CN111470520A - Method for treating waste lithium battery material - Google Patents
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- CN111470520A CN111470520A CN202010429940.8A CN202010429940A CN111470520A CN 111470520 A CN111470520 A CN 111470520A CN 202010429940 A CN202010429940 A CN 202010429940A CN 111470520 A CN111470520 A CN 111470520A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
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- 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
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- 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
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Abstract
The invention discloses a method for treating waste lithium battery materials. The method comprises the following steps: mixing a powder material obtained by disassembling a waste lithium battery, water and nitric acid, carrying out acid dissolution, carrying out solid-liquid separation on an acid-dissolved product, and collecting a liquid product; adding a powder material and water into the liquid product, and repeatedly performing acid dissolution and solid-liquid separation to enrich lithium in the liquid product to obtain a lithium nitrate-rich solution; adding alkali liquor to precipitate heavy metals, performing solid-liquid separation to collect lithium nitrate solution, mixing the lithium nitrate solution with alkali and performing constant-temperature crystallization to obtain product solution containing lithium hydroxide crystals, and performing solid-liquid separation to obtain a lithium hydroxide product and a sodium nitrate solution; and (4) evaporating and crystallizing the sodium nitrate solution, and carrying out solid-liquid separation to obtain a sodium nitrate byproduct. The method takes waste lithium battery powder materials as raw materials, prepares the lithium hydroxide through a nitrate system, has simple and easy process, and does not need low-temperature cold crystallization, recrystallization, impurity removal and high-energy-consumption high-temperature evaporation concentration crystallization.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a method for treating waste lithium battery materials.
Background
Lithium hydroxide is an important lithium compound and has previously been used in the largest consumer area for the production of lithium-based greases. With the gradual market occupation of lithium ion batteries adopting high-nickel anode materials, the high-nickel anode materials gradually replace lithium-based lubricating grease, and become the largest consumption field of lithium hydroxide.
Two raw materials are generally used for preparing lithium hydroxide, one is lepidolite and spodumene minerals, a lithium sulfate solution is obtained by mainly adopting sulfuric acid to calcine and leach at high temperature, after impurity removal, alkali is added to convert the lithium sulfate solution into lithium hydroxide, and then the lithium hydroxide is evaporated and crystallized to obtain a product. The other is salt lake brine, which is mainly concentrated by using sunning brine to remove most of salt, the magnesium-lithium ratio of the solution is reduced, impurities such as magnesium and the like are further removed to obtain a lithium chloride solution, the solution is precipitated and converted into lithium hydroxide, and then the lithium hydroxide solution is evaporated and crystallized to obtain a product. Spodumene can be better leached only by sulfuric acid, so that only a lithium sulfate solution can be obtained; because the salt lake brine is a chloride system, only lithium chloride solution can be obtained through concentration and impurity removal. Meanwhile, the two processes need to adopt the steps of evaporation, concentration and crystallization with high energy consumption to obtain the lithium hydroxide product, and the production cost is high.
On the other hand, with the vigorous development of the new energy lithium battery industry, waste lithium ion batteries are continuously required to be recycled in the future, and the lithium recycling method still needs to be further researched.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to propose a method for treating waste lithium battery materials. The method takes waste lithium battery materials as raw materials, prepares the lithium hydroxide through a nitrate system, has simple and easy process, does not need to introduce evaporative concentration crystallization with high energy consumption, and has obvious economic benefit and environmental benefit.
In one aspect of the invention, a method of treating waste lithium battery material is provided. According to an embodiment of the invention, the method comprises: (1) mixing waste lithium battery materials, water and nitric acid, carrying out acid dissolution treatment, carrying out solid-liquid separation on a product obtained by the acid dissolution treatment, and collecting a liquid product; adding waste lithium battery materials and water into the liquid product, and repeatedly performing acid dissolution treatment and solid-liquid separation so as to enrich lithium in the liquid product and obtain a lithium nitrate-rich solution; (2) mixing the lithium nitrate-rich solution with alkali liquor, carrying out precipitation treatment, carrying out solid-liquid separation on a product obtained by the precipitation treatment, and collecting a liquid product to obtain a lithium nitrate solution; (3) mixing the lithium nitrate solution with hydroxide and carrying out constant-temperature crystallization treatment to obtain a mixed product containing lithium hydroxide crystals; (4) and carrying out solid-liquid separation on the mixed product to obtain lithium hydroxide crystals and a first filtrate.
According to the method for treating the waste lithium battery material, disclosed by the embodiment of the invention, firstly, the waste lithium battery material is subjected to acid dissolution treatment by using nitric acid, so that metal elements in the waste lithium battery material are leached to a liquid phase, and lithium in a liquid product is enriched by repeating the acid dissolution treatment for multiple times, so that a lithium-rich solution is obtained. Subsequently, adjusting the pH value of the lithium nitrate-rich solution by using alkali liquor, precipitating impurity ions such as calcium, magnesium, nickel, cobalt, copper, manganese, iron, aluminum and the like which may exist in the lithium nitrate-rich solution, and carrying out solid-liquid separation to obtain the lithium nitrate solution with low impurity content. The lithium nitrate solution has a higher lithium concentration due to the prior enrichment. Further, by adding a sufficient amount of alkali to the lithium nitrate solution, most of lithium in the system is supersaturated and crystallized at a constant temperature in the form of lithium hydroxide by utilizing the property that the solubility of lithium hydroxide is greatly different from that of other solutes in the system, and then lithium hydroxide crystals are obtained by solid-liquid separation. Therefore, the method takes the waste lithium battery material as the raw material, prepares the lithium hydroxide through a nitrate system, has simple and easy process, does not need to introduce evaporative concentration crystallization with high energy consumption, and has obvious economic benefit and environmental benefit.
In addition, the method for processing waste lithium battery materials according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the solid-to-liquid ratio of the waste lithium battery material to the water is 1 (2-5).
In some embodiments of the present invention, the acid dissolution treatment is performed at 70 to 90 ℃ for 1 to 5 hours.
In some embodiments of the invention, the lithium concentration in the lithium nitrate-rich solution is 150-180 g/L.
In some embodiments of the invention, the pH value of the lithium nitrate-rich solution is adjusted to 9-11 by using a hydroxide solution with a concentration of 4-10 mol/L, and the reaction is carried out for 0.5-1 h.
In some embodiments of the invention, the constant temperature crystallization treatment is performed at 60-80 ℃ for 3-6 h.
In some embodiments of the present invention, the method for treating waste lithium battery material further comprises: and washing the lithium hydroxide crystal by using water at the temperature of 15-25 ℃, and drying to obtain a lithium hydroxide product after washing.
In some embodiments of the present invention, the method for treating waste lithium battery material further comprises: (5) adding carbonate into the first filtrate, reacting for 1-3 h at 80-95 ℃, and performing solid-liquid separation to obtain lithium carbonate precipitate and a second filtrate; (6) and adding villiaumite into the second filtrate, reacting for 1-3 h at 75-85 ℃, and performing solid-liquid separation to obtain lithium fluoride precipitate and third filtrate.
In some embodiments of the present invention, the method for treating waste lithium battery material further comprises: and (3) returning the lithium carbonate precipitate and the lithium fluoride precipitate to the step (1) for acid dissolution treatment.
In some embodiments of the present invention, the method for treating waste lithium battery material further comprises: and carrying out evaporative crystallization treatment on the third filtrate to obtain sodium nitrate crystals.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
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The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic flow diagram of a method for treating waste lithium battery materials according to an embodiment of the present invention;
fig. 2 is a schematic flow chart of a method for treating waste lithium battery materials according to still another embodiment of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, a method of treating waste lithium battery material is provided. According to an embodiment of the invention, the method comprises: (1) mixing waste lithium battery materials, water and nitric acid, carrying out acid dissolution treatment, carrying out solid-liquid separation on a product obtained by the acid dissolution treatment, and collecting a liquid product; adding waste lithium battery materials and water into the liquid product, and repeatedly carrying out acid dissolution treatment and solid-liquid separation so as to enrich lithium in the liquid product and obtain a lithium nitrate-rich solution; (2) mixing the lithium nitrate-rich solution with alkali liquor, carrying out precipitation treatment, carrying out solid-liquid separation on a product obtained by the precipitation treatment, and collecting a liquid product to obtain a lithium nitrate solution; (3) mixing a lithium nitrate solution with hydroxide and carrying out constant-temperature crystallization treatment to obtain a mixed product containing lithium hydroxide crystals; (4) and (4) carrying out solid-liquid separation on the mixed product obtained in the step (3) to obtain lithium hydroxide crystals and a first filtrate.
The method for treating the waste lithium battery material will be further described in detail with reference to fig. 1 and 2. According to an embodiment of the invention, the method comprises:
s100: acid dissolution treatment
Mixing waste lithium battery materials, water and nitric acid, carrying out acid dissolution treatment, carrying out solid-liquid separation on a product obtained by the acid dissolution treatment, and collecting a liquid product; adding waste lithium battery materials and water (if necessary, adding a proper amount of concentrated nitric acid), and repeatedly performing acid dissolution treatment and solid-liquid separation to enrich lithium in the liquid product to obtain a lithium nitrate-rich solution. Specifically, the waste lithium battery material is a positive electrode powder material of a waste lithium battery, for example, a positive electrode powder material obtained by disassembling a waste ternary nickel cobalt manganese lithium battery, a waste lithium iron phosphate battery and the like. In this step, after the waste lithium battery material and water (preferably pure water) are mixed according to a predetermined solid-to-liquid ratio, concentrated nitric acid (for example, concentrated nitric acid of 110% to 200% of theoretical amount) in excess of theoretical amount may be added to sufficiently leach the metal in the waste lithium battery material into liquid phase. After the first acid dissolution treatment is finished, carrying out solid-liquid separation on the obtained product, collecting a liquid product, supplementing waste lithium battery materials and water to the liquid product according to actual conditions to a preset solid-liquid ratio, then carrying out acid dissolution treatment and solid-liquid separation, and repeating the operation for multiple times to enrich lithium in the liquid product and fully remove insoluble components in the liquid product to obtain a lithium nitrate-enriched solution.
According to some embodiments of the invention, the solid-to-liquid ratio of the waste lithium battery material to water may be 1 (2-5), for example, 1:2, 1:3, 1:4, 1:5, and the like. By controlling the solid-liquid ratio of the waste lithium battery material to the water within the range, the waste lithium battery material can be fully immersed in the water, and the concentration of the nitric acid cannot be reduced too much after the concentrated nitric acid is added subsequently, so that the metal elements in the waste lithium battery material are fully leached.
According to some embodiments of the present invention, the acid dissolution treatment may be performed at 70-90 ℃ for 1-5 hours. Specifically, the treatment temperature may be 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ and the like, and the treatment time may be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours and the like. Therefore, the method can further facilitate the full leaching of the metal elements in the waste lithium battery materials.
According to some embodiments of the present invention, the concentration of lithium in the lithium nitrate-rich solution may be 150 to 180 g/L, such as 150 g/L, 160 g/L, 170 g/L, 180 g/L, etc. the inventors have found in the research that by enriching lithium in the lithium nitrate-rich solution to the above concentration range, it may be further advantageous to subsequently utilize the property of lithium hydroxide having a large difference in solubility with other solutes in the system, so that most of lithium in the system is supersaturated and crystallized at constant temperature in the form of lithium hydroxide.
S200: precipitation treatment
In the step, the lithium nitrate-rich solution and alkali liquor are mixed and subjected to precipitation treatment, a product obtained by the precipitation treatment is subjected to solid-liquid separation, and a liquid product is collected to obtain a lithium nitrate solution. Specifically, the pH value of the lithium nitrate-rich solution is adjusted by using an alkali liquor, so that impurity ions such as calcium, magnesium, nickel, cobalt, copper, manganese, iron, aluminum and the like which may exist in the lithium nitrate-rich solution can be precipitated, and the lithium nitrate solution with low impurity content is obtained through solid-liquid separation.
According to some embodiments of the present invention, in the precipitation treatment, the lithium nitrate-rich solution may be adjusted to a pH of 9 to 11 (e.g., 9, 9.5, 10, 10.5, 11, etc.) by using a hydroxide solution (preferably a sodium hydroxide solution) having a concentration of 4 to 10 mol/L and reacted for 0.5 to 1 hour, thereby further increasing the precipitation rate of impurity ions such as calcium, magnesium, nickel, cobalt, copper, manganese, iron, aluminum, etc., which may be present in the lithium nitrate-rich solution, without precipitating lithium ions.
S300: constant temperature crystallization treatment
In the step, a lithium nitrate solution and a hydroxide are mixed and subjected to constant temperature crystallization treatment to obtain a mixed product containing lithium hydroxide crystals. Specifically, the lithium nitrate solution subjected to acid-soluble enrichment and precipitation treatment has a high lithium ion concentration and a low impurity ion concentration. Therefore, by adding hydroxide (preferably sodium hydroxide, the amount is not less than 100% of the theoretical amount) to the lithium nitrate solution, most of lithium in the system can be crystallized and precipitated in a supersaturated manner at a constant temperature in the form of lithium hydroxide by utilizing the property that the solubility of lithium hydroxide is greatly different from that of other solutes in the system. The purity of the obtained lithium hydroxide is more than 99 percent, and the lithium hydroxide can be used for producing high-nickel cathode materials of lithium batteries, lithium-based lubricating grease and the like.
According to some embodiments of the present invention, the constant temperature crystallization treatment can be performed at 60-80 ℃ for 3-6 hours. Specifically, the treatment temperature may be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ and the like, and the treatment time may be 3 hours, 4 hours, 5 hours, 6 hours and the like. By carrying out constant temperature crystallization treatment under the above conditions, the crystallization yield of lithium hydroxide can be further improved, and the total lithium precipitation yield in the system is about 80%.
S400: obtaining lithium hydroxide crystals
In this step, the mixed product obtained in S300 is subjected to solid-liquid separation to obtain lithium hydroxide crystals and a first filtrate. Preferably, the solid-liquid separation is performed on the mixed product obtained in S300 while it is hot, whereby the recovery rate of lithium hydroxide can be further improved.
According to some embodiments of the invention, after the lithium hydroxide crystals are obtained by separation, the lithium hydroxide crystals can be washed by using water at 15-25 ℃, and after washing, the lithium hydroxide products are obtained by drying.
Further, according to some embodiments of the present invention, the first filtrate may be subjected to an evaporative crystallization process to precipitate sodium ions and nitrate ions therein in the form of sodium nitrate crystals. Therefore, the pollution to the environment caused by the direct discharge of the first filtrate can be avoided, and the sodium nitrate crystal can be obtained as a byproduct, so that the environmental benefit and the economic benefit of the method are further improved. After the sodium nitrate crystals were precipitated, some lithium ions remained in the liquid phase. For the recovery of this lithium ion, the filtrate obtained after separating the sodium nitrate crystals may be directly returned to S100 to be subjected to acid dissolution treatment, or may be recovered as lithium carbonate and lithium fluoride by adding carbonate and fluorine salt to the filtrate.
Referring to fig. 2, according to an embodiment of the present invention, the method for treating waste lithium battery material of the present invention may further include:
s500: obtaining lithium carbonate
In the step, carbonate is added into the first filtrate obtained in S400, the mixture reacts for 1-3 hours at the temperature of 80-95 ℃, and solid-liquid separation is performed to obtain lithium carbonate precipitate and a second filtrate. As described above, by the operations S100 to S400, about 80% of lithium in the total amount of lithium in the waste lithium battery material can be recovered as lithium hydroxide crystals. Further, by adding carbonate (preferably sodium carbonate, in an amount of not less than 105% of the theoretical amount) to the first filtrate and performing a reaction, lithium in an amount of about 10 to 20% of the total lithium in the waste lithium battery material may be precipitated in the form of lithium carbonate.
S600: obtaining lithium fluoride
In the step, villiaumite is added into the second filtrate obtained in the step S500, the reaction is carried out for 1-3 h at the temperature of 75-85 ℃, and lithium fluoride precipitate and third filtrate are obtained through solid-liquid separation. The second filtrate still contains a small amount of lithium, and lithium in the form of lithium fluoride, about 1% of the total lithium content in the waste lithium battery material, can be precipitated by adding a fluorine salt (preferably sodium fluoride, in an amount of not less than 105% of the theoretical amount) to the second filtrate and carrying out the reaction.
In conclusion, by comprehensively calculating the recovery rates of lithium hydroxide, lithium carbonate and lithium fluoride, the total recovery rate of lithium in the waste lithium battery material by the method provided by the invention is more than 95%.
In addition, according to some embodiments of the present invention, after lithium carbonate is precipitated, a fluorine salt may be directly added to the reaction system without performing solid-liquid separation, and after lithium fluoride is precipitated, a mixture of lithium carbonate and lithium fluoride may be obtained by solid-liquid separation at the same time.
According to some embodiments of the present invention, the method for treating waste lithium battery material of the present invention may further include: and returning the lithium carbonate precipitate and the lithium fluoride precipitate obtained in S500 and S600 to S100 for acid dissolution treatment. Thereby, lithium carbonate and lithium fluoride can be recycled. In addition, the inventors have unexpectedly found in their studies that by returning lithium fluoride to the acid dissolution treatment, it is possible to recover lithium therefrom while increasing the fluoride ion concentration in the system, thereby making it easier to precipitate impurity ions such as calcium and magnesium in the subsequent precipitation treatment.
According to some embodiments of the present invention, the method for treating waste lithium battery material of the present invention may further include: and (4) carrying out evaporative crystallization treatment on the third filtrate obtained in the step (S600) to obtain sodium nitrate crystals. The purity of the byproduct sodium nitrate is more than 98 percent, and the byproduct sodium nitrate can be used as a fluxing agent in the crystal enamel industry, a quick-acting fertilizer applicable to acid soil in the chemical fertilizer industry, a color former for meat processing in the food industry and the like.
Additionally, according to some embodiments of the present invention, the concentrated nitric acid, sodium hydroxide, sodium carbonate, and sodium fluoride used in the above-described method are all of industrial grade purity. The inventor finds in research that the method provided by the invention has low requirement on the purity of the reagent, and a high-quality lithium hydroxide product can be obtained by adopting an industrial-grade reagent. Thus, the process cost can be further reduced.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
Adding battery waste and pure water with a solid-liquid ratio of 1:5 into an acid dissolving tank, adding concentrated nitric acid with a theoretical amount of 150%, heating to 80 ℃, stirring for 3h, filtering, collecting filtrate, adding the filtrate into the acid dissolving tank again, supplementing the battery waste and the pure water into the filtrate, ensuring that the solid-liquid ratio of the battery waste and the water is still 1:5, and repeating acid dissolving treatment and solid-liquid separation for multiple times to obtain a lithium nitrate-rich solution with a lithium ion concentration of 170 g/L.
The pH of the lithium nitrate-rich solution was adjusted to 11.0 with 6 mol/L sodium hydroxide solution and stirring was continued for 1.0h, and the precipitate was removed by filtration and the lithium nitrate solution was collected.
Placing a lithium nitrate solution in a constant-temperature crystallization tank at 70 ℃, adding flaky sodium hydroxide with the theoretical amount of 100%, stirring and crystallizing for 5 hours, filtering, leaching lithium hydroxide crystals once with 0.25 volume part of cold water at 20 ℃, rapidly dehydrating, collecting lithium hydroxide crystals, transferring to a disc type dryer, drying and packaging. Firstly adding 105% of sodium carbonate into the filtrate, reacting for 2 hours at the constant temperature of 80 ℃, then adding 105% of sodium fluoride into the filtrate, reacting for 2 hours, filtering, wherein the filtrate is mainly sodium nitrate solution, and sending the filtrate to evaporative crystallization to prepare sodium nitrate crystals; the filter residue is mainly a mixture of lithium carbonate and lithium fluoride, and is returned to the acid dissolving tank for recycling lithium.
Example 2
Adding battery waste and pure water with a solid-liquid ratio of 1:3 into an acid dissolving tank, adding concentrated nitric acid with a theoretical amount of 130%, heating to 70 ℃, stirring for 3 hours, filtering, collecting filtrate, adding the filtrate into the acid dissolving tank again, supplementing the battery waste and the pure water into the filtrate, ensuring that the solid-liquid ratio of the battery waste and the water is still 1:3, and repeating acid dissolving treatment and solid-liquid separation for multiple times to obtain a lithium nitrate-rich solution with a lithium ion concentration of 160 g/L.
The pH of the lithium nitrate-rich solution was adjusted to 10.0 with 4 mol/L sodium hydroxide solution and stirring was continued for 0.5h, and the precipitate was removed by filtration and the lithium nitrate solution was collected.
Placing a lithium nitrate solution in a constant-temperature crystallization tank at 60 ℃, adding flaky sodium hydroxide with the theoretical amount of 100%, stirring and crystallizing for 4 hours, filtering, leaching lithium hydroxide crystals once with 0.25 volume part of cold water at 20 ℃, rapidly dehydrating, collecting lithium hydroxide crystals, transferring to a disc type dryer, drying and packaging. Firstly adding 105% of sodium carbonate into the filtrate, reacting for 2 hours at the constant temperature of 90 ℃, then adding 105% of sodium fluoride into the filtrate, reacting for 2 hours, filtering, wherein the filtrate is mainly sodium nitrate solution, and sending the filtrate to evaporative crystallization to prepare sodium nitrate crystals; the filter residue is mainly a mixture of lithium carbonate and lithium fluoride, and is returned to the acid dissolving tank for recycling lithium.
Example 3
Adding battery waste and pure water with a solid-liquid ratio of 1:2 into an acid dissolving tank, adding concentrated nitric acid with a theoretical amount of 180%, heating to 90 ℃, stirring for 5 hours, filtering, collecting filtrate, adding the filtrate into the acid dissolving tank again, supplementing the battery waste and the pure water into the filtrate, ensuring that the solid-liquid ratio of the battery waste and the water is still 1:2, and repeatedly performing acid dissolving treatment and solid-liquid separation for multiple times to obtain a lithium nitrate-rich solution with a lithium ion concentration of 180 g/L.
The pH of the lithium nitrate-rich solution was adjusted to 9.5 with 8 mol/L sodium hydroxide solution and stirring was continued for 0.5h, and the precipitate was removed by filtration and the lithium nitrate solution was collected.
Placing a lithium nitrate solution into a constant-temperature crystallization tank at 80 ℃, adding flaky sodium hydroxide with the theoretical amount of 100%, stirring and crystallizing for 6 hours, filtering, leaching lithium hydroxide crystals once with 0.25 volume part of cold water at 20 ℃, rapidly dehydrating, collecting lithium hydroxide crystals, transferring to a disc type dryer, drying and packaging. Firstly adding 105% of sodium carbonate into the filtrate, reacting for 2 hours at the constant temperature of 95 ℃, then adding 105% of sodium fluoride into the filtrate, reacting for 2 hours, filtering, wherein the filtrate is mainly sodium nitrate solution, and sending the filtrate to evaporative crystallization to prepare sodium nitrate crystals; the filter residue is mainly a mixture of lithium carbonate and lithium fluoride, and is returned to the acid dissolving tank for recycling lithium.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for processing waste lithium battery materials is characterized by comprising the following steps:
(1) mixing waste lithium battery materials, water and nitric acid, carrying out acid dissolution treatment, carrying out solid-liquid separation on a product obtained by the acid dissolution treatment, and collecting a liquid product; adding waste lithium battery materials and water into the liquid product, and repeatedly performing acid dissolution treatment and solid-liquid separation so as to enrich lithium in the liquid product and obtain a lithium nitrate-rich solution;
(2) mixing the lithium nitrate-rich solution with alkali liquor, carrying out precipitation treatment, carrying out solid-liquid separation on a product obtained by the precipitation treatment, and collecting a liquid product to obtain a lithium nitrate solution;
(3) mixing the lithium nitrate solution with hydroxide and carrying out constant-temperature crystallization treatment to obtain a mixed product containing lithium hydroxide crystals;
(4) and carrying out solid-liquid separation on the mixed product to obtain lithium hydroxide crystals and a first filtrate.
2. The method as claimed in claim 1, wherein the solid-to-liquid ratio of the waste lithium battery material to the water is 1 (2-5).
3. The method according to claim 1, wherein the acid dissolution treatment is performed at 70 to 90 ℃ for 1 to 5 hours.
4. The method of claim 1, wherein the lithium concentration in the lithium nitrate-rich solution is 150-180 g/L.
5. The method according to claim 1, wherein in the precipitation treatment, the pH value of the lithium nitrate-rich solution is adjusted to 9-11 by using a hydroxide solution with a concentration of 4-10 mol/L, and the lithium nitrate-rich solution is reacted for 0.5-1 h.
6. The method according to claim 1, wherein the constant temperature crystallization treatment is performed at 60 to 80 ℃ for 3 to 6 hours.
7. The method of claim 1, further comprising: and washing the lithium hydroxide crystal by using water at the temperature of 15-25 ℃, and drying to obtain a lithium hydroxide product after washing.
8. The method of claim 1, further comprising:
(5) adding carbonate into the first filtrate, reacting for 1-3 h at 80-95 ℃, and performing solid-liquid separation to obtain lithium carbonate precipitate and a second filtrate;
(6) and adding villiaumite into the second filtrate, reacting for 1-3 h at 75-85 ℃, and performing solid-liquid separation to obtain lithium fluoride precipitate and third filtrate.
9. The method of claim 8, further comprising: and (3) returning the lithium carbonate precipitate and the lithium fluoride precipitate to the step (1) for acid dissolution treatment.
10. The method of claim 8, further comprising: and carrying out evaporative crystallization treatment on the third filtrate to obtain sodium nitrate crystals.
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Cited By (2)
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| CN111994925A (en) * | 2020-08-28 | 2020-11-27 | 贵州大龙汇成新材料有限公司 | Comprehensive utilization method of valuable resources in waste lithium batteries |
| WO2022094696A1 (en) * | 2020-11-03 | 2022-05-12 | Rock Tech Lithium Inc. | Process for the production of lithium hydroxide |
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| CN111470520B (en) | 2023-08-18 |
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