CN107974565B - Method for selective nitric acid leaching of lithium element in aluminum electrolyte - Google Patents
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- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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Abstract
The invention discloses a method for selective nitric acid leaching of lithium element in aluminum electrolyte, and relates to the technical field of extraction and recovery of aluminum electrolyte. Which comprises the following steps: s1, crushing and screening the aluminum electrolyte containing the lithium element; s2, mixing nitric acid and water, and adjusting the pH value of the acid solution to be less than 4 and the potential to be 0.015-0.8V; s3, adding the aluminum electrolyte into the acid solution, stirring and heating for leaching, wherein the reaction temperature is 20-85 ℃, the adding amount of the aluminum electrolyte is controlled according to the concentration and acidity of the fluoride ions in the solution, the acidity is controlled to be a pH value smaller than 4, and the concentration of the fluoride ions is larger than 1 g/L; s4, filtering and washing the mixed solution to obtain filtrate and filtrate; and S5, extracting lithium element from the filtrate, washing and drying the filtrate, and returning the filtrate to an electrolytic aluminum plant for producing aluminum electrolyte and/or returning the filtrate to the leaching process. The method selectively leaches lithium salt, recovers the lithium salt with high added value, obtains the industrial electrolyte with higher purity and suitable for the production of the aluminum electrolyte, and has low energy consumption and extraction cost for the production of the electrolytic aluminum.
Description
Technical Field
The invention relates to the technical field of extraction and recovery of aluminum electrolyte, and relates to a method for selectively leaching lithium element in aluminum electrolyte by using nitric acid.
Background
The rapid development of the electrolytic aluminum industry in China has sharply increased the demand of bauxite resources. China is facing exhaustion of high-grade bauxite, and only a large amount of medium-low grade bauxite is exploited to produce metallurgical-grade alumina. The medium-low grade bauxite contains a large amount of alkali metal elements, and particularly, the bauxite in the main production area of the bauxite in China has high lithium salt content. A large amount of aluminum oxide containing lithium salt is used as a raw material for producing electrolytic aluminum, so that the electrolyte components in an aluminum electrolytic cell are changed, the lithium salt is enriched in the electrolyte in a large amount, the primary crystal temperature and the solubility of the aluminum oxide of the electrolyte are reduced, the aluminum electrolysis temperature is reduced, the precipitation at the furnace bottom is increased, the current efficiency is reduced, the aluminum energy consumption per ton is increased, the economic benefit of the aluminum electrolysis industry in China is directly influenced, and the problem to be solved in the aluminum electrolysis industry in China is urgently solved. Therefore, the method for removing the lithium element in the aluminum electrolyte has important significance for the development of the aluminum electrolysis industry in China. Meanwhile, the industrial application field of lithium salts, such as lithium batteries, aluminum lithium alloys, lithium bromide air conditioners, atomic energy industries, organic synthesis and the like, is continuously expanded, the demand for lithium salts is rapidly developed, and lithium resources also face challenges. If the aluminum-containing electrolyte can be used as a lithium salt resource to extract lithium salt in the lithium salt resource, the method also has important significance for the development of lithium salt industry in China.
At present, lithium salt in the aluminum electrolyte can be leached by adopting a nitric acid solution, but the lithium salt can be leached by adopting the leaching mode, and all components in the aluminum electrolyte can be leached out, so that the acid consumption is increased, and the subsequent separation of the lithium salt and other components is difficult, thereby greatly increasing the production cost.
In summary, there is a need for a method for selective nitric acid leaching of lithium in aluminum electrolyte, which can selectively leach lithium salt, recover high-added-value lithium salt, obtain high-purity industrial electrolyte suitable for aluminum electrolyte production, reduce energy consumption in electrolytic aluminum production, and reduce comprehensive average extraction cost.
Disclosure of Invention
Technical problem to be solved
In order to solve the problems in the prior art, the invention provides a method for selectively leaching lithium element in an aluminum electrolyte by nitric acid, which can effectively extract the lithium element in the electrolyte, recover high-added-value lithium salt, obtain an industrial electrolyte with higher purity and suitable for aluminum electrolyte production, and reduce the energy consumption and extraction cost of electrolytic aluminum production.
(II) technical scheme
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for selectively leaching lithium element by nitric acid in an aluminum electrolyte, which comprises the following steps:
s1, crushing and screening the aluminum electrolyte containing the lithium element;
s2, mixing nitric acid and water, and adjusting the pH value of the acid solution to be less than 4 and the potential to be between 0.015 and 0.8V;
s3, adding the aluminum electrolyte treated in the step S1 into the acid solution obtained in the step S2, stirring and heating for leaching, wherein in the leaching process, the reaction temperature is 20-85 ℃, the adding amount of the aluminum electrolyte is comprehensively controlled according to the concentration of fluoride ions and acidity in the solution, the acidity is that the pH value is less than 4, and the concentration of the fluoride ions is more than 1 g/L;
s4, after the reaction is finished, filtering and washing the mixed solution after the reaction to obtain primary filtrate and primary filtrate after the reaction;
and S5, extracting lithium element from the primary filtrate, washing and drying the primary filtrate, and returning the primary filtrate to an electrolytic aluminum plant for producing aluminum electrolyte and/or returning the primary filtrate to the leaching process.
According to the present invention, in step S1, the aluminum electrolyte is crushed and sieved through a 80-120 mesh sieve.
According to the present invention, before step S1, the aluminum electrolyte is an aluminum electrolyte obtained by mixing the aluminum electrolyte with an additive and calcining the mixture to change the phase of the lithium salt into a soluble lithium salt.
According to the present invention, in step S2, distilled water is used as the water.
According to the invention, in step S3, the pH value at the end of the reaction should be less than 5, and the fluorine ion concentration should be greater than 1 g/L; according to different compositions of materials, the nitric acid is added properly.
According to the present invention, in step S3, the reaction temperature of the mixed solution is adjusted to 30 to 80 ℃.
According to the invention, in step S3, the fluoride ion concentration is 1-80 g/L.
According to the present invention, in step S3, the pH of the mixed solution is controlled by an acidimeter, and the fluoride ion concentration of the mixed solution is controlled by a fluoride ion concentration selection electrode.
(III) advantageous effects
The invention has the beneficial effects that:
different from the existing method for leaching all components in the aluminum electrolyte by adopting nitric acid solution, the method only leaches Li in the aluminum electrolyte by controlling the potential, the pH value and the fluorine ion concentration of the acid solution2O, LiF and Li3AlF6The lithium salt is leached out, other components in the aluminum electrolyte are not dissolved out or the leaching is little, the separation of the lithium salt and the electrolyte main body is realized, so that the lithium element in the aluminum electrolyte is effectively extracted, the recovery of the lithium salt in the aluminum electrolyte is possible, the method is economically feasible, the recovery of the lithium salt with high added value is realized, meanwhile, the industrial electrolyte with higher purity and suitable for the production of the electrolytic aluminum can be obtained, the energy consumption and the comprehensive average extraction cost of the electrolytic aluminum production are greatly reduced, and the method is suitable for application and popularization in the industrial production.
The raw materials used in the method are common raw materials in the chemical field, the price is low, the process is simple, selective leaching (the LiF leaching rate of lithium salt is 70-99%, and the electrolyte leaching rate is lower than 10%) can be realized by controlling the concentration, the potential and the pH value of the solution in the leaching process, the production cost is reduced, various substances can be separated, and the purity of the obtained substances is high.
Based on the purpose of extracting lithium element in the aluminum electrolyte, the invention successfully researches a method for extracting the lithium element in the aluminum electrolyte by selectively leaching nitric acid, solves the problem of influence of the lithium element in the aluminum electrolysis industry, increases the benefit, improves the comprehensive level of the aluminum electrolysis industry in China, and expands the lithium salt resource supply in China.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail below with reference to specific embodiments.
The invention provides a method for selectively leaching lithium element by nitric acid in an aluminum electrolyte, which comprises the following steps:
s1, crushing the aluminum electrolyte containing the lithium element, sieving the crushed aluminum electrolyte with a sieve of 80-120 meshes, removing the sieved material and performing acid leaching.
The selected aluminum electrolyte can be directly from an aluminum electrolyte in an electrolytic cell of an electrolytic aluminum plant, or can be obtained by mixing an aluminum electrolyte raw material from the electrolytic cell of the electrolytic aluminum plant with an additive and roasting at a high temperature to fully convert insoluble lithium salt in the aluminum electrolyte into soluble lithium salt, namely, a transformation electrolyte for changing the phase of the aluminum lithium salt into the soluble lithium salt.
The additive is one or more of alkali metal oxide except lithium, alkali metal oxysalt except lithium capable of being converted into the alkali metal oxide under high-temperature roasting conditions, and alkali metal halide except lithium, and is mixed according to the type of the additive, the molecular ratio of the aluminum electrolyte and the content of lithium salt in the aluminum electrolyte, and the following conditions are met: ensure that the aluminum electrolyte in the mixed material contains alkali metal fluoride and the alkali metal fluoride directly added by the additiveThe molar ratio of the alkali metal fluoride to the aluminum fluoride to which the additive is convertible under high temperature calcination conditions (i.e., (LiF + NaF + KF)/AlF3>3) Greater than 3. Compacting or briquetting the mixed material, and roasting at 300-1200 ℃ for 3-5h, wherein insoluble lithium salt in the aluminum electrolyte is converted into soluble lithium salt in the roasting process.
Wherein, the alkali metal oxide except lithium can be selected from one or a mixture of sodium oxide and potassium oxide. The alkali metal oxide other than lithium may be selected from sodium oxide, potassium oxide, or a mixture of both. The alkali metal halide other than lithium may be selected from one or more of NaF, NaCl, NaBr, KF, KCl, KBr.
S2, mixing industrial nitric acid with water, and adjusting the pH value of the acid solution to be less than 4 and the potential to be between 0.015 and 0.8V.
The water may preferably be distilled water, which can reduce the introduction of new impurity elements into the solution, thereby affecting the leaching of the lithium element.
S3, adding the aluminum electrolyte treated in the step S1 into the acid solution obtained in the step S2, and leaching under the conditions of stirring and heating. Because the electrolyte components have great fluctuation, the LiF content (3-8%) and the additives added during the transformation of the electrolyte are different, the adding amount of the aluminum electrolyte is comprehensively controlled according to the concentration of fluoride ions and the acidity in the solution, wherein the leaching process controls the acidity of the electrolyte to be pH value less than 4 and the concentration of the fluoride ions to be more than 1g/L, preferably 1-80g/L, and simultaneously monitors the potential change of the solution. The reaction temperature of the mixture is controlled between 20 ℃ and 85 ℃, preferably between 30 ℃ and 80 ℃.
In the leaching process, a magnetic stirrer is adopted to stir the mixed solution, the stirring speed is not limited, and the aluminum electrolyte and the acid solution can be uniformly mixed to promote the dissolution of lithium in the aluminum electrolyte. The pH value of the mixed solution is controlled by an acidimeter, and the fluorine ion concentration of the mixed solution is controlled by a fluorine ion concentration selection electrode. The pH value at the end of the reaction should be less than 5, and the fluorine ion concentration should be greater than 1 g/L. According to different compositions of materials, proper amount of nitric acid is added.
And S4, after the reaction is finished, filtering the mixed solution after the reaction, and washing for multiple times (at least two times and three times) to obtain primary filtrate and primary filtrate after the reaction.
The filtration can separate the acid solution with a large amount of lithium salt and a very small amount of aluminum electrolyte components from the precipitate consisting of other components of the aluminum electrolyte. The lithium salt with high added value can be extracted and recovered by repeatedly washing the aluminum cell with distilled water for two or three times, and the aluminum electrolyte with high purity can be obtained at the same time.
And S5, extracting lithium element from the primary filtrate, washing and drying the primary filtrate, and returning the primary filtrate to an electrolytic aluminum plant for producing aluminum electrolyte and/or returning the primary filtrate to the leaching process.
The primary filtrate can be returned to an electrolytic aluminum plant to be used as a raw material for producing aluminum electrolyte after being washed and dried by distilled water, and can also be returned to the leaching process of leaching lithium element by nitric acid solution for multiple cycles, thereby improving the recovery rate of the lithium element.
Different from the existing method for leaching all components in the aluminum electrolyte by adopting nitric acid solution, the method only leaches Li in the aluminum electrolyte by controlling the potential, the pH value and the fluorine ion concentration of the acid solution2O, LiF and Li3AlF6The lithium salt is leached out, other components in the aluminum electrolyte are not dissolved out or the leaching is little, the separation of the lithium salt and the electrolyte main body is realized, so that the lithium element in the aluminum electrolyte is effectively extracted, the recovery of the lithium salt in the aluminum electrolyte is possible, the method is economically feasible, the recovery of the lithium salt with high added value is realized, meanwhile, the industrial electrolyte with higher purity and suitable for the production of the electrolytic aluminum can be obtained, the energy consumption and the comprehensive average extraction cost of the electrolytic aluminum production are greatly reduced, and the method is suitable for application and popularization in the industrial production.
The raw materials used in the method are common raw materials in the chemical field, the price is low, the process is simple, selective leaching (the LiF leaching rate of lithium salt is 78-99%, and the electrolyte leaching rate is lower than 10%) can be realized by controlling the concentration, the potential and the pH value of the solution in the leaching process, the production cost is reduced, various substances can be separated, and the purity of the obtained substances is high.
Based on the purpose of extracting lithium element in the aluminum electrolyte, the invention successfully researches a method for extracting the lithium element in the aluminum electrolyte by selectively leaching nitric acid, solves the problem of influence of the lithium element in the aluminum electrolysis industry, increases the benefit, improves the comprehensive level of the aluminum electrolysis industry in China, and expands the lithium salt resource supply in China.
The following exemplary examples illustrate the extraction of aluminum electrolyte samples from 300kA, 400kA and 200kA cells, respectively, from certain aluminum smelters. The samples are directly crushed and ground for analysis, and the element composition and content of the electrolyte are expressed by molecular ratio, alumina concentration, calcium fluoride concentration, lithium fluoride concentration and the like. The examples are as follows:
example 1
Taking 10g of aluminum electrolyte (the content of LiF in the electrolyte is 5%), crushing, grinding, sieving by a sieve of 80-120 meshes to obtain aluminum electrolyte powder, preparing 100ml of acid solution by using nitric acid and distilled water, wherein the pH value of the acid solution is 3, the potential is 0.05V, putting the aluminum electrolyte powder into the acid solution, heating to 60 ℃, stirring by using a magnetic stirrer, controlling the potential, the pH value and the fluorine ion concentration of the solution, and finishing leaching when the pH value of the solution is 4 and the fluorine ion concentration is 2 g/L. And filtering and washing the mixed solution after the reaction to obtain primary filtrate and primary filtrate after the reaction.
Through analysis and detection, the dissolution rate of LiF converted by lithium salt in the electrolyte is 99%, and the dissolution rate of the electrolyte is 8%.
Example 2
Taking 500g of aluminum electrolyte (the content of LiF in the electrolyte is 7%), crushing, grinding, sieving by a sieve of 80-120 meshes to obtain aluminum electrolyte powder, preparing 1L of acid solution by using nitric acid and distilled water, wherein the pH value of the acid solution is 2, the potential is 0.1V, putting the aluminum electrolyte powder into the acid solution, heating to 70 ℃, stirring by using a magnetic stirrer, controlling the potential, the pH value and the fluorine ion concentration of the solution, and finishing leaching when the pH value of the solution is 1 and the fluorine ion concentration is 50 g/L. And filtering and washing the mixed solution after the reaction to obtain primary filtrate and primary filtrate after the reaction.
Through analysis and detection, the dissolution rate of LiF converted by lithium salt in the electrolyte is 90%, and the dissolution rate of the electrolyte is 10%.
Example 3
Taking 10kg of aluminum electrolyte (the content of LiF in the electrolyte is 4%), crushing, grinding, sieving by a sieve of 80-120 meshes to obtain aluminum electrolyte powder, preparing 100L of acid solution by using nitric acid and distilled water, wherein the pH value of the acid solution is 2, the potential is 0.015V, putting the aluminum electrolyte powder into the acid solution, heating to 85 ℃, stirring by using a magnetic stirrer, controlling the potential, the pH value and the fluorine ion concentration of the solution, and finishing leaching when the pH value of the solution is 4 and the fluorine ion concentration is 30 g/L. And filtering and washing the mixed solution after the reaction to obtain primary filtrate and primary filtrate after the reaction.
Analysis and detection prove that the dissolution rate of LiF converted by lithium salt in the electrolyte is 80%, and the dissolution rate of the electrolyte is 6%.
Example 4
Taking 150kg of aluminum electrolyte (the content of LiF in the electrolyte is 4%), crushing, grinding, sieving by a sieve of 80-120 meshes to obtain aluminum electrolyte powder, preparing 1000L of acid solution by using nitric acid and distilled water, wherein the pH value of the acid solution is 1, the potential is 0.18V, putting the aluminum electrolyte powder into the acid solution, heating to 40 ℃, stirring by using a magnetic stirrer, controlling the pH value and the fluorine ion concentration of the solution, and finishing leaching when the pH value of the solution is 4 and the fluorine ion concentration is 25 g/L. And filtering and washing the mixed solution after the reaction to obtain primary filtrate and primary filtrate after the reaction.
Analysis and detection prove that the dissolution rate of LiF converted by lithium salt in the electrolyte is 88 percent, and the dissolution rate of the electrolyte is 8 percent.
Example 5
Taking 500g of aluminum electrolyte (the content of LiF in the electrolyte is 7%), crushing, grinding, sieving by a sieve of 80-120 meshes to obtain aluminum electrolyte powder, preparing 100ml of acid solution by using nitric acid and distilled water, wherein the pH value of the acid solution is 2, the potential is 0.8V, putting the aluminum electrolyte powder into the acid solution, heating to 20 ℃, stirring by using a magnetic stirrer, controlling the potential, the pH value and the fluorine ion concentration of the solution, and finishing leaching when the pH value of the solution is 3.9 and the fluorine ion concentration is 80 g/L. And filtering and washing the mixed solution after the reaction to obtain primary filtrate and primary filtrate after the reaction.
Through analysis and detection, the dissolution rate of LiF converted by lithium salt in the electrolyte is 78%, and the dissolution rate of the electrolyte is 9%.
Example 6
Taking 2kg of aluminum electrolyte (the content of LiF in the electrolyte is 5%), crushing, grinding, sieving by a sieve of 80-120 meshes to obtain aluminum electrolyte powder, preparing 30L of acid solution by using nitric acid and distilled water, wherein the pH value of the acid solution is 2, the potential is 0.5V, putting the aluminum electrolyte powder into the acid solution, heating to 30 ℃, stirring by using a magnetic stirrer, controlling the pH value and the fluorine ion concentration of the solution, and finishing leaching when the pH value of the solution is 3.8, the potential is 1.5V and the fluorine ion concentration is 1 g/L. And filtering and washing the mixed solution after the reaction to obtain primary filtrate and primary filtrate after the reaction.
Analysis and detection prove that the dissolution rate of LiF converted by lithium salt in the electrolyte is 83 percent, and the dissolution rate of the electrolyte is 5 percent.
Example 7
Taking 800g of aluminum electrolyte (the content of LiF in the electrolyte is 4%), crushing, grinding, sieving by a sieve of 80-120 meshes to obtain aluminum electrolyte powder, preparing 100ml of acid solution by using nitric acid and distilled water, wherein the pH value of the acid solution is 1, the potential is 0.3V, putting the aluminum electrolyte powder into the acid solution, heating to 80 ℃, stirring by using a magnetic stirrer, controlling the potential, the pH value and the fluorine ion concentration of the solution, and finishing leaching when the pH value of the solution is 1.5 and the fluorine ion concentration is 65 g/L. And filtering and washing the mixed solution after the reaction to obtain primary filtrate and primary filtrate after the reaction.
Analysis and detection prove that the dissolution rate of LiF converted by lithium salt in the electrolyte is 86 percent, and the dissolution rate of the electrolyte is 7 percent.
It can be seen from the above examples 1-7 that the dissolution rate of LiF in the electrolyte obtained in example 1 is the highest, up to 99%, the dissolution rate of the obtained aluminum electrolyte is 8%, and the purity is relatively high. The effect of extracting and recovering lithium element in the aluminum electrolyte is optimal.
It should be understood that the above description of specific embodiments of the present invention is only for the purpose of illustrating the technical lines and features of the present invention, and is intended to enable those skilled in the art to understand the contents of the present invention and to implement the present invention, but the present invention is not limited to the above specific embodiments. It is intended that all such changes and modifications as fall within the scope of the appended claims be embraced therein.
Claims (6)
1. A method for selective nitric acid leaching of lithium element in aluminum electrolyte is characterized by comprising the following steps:
s1, crushing and screening the aluminum electrolyte containing the lithium element; the aluminum electrolyte is directly from an electrolytic cell in an electrolytic aluminum plant;
s2, mixing nitric acid and water, and adjusting the pH value of the acid solution to be less than 4 and the potential to be between 0.015 and 0.8V;
s3, adding the aluminum electrolyte treated in the step S1 into the acid solution obtained in the step S2, stirring and heating for leaching, wherein in the leaching process, the reaction temperature is 20-85 ℃, the adding amount of the aluminum electrolyte is comprehensively controlled according to the concentration and acidity of fluoride ions in the solution, and nitric acid is added in a proper supplementary manner according to different material compositions; wherein, the acidity is that the pH value is less than 4, and the concentration of fluorinion is more than 1 g/L;
when the reaction is finished, the pH value is less than 5, and the concentration of fluorine ions is more than 1 g/L; s4, after the reaction is finished, filtering and washing the mixed solution after the reaction to obtain primary filtrate and primary filtrate after the reaction;
and S5, extracting lithium element from the primary filtrate, washing and drying the primary filtrate, and returning the primary filtrate to an electrolytic aluminum plant for producing aluminum electrolyte and/or returning the primary filtrate to the leaching process.
2. The method of selective nitric acid leaching of lithium from aluminum electrolyte as claimed in claim 1 wherein: in step S1, the aluminum electrolyte is crushed and sieved through a 80-120 mesh sieve.
3. The method of selective nitric acid leaching of lithium from aluminum electrolyte as claimed in claim 1 wherein: in step S2, distilled water is used as the water.
4. The method of selective nitric acid leaching of lithium from aluminum electrolyte as claimed in claim 1 wherein: in step S3, the reaction temperature of the mixture is adjusted to 30 to 80 ℃.
5. The method of selective nitric acid leaching of lithium from aluminum electrolyte as claimed in claim 1 wherein: in step S3, the fluoride ion concentration is 1-80 g/L.
6. The method of selective nitric acid leaching of lithium from aluminum electrolyte as claimed in claim 1 wherein: in step S3, in the leaching process, the pH of the mixed solution is controlled by an acidimeter, and the fluoride ion concentration of the mixed solution is controlled by a fluoride ion concentration selection electrode.
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| PCT/CN2018/087340 WO2019100673A1 (en) | 2017-11-21 | 2018-05-17 | Method for selective nitric acid leaching of lithium elements in aluminum electrolyte |
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| CN107974565B (en) * | 2017-11-21 | 2022-03-29 | 东北大学 | Method for selective nitric acid leaching of lithium element in aluminum electrolyte |
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| CN110240182B (en) * | 2019-07-08 | 2021-06-18 | 中南大学 | Resourceful treatment method of lithium-rich aluminum electrolyte |
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| CN114410970A (en) * | 2022-01-21 | 2022-04-29 | 东北大学 | Leaching method of lithium element in aluminum electrolyte |
| CN115558801A (en) * | 2022-10-25 | 2023-01-03 | 白东华 | Processing device and processing technology for lithium removal, purification and lithium recovery of aluminum electrolyte |
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| CN106910959A (en) * | 2017-05-04 | 2017-06-30 | 北京科技大学 | A kind of method of selective recovery lithium in waste material from LiFePO4 |
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| CN107974565B (en) * | 2017-11-21 | 2022-03-29 | 东北大学 | Method for selective nitric acid leaching of lithium element in aluminum electrolyte |
| CN107937722B (en) * | 2017-11-21 | 2019-03-05 | 东北大学 | The method of lithium fluoride is separated from electrolyte acid leaching solution |
| CN107935015A (en) * | 2017-11-21 | 2018-04-20 | 东北大学 | The method that lithium carbonate is separated from electrolyte acid leaching solution |
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| CN104241724A (en) * | 2014-09-02 | 2014-12-24 | 湖南邦普循环科技有限公司 | Method for preparing battery-grade lithium carbonate from recycled lithium ion battery material |
| CN105400956A (en) * | 2015-10-29 | 2016-03-16 | 赣州腾远钴业有限公司 | Treatment method for fluorine-containing and phosphorus-containing wastewater generated during recycling of lithium ion batteries |
| CN105349786A (en) * | 2015-11-16 | 2016-02-24 | 多氟多化工股份有限公司 | Lithium-aluminum-contained electrolyte comprehensive recycling method |
| CN105543504A (en) * | 2015-12-21 | 2016-05-04 | 东北大学 | Method for extracting lithium salt from aluminum electrolyte by utilizing fluoride roasting and acid leaching |
| CN106910959A (en) * | 2017-05-04 | 2017-06-30 | 北京科技大学 | A kind of method of selective recovery lithium in waste material from LiFePO4 |
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