CN113621800A - Method for treating acid leaching solution containing fluorine - Google Patents
Method for treating acid leaching solution containing fluorine Download PDFInfo
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- CN113621800A CN113621800A CN202110918308.4A CN202110918308A CN113621800A CN 113621800 A CN113621800 A CN 113621800A CN 202110918308 A CN202110918308 A CN 202110918308A CN 113621800 A CN113621800 A CN 113621800A
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- 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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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
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- 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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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Abstract
The invention relates to the technical field of chemical metallurgy and comprehensive utilization of mineral resources, in particular to a method for treating fluorine-containing pickle liquor, which comprises the following steps: A) carrying out heat treatment on the fluorine-containing pickle liquor at 50-150 ℃ to obtain defluorinated pickle liquor; B) and carrying out heat treatment on the defluorinated pickle liquor at 180-350 ℃ to obtain a treated leachate. The invention adopts the first-stage heat treatment defluorination and the second-stage heat treatment deacidification, in the first-stage heat treatment defluorination process, the main component of the extracted gas is hydrofluoric acid after absorption, and the gas is concentrated and then is reused in the preparation process of the fluorine-containing pickle liquor, thereby reducing the consumption of fresh fluorine-containing auxiliary agent and improving the utilization rate of the fluorine-containing auxiliary agent; the sulfuric acid gas collected by the second-stage heat treatment is enriched and concentrated and then is recycled in the preparation process of the fluorine-containing pickle liquor, so that the fresh acid consumption is reduced, more importantly, the generation of lithium-containing insoluble fluoride in the defluorination process can be avoided, and the lithium loss of the working section is reduced.
Description
Technical Field
The invention relates to the technical field of chemical metallurgy and comprehensive utilization of mineral resources, in particular to a method for treating a fluorine-containing pickle liquor.
Background
With the development of new energy materials such as lithium ion batteries, the efficient extraction and comprehensive utilization of lithium resources gradually receive wide attention. Spodumene is the most important economic lithium-containing mineral resource, mainly exists in a chemically inert alpha phase in nature, and generally needs to be subjected to high-temperature roasting activation, concentrated acid hydrolysis and other steps, so that the problems of high energy consumption, large subsequent neutralization slag quantity and the like are easily caused. How to enhance the extraction of lithium from spodumene under low temperature condition becomes the key to solve the problem. The fluorine-containing auxiliary agent can react with acid to generate hydrogen fluoride, so that the crystal lattice of spodumene can be destroyed at low temperature. Therefore, the fluorine-containing auxiliary agent is gradually and widely researched in the process of improving the extraction of lithium by a spodumene acid method, but the content of fluorine in the lithium-containing acid leaching solution obtained by the process is high (500 mg/L-500 g/L), and during the neutralization of the subsequent acid leaching solution, fluorine is easy to complex with aluminum and simultaneously coordinates to adsorb lithium, so that obvious lithium loss is caused. Therefore, the realization of defluorination and deacidification of the acid leaching solution containing fluorine is of great significance to the subsequent lithium extraction process.
Disclosure of Invention
In view of the above, the present invention provides a method for treating a fluorine-containing acid immersion liquid, which can effectively reduce lithium loss.
The invention provides a method for treating acid leaching solution containing fluorine, which comprises the following steps:
A) carrying out heat treatment on the fluorine-containing pickle liquor at 50-150 ℃ to obtain defluorinated pickle liquor;
B) and carrying out heat treatment on the defluorinated acid leaching solution at 180-350 ℃ to obtain a lithium-containing leaching solution.
Preferably, in the step A), the fluorine-containing acid leaching solution is a fluorine-containing acid leaching solution generated after lithium is extracted from spodumene;
the fluorine content of the fluorine-containing pickle liquor is 500 mg/L-500 g/L;
the concentration of hydrogen ions in the fluorine-containing pickle liquor is 0.1-10 mol/L.
Preferably, the fluorine-containing pickle liquor is prepared by the following method:
stirring spodumene particles, sulfuric acid and a fluorine-containing auxiliary agent for reaction to obtain a fluorine-containing acid immersion liquid;
the particle size of the spodumene particles is 50-200 meshes;
the mass concentration of the sulfuric acid is 30-80%;
the fluorine-containing auxiliary agent comprises at least one of hydrofluoric acid, fluorite fluorine-containing mineral, fluosilicic acid, fluorosilicate and fluoride salt.
Preferably, the mass ratio of the spodumene particles to the sulfuric acid to the fluorine-containing auxiliary agent is 1: 0.05-5: 0.05 to 5.
Preferably, the stirring reaction is carried out at the temperature of 50-150 ℃ for 0.5-3 h.
Preferably, the spodumene particles, the sulfuric acid and the fluorine-containing auxiliary agent are not required to be subjected to calcination transformation before the stirring reaction.
Preferably, the stirring reaction is carried out in a closed environment.
Preferably, in the step A), the heat treatment time is 0.5-5 h.
Preferably, step a), after the heat treatment, further comprises:
and absorbing the fluorine-containing gas in the system after heat treatment by using water, enriching and concentrating the fluorine-containing gas, and reusing the fluorine-containing gas in the preparation process of the fluorine-containing pickle liquor.
Preferably, in the step B), the heat treatment time is 0.5-12 h;
after the heat treatment, the method further comprises the following steps:
and absorbing the volatile sulfuric acid obtained by the heat treatment with water, enriching and concentrating, and reusing the concentrated sulfuric acid in the preparation process of the fluorine-containing pickle liquor.
The invention provides a method for treating acid leaching solution containing fluorine, which comprises the following steps: A) carrying out heat treatment on the fluorine-containing pickle liquor at 50-150 ℃ to obtain defluorinated pickle liquor; B) and carrying out heat treatment on the defluorinated acid leaching solution at 180-350 ℃ to obtain a treated lithium-containing leaching solution. The invention adopts first-stage heat treatment defluorination (volatilizing fluorine-containing gas) and second-stage heat treatment deacidification (volatilizing dilute sulfuric acid), in the first-stage heat treatment defluorination process, the main component of the extracted gas is hydrofluoric acid after absorption, and the gas is concentrated and then is reused in the preparation process of the fluorine-containing pickle liquor, thereby reducing the consumption of fresh fluorine-containing auxiliary agent and improving the utilization rate of the fluorine-containing auxiliary agent; the sulfuric acid gas collected by the second-stage heat treatment is enriched and concentrated and then is recycled in the preparation process of the fluorine-containing pickle liquor, so that the fresh acid consumption is reduced, more importantly, the generation of lithium-containing insoluble fluoride in the defluorination process can be avoided, and the lithium loss of the working section is reduced.
Drawings
FIG. 1 is an XRD pattern of a solid phase insoluble matter in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for treating acid leaching solution containing fluorine, which comprises the following steps:
A) carrying out heat treatment on the fluorine-containing pickle liquor at 50-150 ℃ to obtain defluorinated pickle liquor;
B) and carrying out heat treatment on the defluorinated acid leaching solution at 180-350 ℃ to obtain a lithium-containing leaching solution.
The fluorine-containing acid leaching solution is generated after lithium is extracted from spodumene. In some embodiments of the invention, the fluorine content of the fluorine-containing pickle liquor is 500 mg/L-500 g/L. In certain embodiments, the fluorine content of the fluorine-containing pickle liquor is 35g/L, 56g/L, 13g/L, 43g/L or 8 g/L. In some embodiments of the invention, the hydrogen ion concentration of the fluorine-containing pickle liquor is 0.1-10 mol/L. In certain embodiments, the fluorine-containing pickle liquor has a hydrogen ion concentration of 1.5mol/L, 5.3mol/L, 0.15mol/L, 8.9mol/L, or 0.5 mol/L.
In certain embodiments of the invention, the fluorine-containing pickle liquor is prepared by the following method:
stirring spodumene particles, sulfuric acid and a fluorine-containing auxiliary agent for reaction to obtain a fluorine-containing acid immersion liquid.
In certain embodiments of the present invention, the spodumene particles have a particle size of 50 to 200 mesh. In certain embodiments, the particle size of the spodumene particles is 100 mesh, 150 mesh, or 200 mesh.
In certain embodiments of the present invention, the sulfuric acid has a mass concentration of 30% to 80%. In certain embodiments, the sulfuric acid is at a concentration of 50%, 70%, or 80% by mass.
In certain embodiments of the present invention, the fluorine-containing promoter comprises at least one of hydrofluoric acid, fluorite fluorine-containing minerals, fluorosilicic acids, fluorosilicates, and fluoride salts. In certain embodiments, the fluorine-containing promoter comprises at least one of hydrofluoric acid, fluorite, fluorosilicic acid, sodium fluorosilicate, and sodium fluoride.
In certain embodiments of the present invention, the spodumene particles, sulfuric acid, and fluorine-containing adjuvant are present in a mass ratio of 1: 0.05-5: 0.05 to 5. In certain embodiments, the spodumene particles, sulfuric acid, and fluorine-containing promoter are present in a mass ratio of 1: 2: 2. 1: 3: 3. 1: 1.5: 1. 1: 5: 5 or 1: 1: 2.
in certain embodiments of the present invention, the spodumene particles need not be subjected to a calcination transformation prior to reacting the spodumene particles, sulfuric acid, and fluorine-containing adjuvant under agitation.
In certain embodiments of the invention, the spodumene particles may be wetted with water prior to agitating the spodumene particles, sulfuric acid, and fluorine-containing adjuvant for reaction. The amount of water used is not particularly limited in the present invention.
In certain embodiments of the invention, the stirring reaction is carried out in a closed environment. The closed environment can avoid the escape of gas containing fluorine, reduce the loss of fluorine element and improve the comprehensive utilization rate of fluorine. In certain embodiments of the invention, the volumetric loading of spodumene particles, sulfuric acid, and fluorine-containing adjuvant in a closed environment is between 40% and 70%.
In some embodiments of the invention, the stirring reaction is performed at a temperature of 50-150 ℃ for 0.5-3 hours. In certain embodiments, the temperature of the stirred reaction is 85 ℃, 100 ℃, 120 ℃, or 150 ℃. In certain embodiments, the stirring reaction time is 3 hours or 0.5 hours.
The stirring method for the stirring reaction is not particularly limited in the present invention, and a stirring method known to those skilled in the art may be used.
And after obtaining the fluorine-containing acid leaching solution, carrying out heat treatment on the fluorine-containing acid leaching solution at 50-150 ℃ to obtain a defluorinated acid leaching solution.
In the invention, the fluorine-containing pickle liquor can be defluorinated by heat treatment at 50-150 ℃. In certain embodiments of the invention, the temperature of the heat treatment for defluorination is 120 ℃ or 150 ℃. In some embodiments of the present invention, the heat treatment time is 0.5 to 5 hours. In certain embodiments, the heat treatment time is 3 hours.
In some embodiments of the present invention, after the heat treatment, the method further comprises:
and absorbing the fluorine-containing gas in the system after heat treatment by using water, enriching and concentrating the fluorine-containing gas, and reusing the fluorine-containing gas in the preparation process of the fluorine-containing pickle liquor. The recycling of the fluorine-containing gas can reduce the use of fresh fluorine-containing auxiliary agent, and avoid the waste of resources.
The method and parameters for enrichment and concentration are not particularly limited in the present invention, and those familiar to those skilled in the art can be used.
And after obtaining the defluorinated acid leaching solution, carrying out heat treatment on the defluorinated acid leaching solution at 180-350 ℃ to obtain the lithium-containing leaching solution.
In the invention, the defluorinated pickle liquor can be deacidified by carrying out heat treatment on the defluorinated pickle liquor at 180-350 ℃. In certain embodiments of the invention, the temperature of the heat treatment is 180 ℃, 200 ℃, or 250 ℃. In some embodiments of the present invention, the heat treatment time is 0.5 to 12 hours. In certain embodiments, the heat treatment time is 3 hours.
In the invention, after the defluorinated acid leaching solution is subjected to heat treatment, solid-phase insoluble substances and a lithium-containing leaching solution are obtained.
In some embodiments of the present invention, after the heat treatment, the method further comprises:
and absorbing the volatile sulfuric acid obtained by the heat treatment with water, enriching and concentrating, and reusing the concentrated sulfuric acid in the preparation process of the fluorine-containing pickle liquor. The recycling of the volatilized sulfuric acid can reduce the use of fresh sulfuric acid and avoid the waste of resources.
The method and parameters for enrichment and concentration are not particularly limited in the present invention, and those familiar to those skilled in the art can be used.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
In order to further illustrate the present invention, the following will describe the method for treating a fluorine-containing pickle liquor in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Step (1), grinding: crushing spodumene, and grinding to 100 meshes to obtain spodumene particles;
acid leaching in step (2): mixing spodumene particles wetted by water, hydrofluoric acid and sulfuric acid with the mass concentration of 50%, and controlling the mass ratio of the spodumene particles to the hydrofluoric acid to the sulfuric acid to be 1: 2: 2; fully stirring the mixed slurry at 100 ℃ for reaction for 3 hours, and keeping the reaction system closed to obtain fluorine-containing pickle liquor; the fluorine content of the fluorine-containing pickle liquor is 35g/L, c (H)+) 1.5mol/L, strong acidity;
step (3) first-stage heat treatment defluorination: directly heating the slurry reacted in the step (2) to 120 ℃, keeping the reaction for 3h, realizing one-stage heat treatment defluorination, absorbing fluorine-containing gas generated by defluorination by water to obtain fluorine-containing acid liquid, enriching and concentrating, and returning to the step (2);
and (4) deacidifying by secondary heat treatment: and (4) continuously heating the defluorination leaching solution obtained in the step (3) to 250 ℃, reacting for 3 hours to realize deacidification, absorbing the extracted sulfuric acid gas by using water, and returning the sulfuric acid gas to the step (2) after the sulfuric acid gas is enriched and concentrated.
Through measurement, the liquid-phase residual rate of fluorine in the leachate obtained in the step (4) is 2.8%, and the pH value of the deacidified leachate obtained in the step (4) is 0.85;
through determination, 50 wt% of aluminum sulfate in the step (4) is separated out because of being insoluble in acid, so that the preliminary separation of lithium and aluminum is realized, and the subsequent separation and impurity removal of lithium-containing leachate are facilitated; the XRD result of the solid insoluble substance obtained after defluorination and deacidification of the spodumene fluoric acid-containing immersion liquid of the present application is shown in fig. 1. FIG. 1 is an XRD pattern of a solid phase insoluble matter in example 1 of the present invention. As is clear from fig. 1, aluminum is mainly precipitated as aluminum sulfate, and lithium-containing fluoroalumine insoluble substances such as lithium sodium cryolite are not detected.
Through determination, the liquid-phase retention rate of the lithium after defluorination in the step (3) and deacidification in the step (4) is 93%.
Example 2
Step (1), grinding: crushing spodumene, and grinding to 150 meshes to obtain spodumene particles;
acid leaching in step (2): mixing spodumene particles wetted by water, fluorite and sulfuric acid with the mass concentration of 70%, wherein the mass ratio of the spodumene particles to the fluorite to the sulfuric acid is controlled to be 1: 3: 3; fully stirring the mixed slurry at 120 ℃ for reaction for 3 hours, and keeping the reaction system closed to obtain fluorine-containing pickle liquor; the fluorine content of the fluorine-containing pickle liquor is 56g/L, c (H)+) 5.3 mol/L;
step (3) first-stage heat treatment defluorination: directly heating the slurry reacted in the step (2) to 150 ℃, keeping the reaction for 3h, realizing one-stage heat treatment defluorination, absorbing fluorine-containing gas generated by defluorination by water to obtain fluorine-containing acid liquid, enriching and concentrating, and returning to the step (2);
and (4) deacidifying by secondary heat treatment: and (4) continuously heating the defluorination leaching solution obtained in the step (3) to 250 ℃, reacting for 3 hours to realize deacidification, absorbing the extracted sulfuric acid gas by using water, and returning the sulfuric acid gas to the step (2) after the sulfuric acid gas is enriched and concentrated.
Through measurement, the liquid-phase residual rate of fluorine in the leachate obtained in the step (4) is 3.4%, and the pH value of the deacidified leachate obtained in the step (4) is 0.35;
as a result, 40 wt% of aluminum sulfate was precipitated in the step (4) as insoluble in acid, and lithium-containing insoluble matter of aluminum fluoride such as lithium sodium cryolite was not detected.
Through determination, the liquid-phase retention rate of the lithium after defluorination in the step (3) and deacidification in the step (4) is 87%.
Example 3
Step (1), grinding: crushing spodumene, and grinding to 200 meshes to obtain spodumene particles;
acid leaching in step (2): spodumene particles moistened with waterMixing granules, fluosilicic acid and sulfuric acid with the mass concentration of 80%, and controlling the mass ratio of spodumene granules, fluosilicic acid and sulfuric acid to be 1: 1.5: 1; fully stirring the mixed slurry at 120 ℃ for reaction for 30min, and keeping the reaction system closed to obtain fluorine-containing pickle liquor; the fluorine content of the fluorine-containing pickle liquor is 13g/L, c (H)+) Is 0.15 mol/L;
step (3) first-stage heat treatment defluorination: directly heating the slurry reacted in the step (2) to 150 ℃, keeping the reaction for 3h, realizing one-stage heat treatment defluorination, absorbing fluorine-containing gas generated by defluorination by water to obtain fluorine-containing acid liquid, enriching and concentrating, and returning to the step (2);
and (4) deacidifying by secondary heat treatment: and (4) continuously heating the defluorination leaching solution obtained in the step (3) to 250 ℃, reacting for 3 hours to realize deacidification, absorbing the extracted sulfuric acid gas by using water, and returning the sulfuric acid gas to the step (2) after the sulfuric acid gas is enriched and concentrated.
Through measurement, the liquid-phase residual rate of fluorine in the leachate obtained in the step (4) is 1.3%, and the pH value of the deacidified leachate obtained in the step (4) is 1;
as a result, 40 wt% of aluminum sulfate was precipitated in the step (4) as insoluble in acid, and lithium-containing insoluble matter of aluminum fluoride such as lithium sodium cryolite was not detected.
Through determination, the liquid-phase retention rate of the lithium after defluorination in the step (3) and deacidification in the step (4) is 95%.
Example 4
Step (1), grinding: crushing spodumene, and grinding to 200 meshes to obtain spodumene particles;
acid leaching in step (2): mixing spodumene particles wetted by water, sodium fluosilicate and sulfuric acid with the mass concentration of 50%, and controlling the mass ratio of the spodumene particles to the sodium fluosilicate to the sulfuric acid to be 1: 5: 5; fully stirring the mixed slurry at 85 ℃ for reaction for 3 hours, and keeping the reaction system closed to obtain fluorine-containing pickle liquor; the fluorine content of the fluorine-containing pickle liquor is 43g/L, c (H)+) Is 8.9 mol/L;
step (3) first-stage heat treatment defluorination: directly heating the slurry reacted in the step (2) to 120 ℃, keeping the reaction for 30min, realizing one-stage heat treatment defluorination, absorbing fluorine-containing gas generated by defluorination by water to obtain fluorine-containing acid liquid, enriching and concentrating, and returning to the step (2);
and (4) deacidifying by secondary heat treatment: and (4) continuously heating the defluorination leaching solution obtained in the step (3) to 200 ℃, reacting for 3 hours to realize deacidification, absorbing the extracted sulfuric acid gas by using water, and returning the sulfuric acid gas to the step (2) after the sulfuric acid gas is enriched and concentrated.
Through measurement, the liquid-phase residual rate of fluorine in the leachate obtained in the step (4) is 5.3%, and the pH value of the deacidified leachate obtained in the step (4) is 1;
it was found that 50 wt% of aluminum sulfate was precipitated in step (4) because it was insoluble in acid, and lithium-containing insoluble aluminum fluoride such as lithium sodium cryolite was not detected.
Through determination, the liquid-phase retention rate of the lithium after defluorination in the step (3) and deacidification in the step (4) is 95%.
Example 5
Step (1), grinding: crushing spodumene, and grinding to 100 meshes to obtain spodumene particles;
acid leaching in step (2): mixing spodumene particles wetted by water, sodium fluoride and sulfuric acid with the mass concentration of 50%, wherein the mass ratio of the spodumene particles to the sodium fluoride to the sulfuric acid is controlled to be 1: 1: 2; fully stirring the mixed slurry at 150 ℃ for reaction for 3h, and keeping the reaction system closed to obtain fluorine-containing pickle liquor; the fluorine content of the fluorine-containing pickle liquor is 8g/L, c (H)+) Is 0.5 mol/L;
step (3) first-stage heat treatment defluorination: directly heating the slurry reacted in the step (2) to 150 ℃, keeping the reaction for 3h, realizing one-stage heat treatment defluorination, absorbing fluorine-containing gas generated by defluorination by water to obtain fluorine-containing acid liquid, enriching and concentrating, and returning to the step (2);
and (4) deacidifying by secondary heat treatment: and (4) continuously heating the defluorination leaching solution obtained in the step (3) to 250 ℃, reacting for 3 hours to realize deacidification, absorbing the extracted sulfuric acid gas by using water, and returning the sulfuric acid gas to the step (2) after the sulfuric acid gas is enriched and concentrated.
Through measurement, the liquid-phase residual rate of fluorine in the leachate obtained in the step (4) is 2.4%, and the pH value of the deacidified leachate obtained in the step (4) is 0.9;
as a result, 40 wt% of aluminum sulfate was precipitated in the step (4) as insoluble in acid, and lithium-containing insoluble matter of aluminum fluoride such as lithium sodium cryolite was not detected.
Through determination, the liquid-phase retention rate of the lithium after defluorination in the step (3) and deacidification in the step (4) is 91%.
Comparative example 1
Step (1), grinding: crushing and grinding lepidolite to 100 meshes to obtain lepidolite particles;
acid leaching in step (2): mixing lepidolite particles wetted with water, hydrofluoric acid and sulfuric acid with the mass concentration of 50%, and controlling the mass ratio of the lepidolite particles to the hydrofluoric acid to the sulfuric acid to be 1: 2: 2; fully stirring the mixed slurry at 85 ℃ for reaction for 3 hours, and keeping the reaction system closed to obtain fluorine-containing pickle liquor; the fluorine content of the fluorine-containing pickle liquor is 34g/L, c (H)+) Is 0.9 mol/L;
step (3) first-stage heat treatment defluorination: directly heating the slurry reacted in the step (2) to 120 ℃, keeping the reaction for 3h, realizing one-stage heat treatment defluorination, absorbing fluorine-containing gas generated by defluorination by water to obtain fluorine-containing acid liquid, enriching and concentrating, and returning to the step (2);
and (4) deacidifying by secondary heat treatment: and (4) continuously heating the defluorination leaching solution obtained in the step (3) to 250 ℃, reacting for 3 hours to realize deacidification, absorbing the extracted sulfuric acid gas by using water, and returning the sulfuric acid gas to the step (2) after the sulfuric acid gas is enriched and concentrated.
Through measurement, the liquid-phase residual rate of fluorine in the leachate obtained in the step (4) is 5.7%, and the pH value of the deacidified leachate obtained in the step (4) is 0.8;
the aluminum sulfate in the step (4) was precipitated by measurement as insoluble in acid, but lithium-containing fluoroalumine insoluble matter such as lithium sodium cryolite was detected, indicating that the two-stage heat treatment is more suitable for defluorination of the fluoric acid-containing immersion liquid of spodumene.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for treating acid leaching solution containing fluorine comprises the following steps:
A) carrying out heat treatment on the fluorine-containing pickle liquor at 50-150 ℃ to obtain defluorinated pickle liquor;
B) and carrying out heat treatment on the defluorinated acid leaching solution at 180-350 ℃ to obtain a lithium-containing leaching solution.
2. The treatment method according to claim 1, wherein in the step A), the fluorine-containing acid leaching solution is a fluorine-containing acid leaching solution generated after lithium is extracted from spodumene;
the fluorine content of the fluorine-containing pickle liquor is 500 mg/L-500 g/L;
the concentration of hydrogen ions in the fluorine-containing pickle liquor is 0.1-10 mol/L.
3. The process according to claim 2, characterized in that the fluorine-containing pickling liquid is prepared according to the following method:
stirring spodumene particles, sulfuric acid and a fluorine-containing auxiliary agent for reaction to obtain a fluorine-containing acid immersion liquid;
the particle size of the spodumene particles is 50-200 meshes;
the mass concentration of the sulfuric acid is 30-80%;
the fluorine-containing auxiliary agent comprises at least one of hydrofluoric acid, fluorite fluorine-containing mineral, fluosilicic acid, fluorosilicate and fluoride salt.
4. The treatment method according to claim 3, wherein the mass ratio of the spodumene particles, the sulfuric acid and the fluorine-containing auxiliary agent is 1: 0.05-5: 0.05 to 5.
5. The treatment method according to claim 3, wherein the stirring reaction is carried out at a temperature of 50 to 150 ℃ for 0.5 to 3 hours.
6. The process according to claim 3, wherein the spodumene particles, the sulfuric acid and the fluorine-containing auxiliary agent are stirred for reaction without subjecting the spodumene particles to calcination transformation.
7. The process of claim 3, wherein the stirring reaction is carried out in a closed environment.
8. The treatment method according to claim 1, wherein the heat treatment time in step A) is 0.5 to 5 hours.
9. The process of claim 1, wherein after the heat treatment in step a), further comprising:
and absorbing the fluorine-containing gas in the system after heat treatment by using water, enriching and concentrating the fluorine-containing gas, and reusing the fluorine-containing gas in the preparation process of the fluorine-containing pickle liquor.
10. The treatment method according to claim 1, wherein in the step B), the time of the heat treatment is 0.5-12 h;
after the heat treatment, the method further comprises the following steps:
and absorbing the volatile sulfuric acid obtained by the heat treatment with water, enriching and concentrating, and reusing the concentrated sulfuric acid in the preparation process of the fluorine-containing pickle liquor.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60228627A (en) * | 1984-04-25 | 1985-11-13 | Mitsui Mining & Smelting Co Ltd | Method for removing fluorine in wet treating of worthy metal |
| WO1988003044A1 (en) * | 1986-10-21 | 1988-05-05 | Arch Development Corp. | Method for the concentration and separation of actinides from biological and environmental samples |
| CA2289967A1 (en) * | 1998-11-17 | 2000-05-17 | Titanium Minerals Of Canada Inc. | Methods for separation of titanium from ore |
| CN102010991A (en) * | 2010-10-29 | 2011-04-13 | 江西本源新材料科技有限公司 | Method for extracting lithium salt and removing potassium from lithium mica raw material |
| CN102952951A (en) * | 2011-08-22 | 2013-03-06 | 中国科学院过程工程研究所 | Method for extracting tantalum and niobium and producing potassium fluosilicate from tungsten smelting slag |
| US20150052739A1 (en) * | 2013-08-20 | 2015-02-26 | University Of Calcutta | Regeneration of cathode material of lithium-ion batteries |
| CN104593586A (en) * | 2014-12-19 | 2015-05-06 | 昆明理工大学 | Method for treating zinc oxide smoke dust to remove fluochloride by virtue of microwave low-temperature roasting and alkali washing processes |
| CN105731704A (en) * | 2016-01-18 | 2016-07-06 | 云南世邦环保科技发展有限公司 | Treatment method for removing fluorine and chlorine ions in acidic wastewater |
| CN106319245A (en) * | 2016-09-19 | 2017-01-11 | 福州大学 | Lepidolite continuous reaction lithium extracting method |
| CN110791664A (en) * | 2019-11-07 | 2020-02-14 | 江西飞宇新能源科技有限公司 | Method for extracting lithium from lepidolite, lithium-containing mother liquor and filler |
| CN111349783A (en) * | 2020-04-21 | 2020-06-30 | 华南理工大学 | Lepidolite defluorination leaching process |
| CN111961857A (en) * | 2020-08-11 | 2020-11-20 | 长沙矿冶研究院有限责任公司 | Method for synchronously defluorinating valuable metals leached from waste lithium ion batteries |
| CN112080654A (en) * | 2020-09-25 | 2020-12-15 | 贵州省地质矿产中心实验室(贵州省矿产品黄金宝石制品质量检验站) | Method for recovering acid and silicon from phosphorus rare earth chemical concentrate leachate |
-
2021
- 2021-08-11 CN CN202110918308.4A patent/CN113621800B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60228627A (en) * | 1984-04-25 | 1985-11-13 | Mitsui Mining & Smelting Co Ltd | Method for removing fluorine in wet treating of worthy metal |
| WO1988003044A1 (en) * | 1986-10-21 | 1988-05-05 | Arch Development Corp. | Method for the concentration and separation of actinides from biological and environmental samples |
| CA2289967A1 (en) * | 1998-11-17 | 2000-05-17 | Titanium Minerals Of Canada Inc. | Methods for separation of titanium from ore |
| CN102010991A (en) * | 2010-10-29 | 2011-04-13 | 江西本源新材料科技有限公司 | Method for extracting lithium salt and removing potassium from lithium mica raw material |
| CN102952951A (en) * | 2011-08-22 | 2013-03-06 | 中国科学院过程工程研究所 | Method for extracting tantalum and niobium and producing potassium fluosilicate from tungsten smelting slag |
| US20150052739A1 (en) * | 2013-08-20 | 2015-02-26 | University Of Calcutta | Regeneration of cathode material of lithium-ion batteries |
| CN104593586A (en) * | 2014-12-19 | 2015-05-06 | 昆明理工大学 | Method for treating zinc oxide smoke dust to remove fluochloride by virtue of microwave low-temperature roasting and alkali washing processes |
| CN105731704A (en) * | 2016-01-18 | 2016-07-06 | 云南世邦环保科技发展有限公司 | Treatment method for removing fluorine and chlorine ions in acidic wastewater |
| CN106319245A (en) * | 2016-09-19 | 2017-01-11 | 福州大学 | Lepidolite continuous reaction lithium extracting method |
| CN110791664A (en) * | 2019-11-07 | 2020-02-14 | 江西飞宇新能源科技有限公司 | Method for extracting lithium from lepidolite, lithium-containing mother liquor and filler |
| CN111349783A (en) * | 2020-04-21 | 2020-06-30 | 华南理工大学 | Lepidolite defluorination leaching process |
| CN111961857A (en) * | 2020-08-11 | 2020-11-20 | 长沙矿冶研究院有限责任公司 | Method for synchronously defluorinating valuable metals leached from waste lithium ion batteries |
| CN112080654A (en) * | 2020-09-25 | 2020-12-15 | 贵州省地质矿产中心实验室(贵州省矿产品黄金宝石制品质量检验站) | Method for recovering acid and silicon from phosphorus rare earth chemical concentrate leachate |
Non-Patent Citations (2)
| Title |
|---|
| 廖力夫 等: "《分析化学 第二版》", 31 August 2008, 华中科技大学出版社 * |
| 张长江 等: "《中学生学习辞典 化学卷》", 30 September 2012, 兴界图书出版社 * |
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