbon is separated from the solution by adopting filtration separation, the active carbon obtained by separation is washed by hydrochloric acid and then roasted for 0.5 to 1 hour at the temperature of 180 to 220 ℃ for regeneration, the regenerated active carbon can be recycled or used as fuel, wherein the regeneration process is as follows: activated carbon + organics- & gtadsorbed activated carbon; adsorption of activated carbon (at 180-220 ℃) -activated carbon + organic ≡.
S400: and adding a certain amount of barium carbonate into the third lithium-containing extracting solution, and precipitating and removing impurities to obtain the refined lithium-containing extracting solution.
The addition amount of the barium carbonate is 1.1 to 2.5 times of the total number of moles of calcium ions and sulfate ions in the reaction system, for example, 1.5 times and 2.0 times of the total number of moles of calcium ions and sulfate ions can be added; after adding the barium carbonate, stirring for 12-36 h under normal temperature, and precipitating and removing impurities, wherein the stirring time can be 18h, 24h and 30h; and removing the precipitate by adopting a filtering mode after the precipitate is completed, so as to obtain the refined lithium-containing extract.
Wherein the main purpose of adding barium carbonate is to remove Ca which is completely removed in the third lithium-containing extract 2+ 、Ba 2+ 、SO 4 2- The impurity ions have low solubility of barium carbonate but low solubility of calcium carbonate and barium sulfate, so that calcium carbonate and barium sulfate precipitate can be formed. Meanwhile, the content of barium ions in the solution can be reduced, environmental pollution and products are avoided, and the specific precipitation process is as follows:
Ca 2+ +CO 3 2- ＝CaCO 3 ↓
Ba 2+ +SO 4 2- ＝BaSO 4 ↓
s3: and adding a precipitant into the refined lithium-containing extracting solution to perform lithium precipitation operation, so as to obtain a lithium carbonate product.
The precipitant is sodium carbonate, and the adding amount of the sodium carbonate is 1.05-1.5 times of the molar amount of lithium ions in the refined lithium-containing extracting solution; wherein the conditions of the lithium precipitation operation are that the lithium precipitation is carried out for 0.5 to 2 hours at the temperature of 90 to 95 ℃, and the lithium carbonate product is obtained by filtering at the temperature of 90 to 95 ℃ after the lithium precipitation.
The lithium precipitation reaction is：2Li + +CO 3 2- ＝Li 2 CO 3 ↓
Further, in order to improve the purity of the lithium carbonate product, the obtained lithium carbonate product is put into hot water for stirring and washing, wherein the mass ratio of solid to liquid is 1:1-3, the temperature of the hot water is 90-95 ℃, the washing is carried out, the filtering is carried out under the condition of 90-95 ℃, and finally the industrial grade lithium carbonate product is obtained after drying.
The following is a detailed description of embodiments.
Example 1
S1: mixing the lithium-containing waste and 30% hydrochloric acid according to the solid-liquid ratio of 2.5:1, and stirring and reacting for 2 hours to obtain a mixed extracting solution;
s2: adding hydrogen peroxide (the addition amount of the hydrogen peroxide is 1wt% of the lithium-containing waste) into the mixed extracting solution to perform deodorization, so as to obtain a first lithium-containing extracting solution;
adding lithium hydroxide into the first lithium-containing extracting solution to adjust the pH to 7.0, and filtering after precipitation is completed to obtain a second lithium-containing extracting solution;
adding active carbon (the addition amount of the active carbon is 2wt% of the lithium-containing waste) into the second lithium-containing extract, stirring for 6 hours to perform adsorption and impurity removal, and then filtering to obtain a third lithium-containing extract;
adding barium carbonate (the adding amount of the barium carbonate is 1.5 times of the total mole number of calcium ions and sulfate ions) into the third lithium-containing extracting solution, stirring for 24 hours, precipitating and removing impurities, and filtering to obtain refined lithium-containing extracting solution;
s3: adding sodium carbonate (the adding amount of the sodium carbonate is 1.05 times of the molar amount of lithium ions in the refined lithium-containing extracting solution) into the refined lithium-containing extracting solution, precipitating lithium for 45min at 95 ℃, filtering while the solution is hot, washing the precipitate with hot water, and drying to obtain an industrial-grade lithium carbonate product.
Example 2
S1: mixing the lithium-containing waste and 20% hydrochloric acid according to the solid-liquid ratio of 2:1, and stirring and reacting for 6 hours to obtain a mixed extracting solution;
s2: adding hydrogen peroxide (the addition amount of the hydrogen peroxide is 4wt% of the lithium-containing waste) into the mixed extracting solution to perform deodorization, so as to obtain a first lithium-containing extracting solution;
adding lithium hydroxide into the first lithium-containing extracting solution to adjust the pH to 6.5, and filtering after precipitation is completed to obtain a second lithium-containing extracting solution;
adding active carbon (the addition amount of the active carbon is 3wt% of the lithium-containing waste) into the second lithium-containing extract, stirring for 10 hours to perform adsorption and impurity removal, and then filtering to obtain a third lithium-containing extract;
adding barium carbonate (the adding amount of the barium carbonate is 1.1 times of the total mole of calcium ions and sulfate ions) into the third lithium-containing extracting solution, stirring for 36h, precipitating and removing impurities, and filtering to obtain refined lithium-containing extracting solution;
s3: adding sodium carbonate (the adding amount of the sodium carbonate is 1.2 times of the molar amount of lithium ions in the refined lithium-containing extracting solution) into the refined lithium-containing extracting solution, precipitating lithium for 1h at 95 ℃, filtering while the solution is hot, washing the precipitate with hot water, and drying to obtain an industrial-grade lithium carbonate product.
Example 3
S1: mixing the lithium-containing waste and 25% hydrochloric acid according to the solid-liquid ratio of 4:1, and stirring and reacting for 4 hours to obtain a mixed extracting solution;
s2: adding hydrogen peroxide (the addition amount of the hydrogen peroxide is 2wt% of the lithium-containing waste) into the mixed extracting solution to perform deodorization, so as to obtain a first lithium-containing extracting solution;
adding lithium hydroxide into the first lithium-containing extracting solution to adjust the pH to 7.5, and filtering after precipitation is completed to obtain a second lithium-containing extracting solution;
adding active carbon (the addition amount of the active carbon is 4wt% of the lithium-containing waste) into the second lithium-containing extract, stirring for 8 hours to perform adsorption and impurity removal, and then filtering to obtain a third lithium-containing extract;
adding barium carbonate (the addition amount of the barium carbonate is 2.0 times of the total mole number of calcium ions and sulfate ions) into the third lithium-containing extracting solution, stirring for 12 hours, precipitating and removing impurities, and filtering to obtain refined lithium-containing extracting solution;
s3: adding sodium carbonate (the adding amount of the sodium carbonate is 1.5 times of the molar amount of lithium ions in the refined lithium-containing extracting solution) into the refined lithium-containing extracting solution, precipitating lithium for 30min at 95 ℃, filtering while the solution is hot, washing the precipitate with hot water, and drying to obtain an industrial-grade lithium carbonate product.
Comparative example 1
Comparative example 1 differs from example 1 in that the impurity removal by activated carbon adsorption is not performed in step S2.
Comparative example 2
Comparative example 2 differs from example 1 in that no barium carbonate precipitation was used to remove impurities in step S2.
The lithium carbonate prepared in examples 1 to 3 and comparative examples 1 to 2 was subjected to content measurement according to GB/T11064.1-2013. The specific results are shown in Table 1.
Table 1 results of lithium carbonate content test for each of examples and comparative examples
| Project | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Li 2 CO 3 Purity of | 96.93％ | 95.92％ | 97.91％ | 87.45％ | 92.61％ |
| Recovery% | 92.24％ | 92.12％ | 91.84％ | 91.67％ | 89.67％ |
As can be seen from the data in Table 1, the method provided by the invention can well recover lithium elements in lithium-containing waste, wherein the recovery rate can reach more than 90%, the purity of the recovered lithium carbonate can reach more than 95%, not only can the lithium resource be well recovered, but also hydrogen sulfite, organic matters, heavy metals and the like can be treated to prevent the pollution of the environment, the extraction liquid is not used for carrying out adsorption and impurity removal by the active carbon in comparative example 1, the purity of the finally obtained lithium carbonate is not ideal, the active carbon has strong adsorption effect, the organic matters, phosphorus, heavy metals and the like are well adsorbed, the impurity of the extraction liquid after the active carbon treatment is obviously reduced, the extraction liquid is not used for carrying out precipitation and impurity removal by the barium carbonate in comparative example 2, the impurity content of the finally obtained lithium carbonate is relatively high, namely, most impurity ions are removed in the previous step, but Ca 2+ The hydroxide precipitate of the ion is slightly soluble in water, ba 2+ Is poorly soluble in water, SO 4 2- The lithium carbonate is difficult to remove, and three impurity ions can be removed better after the precipitation and impurity removal of the barium carbonate, so that the purity of the lithium carbonate is improved finally.
In summary, the comprehensive treatment method of lithium-containing waste adopted in the embodiment not only can well recover lithium resources, the recovery rate is more than 90%, but also the purity of the recovered lithium carbonate is higher and can be more than 95% through a specific impurity removal and purification process.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the scope of the present invention.
Claims (4)
1. The comprehensive treatment method of the lithium-containing waste is characterized by comprising the following steps of:
s1: mixing and stirring lithium-containing waste and hydrochloric acid to react to obtain a mixed extract, wherein the concentration of the hydrochloric acid is 20-30%;
s2: deodorizing and removing impurities from the mixed extracting solution to obtain refined lithium-containing extracting solution;
s3: adding a precipitant into the refined lithium-containing extracting solution to perform lithium precipitation operation, so as to obtain a lithium carbonate product;
the deodorizing and impurity removing operation in the step S2 comprises the following steps:
s100: adding a certain amount of hydrogen peroxide into the mixed extracting solution to perform deodorization to obtain a first lithium-containing extracting solution, wherein the adding amount of the hydrogen peroxide is 0.5-5 wt% of the mass of the lithium-containing waste;
s200: adding an alkali reagent into the first lithium-containing extracting solution to adjust the pH to 6.5-7.5, and precipitating and removing impurities to obtain a second lithium-containing extracting solution, wherein the alkali reagent is at least one of lithium hydroxide, sodium hydroxide and potassium hydroxide;
s300: adding a certain amount of activated carbon into the second lithium-containing extracting solution, adsorbing and removing impurities to obtain a third lithium-containing extracting solution, wherein the adding amount of the activated carbon is 0.5-5 wt% of the mass of the lithium-containing waste, and continuously stirring for 6-12 h after adding the activated carbon;
s400: adding a certain amount of barium carbonate into the third lithium-containing extracting solution, precipitating and removing impurities to obtain the refined lithium-containing extracting solution, wherein the adding amount of the barium carbonate is 1.1-2.5 times of the total number of moles of calcium ions and sulfate ions in a reaction system.
2. The comprehensive treatment method of lithium-containing waste according to claim 1, wherein: the step of mixing and stirring reaction in the step S1 is as follows: mixing the hydrochloric acid and the lithium-containing waste in a solid-liquid ratio of (2-4) to 1, and then reacting for 2-6 h under the stirring condition.
3. The comprehensive treatment method of lithium-containing waste according to claim 1, wherein: and S3, the precipitant is sodium carbonate, and the adding amount of the sodium carbonate is 1.05-1.5 times of the molar amount of lithium ions in the refined lithium-containing extracting solution.
4. The comprehensive treatment method of lithium-containing waste according to claim 1, wherein: and S3, the conditions of the lithium precipitation operation in the step are that the lithium precipitation is carried out for 0.5 to 2 hours at the temperature of 90 to 95 ℃, and the filtration is carried out at the temperature of 90 to 95 ℃ after the lithium precipitation.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012172223A (en) * | 2011-02-23 | 2012-09-10 | Jx Nippon Mining & Metals Corp | Method for recovering lithium |
| KR101713600B1 (en) * | 2016-03-04 | 2017-03-09 | 재단법인 포항산업과학연구원 | Method of recovering lithium in wastewater obtained from waste lithium battery recycling process |
| CN106848472A (en) * | 2017-04-18 | 2017-06-13 | 中科过程（北京）科技有限公司 | A kind of method that lithium is reclaimed in waste lithium iron phosphate battery |
| CN109065999A (en) * | 2018-08-17 | 2018-12-21 | 湖南金凯循环科技有限公司 | A method of recycling waste and old lithium titanate battery |
| CN111186849A (en) * | 2019-12-30 | 2020-05-22 | 江西赣锋循环科技有限公司 | Method for recovering organic complexing agent from lithium precipitation mother liquor |
| CN112410556A (en) * | 2020-09-25 | 2021-02-26 | 湖北金泉新材料有限公司 | Method for recovering waste lithium iron phosphate powder |
| CN112441572A (en) * | 2019-08-27 | 2021-03-05 | 比亚迪股份有限公司 | Method for recovering waste lithium iron phosphate anode material |
| CN112725621A (en) * | 2020-09-17 | 2021-04-30 | 湖北金泉新材料有限公司 | Method for separating nickel, cobalt and manganese from waste lithium battery based on carbonate solid-phase conversion method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007074513A1 (en) * | 2005-12-27 | 2007-07-05 | Kawasaki Plant Systems Kabushiki Kaisha | Apparatus and method for recovering valuable substance from lithium rechargeable battery |
| JP7217612B2 (en) * | 2018-10-31 | 2023-02-03 | Ｊｘ金属株式会社 | Method for processing positive electrode active material waste of lithium ion secondary battery |
-
2022
- 2022-02-28 CN CN202210189729.2A patent/CN114589186B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012172223A (en) * | 2011-02-23 | 2012-09-10 | Jx Nippon Mining & Metals Corp | Method for recovering lithium |
| KR101713600B1 (en) * | 2016-03-04 | 2017-03-09 | 재단법인 포항산업과학연구원 | Method of recovering lithium in wastewater obtained from waste lithium battery recycling process |
| CN106848472A (en) * | 2017-04-18 | 2017-06-13 | 中科过程（北京）科技有限公司 | A kind of method that lithium is reclaimed in waste lithium iron phosphate battery |
| CN109065999A (en) * | 2018-08-17 | 2018-12-21 | 湖南金凯循环科技有限公司 | A method of recycling waste and old lithium titanate battery |
| CN112441572A (en) * | 2019-08-27 | 2021-03-05 | 比亚迪股份有限公司 | Method for recovering waste lithium iron phosphate anode material |
| CN111186849A (en) * | 2019-12-30 | 2020-05-22 | 江西赣锋循环科技有限公司 | Method for recovering organic complexing agent from lithium precipitation mother liquor |
| CN112725621A (en) * | 2020-09-17 | 2021-04-30 | 湖北金泉新材料有限公司 | Method for separating nickel, cobalt and manganese from waste lithium battery based on carbonate solid-phase conversion method |
| CN112410556A (en) * | 2020-09-25 | 2021-02-26 | 湖北金泉新材料有限公司 | Method for recovering waste lithium iron phosphate powder |
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