CN115198109A - Method for extracting lithium from lithium-containing clay by mixed acid - Google Patents
Method for extracting lithium from lithium-containing clay by mixed acid Download PDFInfo
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- CN115198109A CN115198109A CN202210592606.3A CN202210592606A CN115198109A CN 115198109 A CN115198109 A CN 115198109A CN 202210592606 A CN202210592606 A CN 202210592606A CN 115198109 A CN115198109 A CN 115198109A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—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
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a method for extracting lithium from lithium-containing clay step by using mixed acid, which comprises the following steps: s1, crushing and screening the lithium-containing clay into mineral powder; s2, fully mixing the lithium-containing clay mineral powder with mixed acid; s3, leaching the mixture obtained in the step S2 at the temperature of 50-150 ℃ for reaction; and S4, carrying out solid-liquid separation on the product obtained in the step S3 to obtain a lithium-containing filtrate. The invention takes the lithium-containing clay as the raw material, adopts non-roasting and direct acid leaching for lithium extraction under the condition of low-temperature mixed acid, has simple process, strong operability and low production cost, and breaks through the process short board with high energy consumption.
Description
Technical Field
The invention relates to the field of lithium extraction methods, in particular to a method for extracting lithium from lithium-containing clay by mixed acid.
Background
Lithium ore is an extremely rare white light metal resource called white petroleum, and has great strategic significance for national economy and national defense construction. The method is widely applied to the fields of high-energy batteries, clean production, high-end equipment, photovoltaic energy storage and the like. At present, the production scale of extracting lithium by adopting domestic solid lithium ore is smaller and can not meet the demand, so in recent years, the ores required by lithium production enterprises in China mainly depend on import, and the production cost of imported lithium is increased year by year.
Natural lithium resources in China mainly comprise brine resources, and lithium extraction from brine replaces lithium extraction from ores due to the advantages of low cost, short flow and high recovery rate, so that the method becomes a mainstream lithium extraction mode. However, with the rapid development of electronic devices and electric vehicles, the demand of the market for lithium is increasingly expanding, and lithium-containing clay has received more and more attention because lithium extracted from brine cannot meet the market demand due to its own defects (such as complex brine components, low lithium content, difficult separation of magnesium and lithium, etc.). The lithium-containing clay has the main advantages of large total resource amount, convenient mining and no need of blasting, the early mining link has cost advantage, and the lithium resource in the lithium-containing clay has wide development and application prospects in China.
In the research on the process for preparing lithium carbonate by leaching lithium from lepidolite, shu Qiyi and the like are prepared by mixing lepidolite, K 2 SO 4 、Na 2 SO 4 Mixing with CaO, calcining in a muffle furnace at 950 ℃ for 2h, acidifying and calcining with concentrated sulfuric acid for 3h, and decocting in water for 4h to obtain the final product with a lithium leaching rate of about 90%. The method selects high-temperature roasting, has complex operation and consumes a large amount of cost.
In the technical development of lithium extraction in literature, YAN and the like are subjected to autoclaving and leaching experiments of defluorinated lepidolite and lime milk in a high-pressure reaction kettle, and the like, and the fact that about 42.3 percent of fluorine can be removed by defluorination and roasting of lepidolite at 860 ℃ for 0.5h is found, then the lepidolite is subjected to ball milling for 100min and is subjected to pressure leaching reaction with the lime milk at 1:1 in the high-pressure reaction kettle, and the leaching rate of Li can reach 98.9 percent by reacting at 150 ℃ for 1h with the liquid-solid ratio of 4:1. However, the pressure cooking method adopted in the process needs defluorination roasting to exert pressure on environment protection, and the reaction needs to be carried out under high temperature and high pressure, so that the reaction conditions are harsh, potential safety hazards exist, and higher requirements on equipment and operation processes are met; the disadvantages of this method prevent further industrial application.
Disclosure of Invention
The invention aims to provide a method for extracting lithium from lithium-containing clay by mixed acid, which solves the problems that high-temperature roasting is required and reaction is required under high-pressure environment when lithium is extracted from a lithium-containing raw material in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for extracting lithium from a lithium-containing clay by mixed acid, comprising the steps of:
s1, taking unfired lithium-containing clay mineral powder;
s2, fully mixing the lithium-containing clay mineral powder with mixed acid according to a solid-liquid ratio of 1 to 3 to 1;
s3, carrying out leaching reaction on the mixture obtained in the step S2 at the temperature of 50-150 ℃;
and S4, carrying out solid-liquid separation on the reactant obtained in the step S3 to obtain a filtrate which is a lithium-containing solution.
Further, in step S1, the mesh number of the lithium-containing clay mineral powder is less than or equal to 200 meshes.
Further, in step S2, the mixed acid is a mixture of concentrated sulfuric acid and concentrated phosphoric acid, and the dosage ratio of the concentrated sulfuric acid to the concentrated phosphoric acid is 1:1.
Furthermore, the volume fraction of the mixed acid is 10% -80%.
Further, in step S3, the leaching reaction time is 2 to 6h.
The invention uses the lithium-containing clay as the raw material, adopts the non-roasted lithium-containing clay mineral powder, and directly extracts lithium by acid leaching under the condition of low-temperature mixed acid, thereby omitting the high-temperature roasting process, providing an acid environment by using sulfuric acid in the mixed acid, and destroying the clay structure by phosphoric acid under the acid condition.
The method has the advantages of simple process, strong operability and low production cost. The invention breaks through the processes of high-temperature roasting, high-pressure reaction and other high energy consumption processes in the process of extracting lithium from lithium-containing mineral resources, opens up a new way for extracting the lithium resources, greatly simplifies the process flow, saves a large amount of cost, can be used for large-scale production, and breaks through process short plates with high energy consumption.
The invention solves the problem of lithium resource shortage in China based on improving the utilization value of mineral resources, and achieves the purpose of purification. The invention successfully researches a method for directly leaching lithium from the lithium-containing clay under the condition of low-temperature mixed acid leaching by adopting a no-roasting method. The invention can be applied to industrial production, greatly saves cost and increases production benefit.
Drawings
FIG. 1 is a block flow diagram of an embodiment of the invention.
FIG. 2 is a graph comparing leaching rates of 5 examples of the present invention.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the drawings.
Example 1
As shown in fig. 1, this embodiment 1 includes the following steps:
(1) Crushing and screening the lithium-containing clay, and taking 200-mesh lithium-containing clay mineral powder.
(2) Adding the lithium-containing clay mineral powder obtained in the step (1) and mixed acid into a conical flask according to the solid-to-liquid ratio of 1:3. Wherein the mixed acid is formed by mixing sulfuric acid and phosphoric acid according to the volume ratio of 1:1, and the volume fraction of the mixed acid is 25 percent.
(3) And (3) placing the conical flask obtained in the step (2) at 100 ℃ for leaching reaction for 3h to obtain a reactant.
(4) And (4) after the reactant obtained in the step (3) is cooled, carrying out suction filtration, and obtaining filtrate which is lithium-containing solution. And (3) measuring the volume of the filtrate obtained in the step (4), diluting the filtrate to a proper multiple, and performing an atomic absorption test to obtain the leaching rate of the lithium of 60.58%.
Example 2
This example 2 includes the following steps:
(1) Crushing and screening the lithium-containing clay, and taking 200-mesh lithium-containing clay mineral powder.
(2) Adding the lithium-containing clay mineral powder obtained in the step (1) and mixed acid into a conical flask according to the solid-to-liquid ratio of 1:4. Wherein the mixed acid is formed by mixing sulfuric acid and nitric acid according to the volume ratio of 1:1, and the volume fraction of the mixed acid is 60%.
(3) And (3) placing the conical flask obtained in the step (2) at 100 ℃ for leaching reaction for 3h to obtain a reactant.
(4) And (4) carrying out suction filtration after the reactant obtained in the step (3) is cooled, wherein the obtained filtrate is a lithium-containing solution. And (5) measuring the volume of the filtrate obtained in the step (4), diluting the filtrate to a proper multiple, and performing an atomic absorption test to obtain the leaching rate of the lithium of 52.12%.
Example 3
This example 3 includes the following steps:
(1) And (3) crushing and screening the lithium-containing clay, and taking 200-mesh lithium-containing clay mineral powder.
(2) And (2) adding the lithium-containing clay mineral powder obtained in the step (1) and mixed acid into a conical flask according to the solid-liquid ratio of 1:4. Wherein the mixed acid is formed by mixing sulfuric acid and phosphoric acid according to the volume ratio of 1:1, and the volume fraction of the mixed acid is 60%.
(3) And (3) placing the conical flask obtained in the step (2) at 120 ℃ for leaching reaction for 3h to obtain a reactant.
(4) And (4) carrying out suction filtration after the reactant obtained in the step (3) is cooled, wherein the obtained filtrate is a lithium-containing solution. And (3) measuring the volume of the filtrate obtained in the step (4), diluting the filtrate to a proper multiple, and performing an atomic absorption test to obtain the leaching rate of the lithium of 91.02%.
Example 4
This example 4 includes the following steps:
(1) Crushing and screening the lithium-containing clay, and taking 200-mesh lithium-containing clay mineral powder.
(2) Adding the lithium-containing clay mineral powder obtained in the step (1) and mixed acid into a conical flask according to the solid-to-liquid ratio of 1:3. Wherein the mixed acid is prepared by mixing hydrochloric acid and phosphoric acid according to the volume ratio of 1:1, and the volume fraction of the mixed acid is 30 percent.
(3) And (3) placing the conical flask obtained in the step (2) at 120 ℃ for leaching reaction for 2h to obtain a reactant.
(4) And (4) carrying out suction filtration after the reactant obtained in the step (3) is cooled, wherein the obtained filtrate is a lithium-containing solution. And (3) measuring the volume of the filtrate obtained in the step (4), diluting the filtrate to a proper multiple, and performing an atomic absorption test to obtain the leaching rate of the lithium of 55.96%.
Example 5
This example 5 includes the following steps:
(1) Crushing and screening the lithium-containing clay, and taking 200-mesh lithium-containing clay mineral powder.
(2) Adding the lithium-containing clay mineral powder obtained in the step (1) and mixed acid into a conical flask according to the solid-to-liquid ratio of 1:4. Wherein the mixed acid is formed by mixing sulfuric acid and phosphoric acid according to the volume ratio of 1:1, and the volume fraction of the mixed acid is 60 percent.
(3) And (3) placing the conical flask obtained in the step (2) at 120 ℃ for leaching reaction for 3h to obtain a reactant.
(4) And (4) carrying out suction filtration after the reactant obtained in the step (3) is cooled, wherein the obtained filtrate is a lithium-containing solution. And (5) measuring the volume of the filtrate obtained in the step (4), diluting the filtrate to a proper multiple, and performing an atomic absorption test to obtain the leaching rate of lithium of 77.83%.
As shown in FIG. 2, it can be seen from the above 5 examples that when the acid is selected to be sulfuric acid and phosphoric acid, an acidic environment is provided for phosphoric acid to destroy the structure of the ore due to strong acidity of sulfuric acid, and a good lithium extraction effect can be obtained under the conditions that the leaching reaction temperature is 120 ℃, the reaction time is 3 hours, and the reaction solid-to-liquid ratio is 1:4.
The embodiments of the present invention are described only for the preferred embodiments of the present invention, and not for the limitation of the concept and scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall into the protection scope of the present invention, and the technical content of the present invention which is claimed is fully set forth in the claims.
Claims (5)
1. A method for extracting lithium from a lithium-containing clay by mixed acid, comprising the steps of:
s1, taking unfired lithium-containing clay mineral powder;
s2, fully mixing the lithium-containing clay mineral powder with mixed acid according to a solid-liquid ratio of 1 to 3 to 1;
s3, carrying out leaching reaction on the mixture obtained in the step S2 at the temperature of 50-150 ℃;
and S4, carrying out solid-liquid separation on the reactant obtained in the step S3 to obtain a filtrate which is a lithium-containing solution.
2. The method of claim 1, wherein in step S1, the mesh size of the lithium-containing clay mineral powder is less than or equal to 200 meshes.
3. The method of claim 1, wherein in step S2, the mixed acid is a mixture of concentrated sulfuric acid and concentrated phosphoric acid, and the ratio of the concentrated sulfuric acid to the concentrated phosphoric acid is 1:1.
4. The method of claim 1 or 3, wherein the volume fraction of the mixed acid is 10% to 80%.
5. The method for extracting lithium from lithium-containing clay by mixed acid according to claim 1 or 3, wherein in the step S3, the leaching reaction time is 2 to 6h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116477858A (en) * | 2023-02-28 | 2023-07-25 | 四川顺应锂材料科技有限公司 | Method for preparing battery-grade lithium carbonate by pressure leaching of clay lithium ore |
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