CN113582206A - Method for recovering and preparing crude lithium carbonate from battery material raffinate - Google Patents
Method for recovering and preparing crude lithium carbonate from battery material raffinate Download PDFInfo
- Publication number
- CN113582206A CN113582206A CN202110814246.2A CN202110814246A CN113582206A CN 113582206 A CN113582206 A CN 113582206A CN 202110814246 A CN202110814246 A CN 202110814246A CN 113582206 A CN113582206 A CN 113582206A
- Authority
- CN
- China
- Prior art keywords
- lithium
- raffinate
- carbonate
- recovering
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
-
- 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
-
- 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 discloses a method for recovering and preparing crude lithium carbonate from battery material raffinate. According to the invention, the zirconium-based fluorine removal agent is used for removing fluorine brought into raffinate in the battery recovery process, a sodium sulfate product is obtained through evaporation separation, the evaporation cycle mother liquor is added with carbonate to precipitate lithium, and the sodium content in the lithium carbonate product is reduced by adopting a multipoint scattering addition mode of a lithium precipitation front liquid in the lithium precipitation process. The method has the characteristics of short process flow, low product impurity, realization of internal cyclic utilization of the lithium precipitation mother liquor, low production cost and the like. The content of sodium lithium carbonate prepared by the method is lower than 0.1%, the main content of lithium carbonate is higher than 98.50%, the fluorine content is lower than 0.020%, and all indexes meet the level requirement of industrial-grade lithium carbonate.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for preparing low-sodium low-fluorine crude lithium carbonate from low-lithium high-sodium battery material raffinate at low cost.
Background
Lithium ion batteries have been developed well as the most favored secondary batteries. At present, a large amount of waste batteries flow into the market in the period of retirement of power batteries, and the recovery of valuable metals such as nickel, cobalt, manganese, lithium and the like in the batteries is a great measure for realizing the recycling of limited resources and sustainable development.
Because of the defects of great pollution, low resource utilization rate and the like of the pyrogenic process, valuable metals such as nickel, cobalt, manganese and the like in the battery material are generally recycled by wet processes such as leaching and extraction. Lithium as a light metal is difficult to recover by extraction, but lithium metal in the raffinate can be recovered by adding carbonate according to the property that lithium metal combines with carbonate to form precipitate.
The lithium content in the scrapped lithium ion power battery is 5% -7%, the lithium content in the raffinate finally entering the waste battery after the cobalt, nickel and manganese are recovered through pretreatment, leaching and extraction is extremely low, the sodium content is extremely high, and the sodium-lithium ratio is up to 18-22: 1, the raffinate with low lithium and high sodium content is not feasible to be directly used in the lithium carbonate precipitation process.
Chinese patent publication No.: CN108002410B discloses a recycling method for recovering lithium from low-content extraction tail water and extraction tail water, and relates to a tail water lithium extraction and industrial wastewater recycling technology. In the patent, calcium is added into extraction tail liquid to remove fluorine, evaporation crystallization and precipitation of lithium are carried out to realize recovery of lithium. The patent has the following defects: the fluorine removal agent adopts calcium, has low fluorine removal efficiency, large fluorine removal amount and no phosphorus removal process (phosphorus in extraction tail liquid is higher), and the processes of crystallization, impurity removal and lithium deposition are adopted, so that the impurities in the sodium sulfate are higher, the sodium content in the lithium carbonate product is high and the main content is lower.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art, and provide a method for preparing low-sodium low-fluorine crude lithium carbonate from the raffinate of the low-lithium high-sodium battery material, so that the lithium precipitation efficiency is improved, the lithium extraction production cost is effectively reduced, and the recycling of lithium in the raffinate of the battery material is realized.
Therefore, the invention adopts the following technical scheme: a method for recovering and preparing crude lithium carbonate from a battery feed raffinate, comprising the steps of:
1) removing fluorine, namely adding zirconium-based fluorine removing agent into the battery raffinate to remove fluorine to obtain a fluorine-removed liquid with the fluorine content of less than 3 mg/L;
2) removing phosphorus, wherein the liquid after the fluorine removal is subjected to phosphorus removal through a phosphorus removing agent, and the obtained slag is scrapped after being stirred, washed and filter-pressed;
3) heavy metals, namely adding liquid auxiliary materials into the dephosphorized solution to carry out heavy metals, precipitating the heavy metals, and then carrying out filter pressing separation to obtain heavy metal mother liquor and heavy metal slag;
4) adjusting acid and alkali, adding an acidic solution into heavy metal mother liquor to adjust the pH value to acidity, removing residual carbonate, and adding an alkaline solution to adjust the pH value to neutrality;
5) evaporating and concentrating, namely performing two-effect circulating evaporation on the battery material raffinate after the acid and the alkali are adjusted to separate out sodium sulfate and simultaneously improve the lithium concentration;
6) precipitating lithium, namely adding carbonate into the concentrated mother liquor obtained in the step 5) to precipitate lithium, and filtering and separating to obtain a crude lithium carbonate product;
in the battery material raffinate, the Li content is 0.5-5 g/L, the sodium content is 30-80 g/L, the heavy metal content is 0.5-2 g/L, the fluorine content is 50-150 mg/L, and the phosphorus content is 30-60 mg/L.
Further, in the step 1), the zirconium-based fluorine removal agent is regenerated and recycled after reaching the upper adsorption limit.
Further, in the step 1), the concentration of sodium hydroxide in a regeneration liquid adopted in the regeneration process of the zirconium-based fluorine removal agent is 0.1-2 mol/L, and the mass ratio of the regeneration liquid to the zirconium-based fluorine removal agent is 2-8: 1, the regeneration temperature is normal temperature, and the regeneration time is 30-60 min.
Further, in the step 2), valuable metals are recovered from the heavy metal slag through a leaching process.
Further, in the step 1), the mass of the added zirconium-based defluorinating agent is 1-10% of the mass of the battery raffinate, the pH value is controlled to be 3-8 in the defluorination process, the temperature is normal temperature, and the time is 10-90 min.
Further, step 1), the zirconium-based fluorine removing agent mainly contains ZrO2+TIO2≥33％。
Further, in the step 2), the phosphorus removing agent is one or a mixture of several of ferric sulfate, calcium hydroxide and aluminum sulfate, the mixture is prepared into a solution with a mass concentration of 10% -30% for use, the added mass of the phosphorus removing agent solution is 0.01% -0.02% of the mass of the battery raffinate, the phosphorus removing pH is 3-10, the temperature is normal temperature, and the reaction time is 10-90 min.
Further, in the step 3), the liquid auxiliary material is a lithium precipitation mother liquor containing carbonate, and the adding ratio of the lithium precipitation mother liquor to the phosphorus-removed liquor is 1/5-1: 1, the reaction temperature is 50-70 ℃, the reaction time is 50-120 min, and the reaction pH is 8.5-13.
Further, in the step 4), the acid solution is 95-98% sulfuric acid solution, the alkaline solution is 30-32% liquid sodium hydroxide, the pH value of the acid is adjusted to 3-6, and the pH value of the alkali is adjusted to 6-9.
Further, in the step 5), the evaporation concentration ratio is 3-10 times, the concentration of lithium in the evaporation mother liquor is 10-20 g/L, and the concentration of sodium is 90-125 g/L.
Further, in the step 6), the selected carbonate is sodium carbonate, the mass concentration is 25-32%, the concentrated mother liquor (namely the solution before lithium deposition) is added in the lithium deposition process in a multi-point scattering mode, the lithium deposition temperature is higher than 80 ℃, the lithium deposition time is 0.5-3 h, and the addition amount of the soda ash is 1.05-1.15 times of the theoretical amount.
The invention has the following beneficial effects:
the zirconium-based fluorine removal agent is used in the lithium extraction of the battery material for the first time, and the fluorine removal rate is high.
The invention has short lithium extraction process, and the phosphorus removal agent adopts one or a mixture of iron base, calcium base and aluminum base, so that the phosphorus removal rate is high.
According to the invention, according to the characteristic that lithium in the battery raffinate is low and high in sodium, the concentration of the raw material lithium is increased while sodium sulfate is produced by cyclic evaporation, and then lithium is precipitated by using carbonate, so that the primary recovery rate of the metal lithium in the battery raffinate is greatly increased, and the recovery cost of the metal lithium in the battery raffinate is reduced.
In the invention, the concentrated mother liquor is added in a multipoint scattering manner, so that the probability of sodium wrapping the lithium carbonate product in a sodium sulfate system is effectively reduced, and the sodium content in the produced industrial-grade lithium carbonate product is lower than 0.1%.
The invention utilizes the characteristic of containing carbonate in the lithium precipitation mother liquor to carry out heavy metals in the battery raffinate, realizes the recycling of the carbonate in the lithium precipitation mother liquor and reduces the consumption of heavy metal accessories.
The content of sodium lithium carbonate prepared by the method is lower than 0.1%, the main content of lithium carbonate is higher than 98.50%, the fluorine content is lower than 0.020%, and all indexes meet the level requirement of industrial-grade lithium carbonate.
Drawings
FIG. 1 is a flow chart of a process for recovering lithium from battery raffinate in an embodiment of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the examples described are only for the aid of understanding the present invention and should not be construed as specifically limiting the present invention.
Example 1
Under the condition of normal temperature, adding 3% of defluorination agent into the battery material raffinate, starting stirring to control the pH value of defluorination to be 4.5, carrying out filter pressing on defluorination slurry after reaction time is 0.5h, regenerating the defluorination agent carrying fluorine by 0.5mol/L sodium hydroxide solution to remove fluorine, pulping the regenerated defluorination agent through the battery material raffinate, and returning to a defluorination working section for recycling; adding a phosphorus removal agent solution with the mass concentration of 15% into the fluorine-removed liquid obtained by filter pressing separation, controlling the pH to be 3.99, removing phosphorus within 30min, and separating phosphorus removal slurry by filter pressing. Adding a lithium precipitation mother solution (the mass ratio of the phosphorus-removed solution to the lithium precipitation mother solution is 3:1) into the phosphorus-removed and pressure-filtered solution, adjusting the pH to 10.0, controlling the temperature to be 60 ℃, carrying out pressure filtration on heavy metal slurry after reacting for 60min, and recovering nickel-containing heavy metal slag through leaching.
After heavy metals are subjected to filter pressing, 98% sulfuric acid is added into the solution to adjust the pH value to 4.0, 32% liquid alkali is added into the solution to adjust the pH value to 7.0, the solution after acid and alkali adjustment is evaporated by a two-effect circulation evaporator, the concentration ratio is controlled to be 4 times in the evaporation process, 30% sodium carbonate solution is added into the evaporation mother solution according to 1.1 time of the theoretical amount for lithium precipitation, the lithium precipitation temperature is 80 ℃, the lithium precipitation time is 2 hours, and the mother solution is added into a lithium precipitation container through multi-point scattering. The produced lithium carbonate reaches the national industrial grade lithium carbonate standard (GB/T11075-2013).
TABLE 1 battery raffinate composition Table
| Content (wt.) | Li/g/L | Na/g/L | F/mg/L | Cl/g/L | P/mg/L | Ni/g/L |
| Raffinate of battery material | 2.82 | 46.6 | 38.95 | 0.17 | 17.45 | 0.53 |
TABLE 2 fluorine and phosphorus removal filter-pressed liquid composition table
| Content (wt.) | F/mg/L | P/mg/L | pH |
| Fluorine and phosphorus removing filter pressing liquid | 1.63 | 3.25 | 3.99 |
TABLE 3 lithium carbonate Components TABLE
TABLE 4 sodium sulfate ingredient Table
| Content (%) | Na2SO4 | Ca | Mg | Li | Chloride compound |
| Sodium sulfate | 99.71 | 0.0001 | 0.0001 | 0.036 | 0.019 |
Example 2
Under the condition of normal temperature, adding 5% of defluorination agent into the battery material raffinate, starting stirring to control the pH value of defluorination to be 5.0, carrying out filter pressing on defluorination slurry after reaction time is 1h, regenerating the defluorination agent carrying fluorine by 1mol/L sodium hydroxide solution to remove fluorine, slurrying the regenerated defluorination agent through the battery material raffinate, and returning to a defluorination working section for recycling; adding a phosphorus removal agent solution with the mass concentration of 10% into the fluorine-removed liquid obtained by filter pressing separation, controlling the pH to be 4.12, removing phosphorus within 50min, and carrying out filter pressing separation on phosphorus removal slurry. Adding a lithium precipitation mother solution (the mass ratio of the phosphorus-removed solution to the lithium precipitation mother solution is 3:1) into the phosphorus-removed and pressure-filtered solution, adjusting the pH to 11.0, controlling the temperature to be 50 ℃, carrying out pressure filtration on heavy metal slurry after reacting for 90min, and recovering nickel-containing heavy metal slag through leaching.
After heavy metal is subjected to filter pressing, adding 98% sulfuric acid into the solution to adjust the pH value to 3.5, adding 32% liquid alkali to adjust the pH value to 7.5, adjusting the acid and alkali, evaporating the solution by a two-effect circulation evaporator, controlling the concentration ratio to be 5 times in the evaporation process, adding 28% sodium carbonate solution into the evaporation mother solution according to 1.05 times of the theoretical amount to precipitate lithium, wherein the lithium precipitation temperature is 85 ℃, the lithium precipitation time is 1h, and adding the mother solution into a lithium precipitation container through multi-point scattering. The produced lithium carbonate reaches the national industrial grade lithium carbonate standard (GB/T11075-2013).
TABLE 5 battery raffinate composition Table
| Content (wt.) | Li/g/L | Na/g/L | F/mg/L | Cl/g/L | P/mg/L | Ni/g/L |
| Raffinate of battery material | 3.15 | 50.57 | 67.5 | 0.11 | 14.35 | 0.47 |
TABLE 6 fluorine and phosphorus removal filter-pressed liquid composition table
| Content (wt.) | F/mg/L | P/mg/L | pH |
| Fluorine and phosphorus removing filter pressing liquid | 2.55 | 2.88 | 4.12 |
TABLE 7 lithium carbonate Components TABLE
| Content (%) | Li2CO3 | Na | SO4 2- | F | Cl | Ca | Mg | Fe | Hydrochloric acid insoluble substance | Ni |
| Lithium carbonate | 98.59 | 0.08 | 0.39 | 0.012 | 0.003 | 0.008 | 0.013 | 0.004 | 0.015 | 0.011 |
TABLE 8 sodium sulfate ingredient Table
| Content (%) | Na2SO4 | Ca | Mg | Li | Chloride compound | Li |
| Sodium sulfate | 99.68 | 0.0002 | 0.0001 | 0.052 | 0.012 | 0.052 |
The foregoing embodiments have described some of the details of the present invention, but it should not be construed as limiting the invention, and those skilled in the art may make variations, modifications, substitutions and alterations herein without departing from the principles and spirit of the invention.
Claims (10)
1. A method for recovering and preparing crude lithium carbonate from battery material raffinate, comprising the steps of:
1) removing fluorine, namely adding zirconium-based fluorine removing agent into the battery raffinate to remove fluorine to obtain a fluorine-removed liquid with the fluorine content of less than 3 mg/L;
2) removing phosphorus, wherein the liquid after the fluorine removal is subjected to phosphorus removal through a phosphorus removing agent, and the obtained slag is scrapped after being stirred, washed and filter-pressed;
3) heavy metals, namely adding liquid auxiliary materials into the dephosphorized solution to carry out heavy metals, precipitating the heavy metals, and then carrying out filter pressing separation to obtain heavy metal mother liquor and heavy metal slag;
4) adjusting acid and alkali, adding an acidic solution into heavy metal mother liquor to adjust the pH value to acidity, removing residual carbonate, and adding an alkaline solution to adjust the pH value to neutrality;
5) evaporating and concentrating, namely performing two-effect circulating evaporation on the battery material raffinate after the acid and the alkali are adjusted to separate out sodium sulfate and simultaneously improve the lithium concentration;
6) precipitating lithium, namely adding carbonate into the concentrated mother liquor obtained in the step 5) to precipitate lithium, and filtering and separating to obtain a crude lithium carbonate product;
in the battery material raffinate, the Li content is 0.5-5 g/L, the sodium content is 30-80 g/L, the heavy metal content is 0.5-2 g/L, the fluorine content is 50-150 mg/L, and the phosphorus content is 30-60 mg/L.
2. The method for recovering and preparing crude lithium carbonate from battery raffinate according to claim 1, wherein in the step 1), the zirconium-based fluorine removal agent is regenerated and recycled after reaching the upper adsorption limit.
3. The method for recovering and preparing crude lithium carbonate from battery raffinate according to claim 1, wherein in the step 1), the sodium hydroxide concentration of the regeneration liquid adopted in the regeneration process of the zirconium-based fluorine removal agent is 0.1-2 mol/L, and the mass ratio of the regeneration liquid to the zirconium-based fluorine removal agent is 2-8: 1, the regeneration temperature is normal temperature, and the regeneration time is 30-60 min; in the zirconium-based fluorine removing agent, the main content of ZrO2+TIO2≥33％。
4. The method for recovering and preparing crude lithium carbonate from battery material raffinate according to claim 1 or 2, wherein in the step 2), the heavy metal slag is used for recovering valuable metals through a leaching process.
5. The method for recovering and preparing crude lithium carbonate from battery raffinate according to claim 1 or 2, wherein in the step 1), the mass of the added zirconium-based fluorine removal agent is 1-10% of the mass of the battery raffinate, the pH value of the fluorine removal process is controlled to be 3-8, the temperature is normal temperature, and the time is 10-90 min.
6. The method for recovering and preparing crude lithium carbonate from battery material raffinate according to claim 1 or 2, characterized in that in step 2), the phosphorus removal agent is one or a mixture of several of ferric sulfate, calcium hydroxide and aluminum sulfate, and is used after being configured to have a mass concentration of 10-30%, the added mass of the phosphorus removal agent solution is 0.01-0.02% of the mass of the battery material raffinate, the phosphorus removal pH is 3-10, the temperature is normal temperature, and the reaction time is 10-90 min.
7. The method for recovering and preparing crude lithium carbonate from battery material raffinate according to claim 1 or 2, characterized in that in step 3), the liquid auxiliary material is a carbonate-containing lithium precipitation mother liquor, and the addition ratio of the lithium precipitation mother liquor to the phosphorus removal liquor is 1/5-1: 1, the reaction temperature is 50-70 ℃, the reaction time is 50-120 min, and the reaction pH is 8.5-13.
8. The method for recovering and preparing crude lithium carbonate from battery raffinate according to claim 1 or 2, wherein in the step 4), the acid solution is 95-98% sulfuric acid solution, the alkaline solution is 30-32% liquid sodium hydroxide, the acid pH is adjusted to 3-6, and the alkali pH is adjusted to 6-9.
9. The method for recovering and preparing crude lithium carbonate from battery material raffinate according to claim 1 or 2, wherein in the step 5), the evaporation concentration ratio is 3-10 times, and the lithium concentration of evaporation mother liquor is 10-20 g/L.
10. The method for recovering and preparing crude lithium carbonate from battery raffinate according to claim 1 or 2, wherein in the step 6), the selected carbonate is sodium carbonate, the mass concentration is 25-32%, the concentrated mother liquor is added in the lithium precipitation process in a multi-point scattering mode, the lithium precipitation temperature is higher than 80 ℃, the lithium precipitation time is 0.5-3 h, and the addition amount of the soda ash is 1.05-1.15 times of the theoretical amount.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110814246.2A CN113582206A (en) | 2021-07-19 | 2021-07-19 | Method for recovering and preparing crude lithium carbonate from battery material raffinate |
| KR1020210125166A KR20220140396A (en) | 2021-07-19 | 2021-09-17 | Method for recovering and manufacturing crude lithium carbonate from the battery meterial raffinate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110814246.2A CN113582206A (en) | 2021-07-19 | 2021-07-19 | Method for recovering and preparing crude lithium carbonate from battery material raffinate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113582206A true CN113582206A (en) | 2021-11-02 |
Family
ID=78248096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110814246.2A Pending CN113582206A (en) | 2021-07-19 | 2021-07-19 | Method for recovering and preparing crude lithium carbonate from battery material raffinate |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR20220140396A (en) |
| CN (1) | CN113582206A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114956425A (en) * | 2022-05-31 | 2022-08-30 | 昆山三一环保科技有限公司 | Treatment system and treatment method for waste lithium battery recovery wastewater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203635187U (en) * | 2013-10-16 | 2014-06-11 | 抚顺市禄通化工有限公司 | High-efficiency reaction kettle |
| CN108002410A (en) * | 2016-10-31 | 2018-05-08 | 湖南金源新材料股份有限公司 | The circulation utilization method that lithium and extraction tail water are recycled in tail water is extracted from low content |
-
2021
- 2021-07-19 CN CN202110814246.2A patent/CN113582206A/en active Pending
- 2021-09-17 KR KR1020210125166A patent/KR20220140396A/en not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203635187U (en) * | 2013-10-16 | 2014-06-11 | 抚顺市禄通化工有限公司 | High-efficiency reaction kettle |
| CN108002410A (en) * | 2016-10-31 | 2018-05-08 | 湖南金源新材料股份有限公司 | The circulation utilization method that lithium and extraction tail water are recycled in tail water is extracted from low content |
Non-Patent Citations (2)
| Title |
|---|
| 苏会东等: "《水污染控制工程》", 31 May 2017, 中国建材工业出版社 * |
| 陈家凯等: ""树脂基纳米钛锆氧化物复合吸附剂同步去除水中磷和氟"", 《环境科学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114956425A (en) * | 2022-05-31 | 2022-08-30 | 昆山三一环保科技有限公司 | Treatment system and treatment method for waste lithium battery recovery wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20220140396A (en) | 2022-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107267759B (en) | A kind of comprehensive recovering process of anode material for lithium-ion batteries | |
| CN111092273B (en) | Novel method for comprehensively recovering cobalt, nickel, manganese and lithium elements from ternary battery waste | |
| CN112662877B (en) | Method for preparing high-purity nickel sulfate from electrolytic manganese sulfide slag | |
| CN112575208B (en) | Method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag | |
| JP2019099874A (en) | Recovery method of lithium | |
| CN104659438A (en) | Method for preparing ternary positive electrode material precursor by virtue of waste batteries | |
| CN102070198A (en) | Method for preparing high-purity manganese sulfate and high-purity manganese carbonate by reduction leaching of pyrolusite through scrap iron | |
| CN114655969B (en) | Method for preparing lithium carbonate and iron phosphate by recycling high-impurity lithium iron phosphate positive electrode waste material | |
| CN111118311B (en) | Manganese-lithium separation method in comprehensive recovery of ternary battery waste | |
| CN111137909B (en) | Method for stepwise recovering lithium and magnesium in salt lake brine | |
| KR102558770B1 (en) | Manufacturing method of battery level Ni-Co-Mn mixed solution and battery level Mn solution | |
| CN114314661A (en) | Method for producing high-purity ammonium metavanadate by deeply removing cobalt from vanadium raw material | |
| CN112410555A (en) | Comprehensive recovery method for flotation silver concentrate from zinc hydrometallurgy acidic leaching residue | |
| WO2004099079A1 (en) | A method for producing an electrolytic solution containing vanadium | |
| CN108517538B (en) | The method of waste solution of copper electrolysis synthetical recovery processing | |
| CN111778413B (en) | Method for extracting gallium from fly ash based on resin method | |
| CN112838289B (en) | Method for recovering lithium and ferrous phosphate from lithium iron phosphate positive electrode material | |
| CN113582206A (en) | Method for recovering and preparing crude lithium carbonate from battery material raffinate | |
| CN112342383B (en) | Method for separating and recovering nickel, cobalt, manganese and lithium in ternary waste | |
| CN113603120A (en) | Method for recovering battery-grade lithium from waste lithium iron phosphate through short-process acid leaching | |
| CN109650458B (en) | Preparation method and application of battery-grade manganese sulfate | |
| CN217323729U (en) | System for ferric phosphate contains full element resourceful treatment of ammonia nitrogen waste water | |
| CN110615453B (en) | Method for directly preparing battery-grade lithium carbonate | |
| CN113666397A (en) | Method for economically recycling lithium from waste lithium iron phosphate material by acid process | |
| CN110092423B (en) | Method for producing nickel sulfate solution by quickly dissolving nickel oxide and deacidifying and removing impurities with nickel soap |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |