CN117758062A - Method for extracting valuable metal from solid lithium-containing material - Google Patents
Method for extracting valuable metal from solid lithium-containing material Download PDFInfo
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- CN117758062A CN117758062A CN202311798856.3A CN202311798856A CN117758062A CN 117758062 A CN117758062 A CN 117758062A CN 202311798856 A CN202311798856 A CN 202311798856A CN 117758062 A CN117758062 A CN 117758062A
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- leaching
- lithium
- solid lithium
- containing material
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 155
- 239000000463 material Substances 0.000 title claims abstract description 117
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 116
- 239000002184 metal Substances 0.000 title claims abstract description 116
- 239000007787 solid Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 75
- 238000002386 leaching Methods 0.000 claims abstract description 302
- 239000007788 liquid Substances 0.000 claims abstract description 77
- 150000002739 metals Chemical class 0.000 claims abstract description 70
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 238000000605 extraction Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 75
- 238000005406 washing Methods 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 22
- 239000010436 fluorite Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 239000002699 waste material Substances 0.000 claims description 18
- 229910052629 lepidolite Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 229910052642 spodumene Inorganic materials 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 4
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims description 3
- -1 lithange Chemical compound 0.000 claims description 3
- 229910052670 petalite Inorganic materials 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 56
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 32
- 230000008569 process Effects 0.000 description 31
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 20
- 229910052700 potassium Inorganic materials 0.000 description 20
- 239000011591 potassium Substances 0.000 description 20
- 239000002893 slag Substances 0.000 description 16
- 238000012545 processing Methods 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 12
- 238000001914 filtration Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 230000008901 benefit Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052792 caesium Inorganic materials 0.000 description 8
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 229910052701 rubidium Inorganic materials 0.000 description 8
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 8
- 238000005265 energy consumption Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000007865 diluting Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010433 feldspar Substances 0.000 description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 4
- 229910001947 lithium oxide Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000001360 synchronised effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052644 β-spodumene Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The application discloses a method for extracting valuable metals from solid lithium-containing materials, and belongs to the technical field of mineral comprehensive utilization. The method comprises the following steps: mixing the solid lithium-containing material with a leaching agent and a leaching auxiliary agent, and carrying out pressure leaching to obtain a leaching mixed solution; and carrying out solid-liquid separation on the leaching mixed liquid to obtain valuable metal leaching liquid. The method solves the technical problem that the extraction efficiency of valuable metals in the conventional solid lithium-containing materials is low.
Description
Technical Field
The application relates to the technical field of mineral comprehensive utilization, in particular to a method for extracting valuable metals from solid lithium-containing materials.
Background
Spodumene and lepidolite are the main solid lithium-containing materials for producing lithium salts, and the lithium-containing materials can be treated by a wet process to extract lithium and other valuable metals from the lithium-containing materials.
The conventional wet process is to soak the lithium-containing material in a chemical reagent to make the valuable metals in the lithium-containing material react with the chemical reagent, thereby extracting the valuable metals from the lithium-containing material; however, the leaching time required by the process is long, so that the extraction efficiency of valuable metals is low.
The foregoing is merely provided to facilitate an understanding of the principles of the present application and is not admitted to be prior art.
Disclosure of Invention
The main purpose of the application is to provide a method for extracting valuable metals from solid lithium-containing materials, which aims to solve the technical problem of lower extraction efficiency of valuable metals in conventional solid lithium-containing materials.
To achieve the above object, the present application provides a method for extracting valuable metals from a solid lithium-containing material, the method comprising the steps of:
mixing the solid lithium-containing material with a leaching agent and a leaching aid, and carrying out pressure leaching;
and obtaining valuable metal leaching liquid after solid-liquid separation.
Optionally, the mass ratio of the solid lithium-containing material, the leaching agent and the leaching auxiliary agent is 1 (1-2) (0.1-0.5).
Optionally, the leaching aid comprises: a fluorite tailings having a lithium content of greater than or equal to 0.3wt.%.
Optionally, the leaching agent includes: sulfuric acid.
Optionally, the mass concentration of sulfuric acid in the leaching agent is 70-85%.
Optionally, after the step of obtaining the valuable metal leaching solution after the solid-liquid separation, the method further comprises:
collecting leaching residues after the solid-liquid separation, and adding water to wash the leaching residues to obtain washing liquid;
the leaching agent is prepared by the washing liquid.
Optionally, the washing liquid is used to dilute the leaching mixture prior to solid-liquid separation of the leaching mixture.
Optionally, the leaching temperature of the pressure leaching is: the leaching pressure is 150-190 ℃, and the leaching pressure is: the leaching time is 0.2-0.8 Mpa: 0.5-3h.
Optionally, the solid lithium-containing material comprises: one or more of lepidolite, beta-phase spodumene, lithange, petalite, waste aluminum electrolyte, waste lithium-containing glass frit and waste polishing powder.
Optionally, the solid lithium-containing material is a finely ground lithium-containing material, and more than 200 mesh particles in the particle size distribution of the solid lithium-containing material are greater than 50%.
The application discloses a valuable metal extraction method in solid lithium-containing materials, which comprises the steps of mixing the solid lithium-containing materials with a leaching agent and a leaching aid, and carrying out pressure leaching, wherein the leaching reaction is promoted by using the pressure and the leaching aid, so that the processing adaptability to the solid lithium-containing materials is enhanced, and compared with a conventional wet process, the leaching rate of valuable metals is effectively improved, the leaching time is greatly shortened, and the extraction efficiency of the valuable metals is improved by adding the pressure and the leaching aid; and then directly obtaining valuable metal leaching liquid after solid-liquid separation, so as to realize the rapid and synchronous extraction of valuable metals in the solid lithium-containing material; the method adopts the full wet process, avoids the problem that sulfuric acid is decomposed and tail gas treatment is required due to the conventional high-temperature roasting process, reduces energy consumption and greatly reduces process cost; and because of the reduction of the process cost and the higher leaching rate of valuable metals, the method can obtain better economic benefit for extracting lithium and other valuable metals from the low-grade lithium-containing material, and has better adaptability to the processing raw materials.
Drawings
Fig. 1 is a schematic flow chart of a method for extracting valuable metals from a solid lithium-containing material according to an embodiment of the present application;
fig. 2 is a process flow diagram of a method for extracting valuable metals from a solid lithium-containing material according to an embodiment of the present application.
The realization, functional characteristics and advantages of the present application will be further described with reference to the embodiments, referring to the attached drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be regarded as not exist and not within the protection scope of the present application. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
With the rapid development of new energy industry, the demand of lithium ion batteries is rapidly increased, and the production scale of lithium salt is rapidly enlarged, so that the reserves of high-grade lithium ores are continuously reduced. The use of low grade lithium-containing ores and other lithium-containing materials is therefore becoming increasingly important.
The conventional extraction method of valuable metals in the solid lithium-containing material comprises the following steps: roasting and wet processes; wherein, the sulfuric acid roasting method in the roasting method is to perform transformation roasting on spodumene at 1150-1200 ℃, uniformly mixing the roasted spodumene concentrate with concentrated sulfuric acid according to a certain proportion, adding the mixture into an acidification roasting chamber, performing closed acidification roasting for 30-60 min at the temperature of about 250-300 ℃, and reacting beta-spodumene in the roasting material with sulfuric acid to obtain water-soluble Li 2 SO 4 . However, the method needs high-temperature roasting, has high energy consumption, and has the phenomenon of sulfuric acid decomposition in the sulfuric acid roasting process, so that a tail gas treatment system is large, and the tail gas treatment cost is high. And roastingThe sulfate roasting method in the method is that lepidolite concentrate and sulfate are matched and stirred together, the mixture is stirred by a stirrer and then enters a kiln to be roasted at 800-900 ℃, and crystal form conversion roasting is carried out during roasting to obtain Li which is soluble in water 2 SO 4 . However, the method also needs high-temperature roasting, and has high energy consumption, so that the production cost is high; in addition, because a large amount of sulfate is added, the content of alkali metal in leaching slag is high, and the leaching slag is difficult to directly use. Because the process cost for extracting valuable metals in the conventional solid lithium-containing materials is high, the method is mostly suitable for high-grade solid lithium-containing materials, and low-grade solid lithium-containing materials are difficult to treat, so that the low-grade solid lithium-containing materials are difficult to utilize. In addition, in the roasting method, after the solid lithium-containing material is roasted, only lithium in the material can form soluble lithium salt, and other valuable metals can be converted into solid slag, so that more process flows are required to be added to extract the valuable metals in the solid slag, and synchronous extraction of the valuable metals in the solid lithium-containing material is difficult to realize.
The wet rule is to soak the lithium-containing material in a chemical reagent to make the valuable metals in the lithium-containing material react with the chemical reagent, thereby extracting the valuable metals from the lithium-containing material. However, the method has low leaching rate of valuable metals, and the required leaching time is long, and the conventional reaction time is about 6 hours, so that the extraction efficiency of the valuable metals is low.
In view of the above, the method for extracting valuable metals from the solid lithium-containing material comprises the steps of mixing the solid lithium-containing material with a leaching agent and a leaching aid, and carrying out pressure leaching, wherein the leaching reaction is promoted by using the pressure and the leaching aid, so that the processing adaptability to the solid lithium-containing material is enhanced, and compared with a conventional wet process, the leaching rate of the valuable metals is effectively improved by adding the pressure and the leaching aid, the leaching time is greatly shortened, and the extraction efficiency of the valuable metals is improved; and then directly obtaining valuable metal leaching liquid after solid-liquid separation, so as to realize the rapid and synchronous extraction of valuable metals in the solid lithium-containing material; the method adopts the full wet process, avoids the problem that sulfuric acid is decomposed and tail gas treatment is required due to the conventional high-temperature roasting process, reduces energy consumption and greatly reduces process cost; furthermore, due to the reduction of the process cost and the higher leaching rate of valuable metals, the method can obtain better economic benefit for extracting lithium and other valuable metals from the low-grade lithium-containing material, and has better adaptability to the processing raw materials.
An embodiment of the present application provides a method for extracting a valuable metal from a solid lithium-containing material, referring to fig. 1, the method for extracting a valuable metal from a solid lithium-containing material includes:
step S10, mixing the solid lithium-containing material with a leaching agent and a leaching aid, and carrying out pressure leaching;
mixing a solid lithium-containing material with a leaching agent and a leaching aid, and performing pressure leaching, wherein the leaching aid can be fluorite tailings; the pressurizing and leaching auxiliary agent is used for promoting the valuable metals in the solid lithium-containing material to react with the leaching agent under the pressurizing condition so as to generate soluble valuable metal salts, and the leaching rate of the valuable metals is improved, so that the leaching rates of lithium, potassium, aluminum and iron respectively reach more than 95.0%, 70.0%, 77.0% and 89.0%, and for the solid lithium-containing material containing rubidium and cesium, the leaching rates of rubidium and cesium can reach more than 90.0%, the leaching reaction time is greatly shortened, the conventional leaching reaction time is more than 6 hours, and the leaching reaction is promoted by the pressurizing and leaching auxiliary agent, so that the higher leaching rate can be realized within 0.5-3 hours, and the extraction efficiency of the valuable metals is improved.
In a possible implementation mode, the mass ratio of the solid lithium-containing material, the leaching agent and the leaching aid is 1 (1-2): 0.1-0.5.
In this embodiment, if the quality of the leaching agent or the leaching auxiliary agent is low, it is difficult to fully react with the solid lithium-containing material, so as to affect the leaching efficiency of valuable metals in the solid lithium-containing material; if the quality of the leaching agent or the leaching auxiliary agent is higher, the leaching efficiency of valuable metals in the solid lithium-containing material is difficult to further improve, and the required production cost is higher; therefore, the mass ratio of the solid lithium-containing material, the leaching agent and the leaching auxiliary agent is 1 (1-2) (0.1-0.5).
Optionally, the mass ratio of the solid lithium-containing material, the leaching agent, and the leaching aid may be 1:1:0.1, 1:1.2:0.3, 1:1.4:0.4, 1:1.6:0.5, 1:1.8:0.5, 1:2:0.5, etc.
In a possible embodiment, the leaching aid comprises: a fluorite tailings having a lithium content of greater than or equal to 0.3wt.%.
In the embodiment, the main component of the fluorite tailings is calcium fluoride, and hydrogen fluoride generated by decomposition under an acidic condition can thoroughly destroy the crystal structure of the lithium-containing material, so that the reaction of metal oxides in the lithium-containing material and sulfuric acid is promoted, various metal oxides which are originally insoluble can enter the leaching solution in the form of soluble sulfate, the utilization of various valuable metals is realized, and the leaching rate of the valuable metals is improved; and the fluorite tailings are tailings after fluorite ore dressing, so that the method has no industrial value, and the tailings (fluorite tailings) after fluorite ore dressing are used, so that the process cost is further reduced, and the industrial tailings to be treated can be effectively utilized. Further, since a lower lithium content of the fluorite tailings increases additional processing costs, and increasing the lithium content of the fluorite tailings can further increase the lithium content of the leachate, it was determined to use fluorite tailings having a lithium content of greater than or equal to 0.3wt.% as a leaching aid.
In a possible embodiment, the leaching agent comprises: sulfuric acid.
In this example, sulfuric acid is used as the leaching agent to react with the valuable metals in the solid lithium-containing material to form soluble metal salts.
In a possible embodiment, the concentration of sulfuric acid in the leaching agent is 70-85% by mass.
In the embodiment, if the concentration of sulfuric acid in the leaching agent is low, valuable metals in the solid lithium-containing material are difficult to fully replace, and the reaction effect is poor; if the concentration of sulfuric acid in the leaching agent is higher, the corresponding processing risk is increased, sulfuric acid is easily enriched on the surface of the metal oxide, so that the reaction is difficult to continue, and harmful sulfur dioxide gas is easily generated under the high-temperature condition; therefore, the mass concentration of the sulfuric acid in the leaching agent is determined to be 70-85%, and in the leaching reaction process, the sulfuric acid is utilized to dilute heat production and chemical reaction heat, so that the consumption of steam heating is reduced, and the cost is further reduced.
In one possible embodiment, after the step of obtaining the valuable metal leaching solution after the solid-liquid separation in step S20, the method further includes:
s21, collecting leaching residues after solid-liquid separation, and adding water to wash the leaching residues to obtain a washing liquid;
mixing a solid lithium-containing material with a leaching agent and a leaching auxiliary agent, performing pressure leaching to obtain a leaching mixed solution, and performing solid-liquid separation on the leaching mixed solution to obtain valuable metal leaching solution and leaching residues; because valuable metal salts, a leaching agent and a leaching aid possibly are attached to the surface of the leaching slag, the leaching slag is collected, and the leaching slag is washed by adding water to obtain a washing liquid after washing the leaching slag.
And step S22, preparing the leaching agent by using the washing liquid.
The washing liquid is mixed with sulfuric acid to prepare the leaching agent.
Optionally, the mass ratio of sulfuric acid in the leaching agent to the washing liquid is (0.8-1.5): 0.2-0.5. The mass ratio of sulfuric acid in the leaching agent to the washing liquid is controlled to control the mass concentration of sulfuric acid in the leaching agent to be 70-85%, so that a higher leaching rate of valuable metals is obtained. For example, the mass ratio of sulfuric acid to the wash liquor in the leaching agent may be 0.8:0.2, 1:0.3, 1.2:0.4, 1.5:0.5, etc.
Optionally, the mass ratio of the solid lithium-containing material, sulfuric acid, the washing liquid and the leaching aid is 1 (0.8-1.5) (0.1-0.5) (0.2-0.5).
In this embodiment, the leaching residue after the solid-liquid separation is collected, and water is added to wash the leaching residue to obtain a washing solution, and the leaching agent is further configured by using the washing solution, so as to adjust the mass concentration of sulfuric acid in the leaching agent, and realize recycling of valuable metal salts, the leaching agent and the leaching aid attached to the surface of the leaching residue.
In a possible embodiment, the washing liquid is used to dilute the leaching mixture prior to solid-liquid separation of the leaching mixture.
Mixing the solid lithium-containing material with a leaching agent and a leaching aid, and carrying out pressure leaching to obtain a leaching mixed solution; the leaching mixed solution obtained after the leaching reaction is very thick, the solid content is close to 80%, so that direct solid-liquid separation is not facilitated, the acidity and the temperature of the mixture after leaching are high, the corrosion resistance requirement on equipment during solid-liquid separation is high, therefore, washing liquid is added into the leaching mixed solution for dilution, and solid-liquid separation is performed after dilution, so that valuable metal leaching solution is obtained; in addition, the washing liquid obtained by washing the leaching residue after solid-liquid separation can be directly used for dilution, so that the washing liquid can be reused.
In a possible embodiment, the leaching temperature of the pressure leaching is: 150-190 ℃.
In this embodiment, by increasing the leaching temperature, the occurrence of the leaching reaction is promoted; if the leaching temperature is too low, the leaching reaction is not facilitated, and the leaching rate of valuable metals is reduced; if the leaching temperature is too high, the leaching rate of valuable metals is not further improved, the required energy consumption is higher, and the cost is increased; the leaching temperature of the pressure leaching is thus determined as: 150-190 ℃.
Alternatively, the leaching temperature of the pressure leaching may be: 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ and the like.
In one possible embodiment, the leaching pressure is: 0.2-0.8Mpa.
In the embodiment, the leaching reaction is promoted by increasing the leaching pressure, and the reaction system can be stabilized to a certain extent, so that the fluctuation and the instability of the reaction are reduced; if the leaching pressure is lower, the leaching reaction is not facilitated, the leaching rate of valuable metals is reduced, and the leaching time is prolonged; if the leaching pressure is too high, the leaching rate of valuable metals is not further improved, the risk of the process operation with too high pressure is increased, and the requirement on the reaction vessel is also increased. The leaching pressure was thus determined as: 0.2-0.8Mpa.
Alternatively, the leaching pressure is 0.2Mpa, 0.3Mpa, 0.4Mpa, 0.5Mpa, 0.6Mpa, 0.7Mpa, 0.8Mpa, etc.
In one possible embodiment, the leaching time is: 0.5-3h.
In this embodiment, if the leaching time is too short, the valuable metals in the solid lithium-containing material are difficult to fully react and leach, so that the leaching rate of the valuable metals is reduced; if the leaching time is too long, the leaching rate of valuable metals is not obviously improved, but the time for process generation is prolonged; compared with the conventional leaching reaction, the leaching reaction time is greatly shortened by adding the leaching auxiliary agent and carrying out pressure leaching, so that the leaching time is only required to be 0.5-3h, and the process cost is reduced.
In a possible embodiment, the solid lithium-containing material comprises: one or more of lepidolite, beta-phase spodumene, lithange, petalite, waste aluminum electrolyte, waste lithium-containing glass frit and waste polishing powder.
In the embodiment, as the extraction method of the valuable metal in the solid lithium-containing material has higher leaching rate of the valuable metal and lower process cost, the processing adaptability to the solid lithium-containing material is improved, and the method can be suitable for different types of solid lithium-containing materials, particularly low-grade lithium-containing materials; the low-grade lithium-containing material has the advantages that as the proportion of effective elements (such as lithium) in the low-grade lithium-containing material to the total weight of the material is low, a large amount of materials are needed to extract a certain amount of effective elements, and the exploitation cost is high; the conventional valuable metal extraction method has higher process cost and poorer economic benefit after processing the low-grade lithium-containing material, so that the low-grade lithium-containing material is difficult to effectively utilize, and resource waste is caused; the method can obtain better economic benefit for extracting lithium and other valuable metals from the low-grade lithium-containing material, and has better adaptability to processing raw materials.
In a possible embodiment, the solid lithium-containing material is a finely ground lithium-containing material, and the solid lithium-containing material has a particle size distribution in which more than 200 mesh particles are greater than 50%.
In the embodiment, before leaching the solid lithium-containing material, grinding the solid lithium-containing material to obtain a ground lithium-containing material, wherein more than 200 meshes of particles in the particle size distribution of the solid lithium-containing material are more than 50%; through grinding the solid lithium-containing material, the particle size of the solid lithium-containing material is reduced, so that the contact area between reactants is increased, the reaction is more thorough, and the reaction rate is increased.
And S20, carrying out solid-liquid separation to obtain valuable metal leaching liquid.
And carrying out pressure leaching on the solid lithium-containing material, and then carrying out solid-liquid separation to obtain valuable metal leaching liquid.
Alternatively, the solid-liquid separation may be performed by filtration.
Optionally, the valuable metal leaching solution comprises: valuable metals such as lithium, potassium, aluminum, iron, rubidium, cesium, and the like.
In the embodiment, the solid lithium-containing material is mixed with the leaching agent and the leaching aid and subjected to pressure leaching, the leaching reaction is promoted by the aid of the pressure and the leaching aid, so that the processing adaptability to the solid lithium-containing material is enhanced, compared with a conventional wet process, the leaching rate of valuable metals is effectively improved by the aid of the pressure and the leaching aid, the leaching time is greatly shortened, and the extraction efficiency of the valuable metals is improved; and then directly obtaining valuable metal leaching liquid after solid-liquid separation, so as to realize the rapid and synchronous extraction of valuable metals in the solid lithium-containing material; the method adopts the full wet process, avoids the problem that sulfuric acid is decomposed and tail gas treatment is required due to the conventional high-temperature roasting process, reduces energy consumption and greatly reduces process cost; furthermore, due to the reduction of the process cost and the higher leaching rate of valuable metals, the method can obtain better economic benefit for extracting lithium and other valuable metals from the low-grade lithium-containing material, and has better adaptability to the processing raw materials.
Further, based on the first embodiment, a more complete embodiment of the extraction method of valuable metals in the solid lithium-containing material is provided, referring to fig. 2, the solid lithium-containing material is mixed with a leaching agent and a leaching aid, and is leached under pressure, so as to obtain a leaching mixed solution, wherein the leaching agent comprises: sulfuric acid and washing liquid obtained by washing leaching residues obtained by subsequent dilution and filtration with water; because the leaching mixed solution obtained after the leaching reaction is very thick and has higher acidity and temperature, the leaching mixed solution is diluted and then filtered and subjected to solid-liquid separation to obtain valuable metal leaching solution and leaching slag, thereby realizing the efficient extraction of valuable metals in the solid lithium-containing material. Further, since valuable metal salts, a leaching agent and a leaching aid may be further attached to the surface of the leaching slag, the leaching slag is collected, and the leaching slag is washed with water to obtain a washing liquid containing the valuable metal salts, the leaching agent and the leaching aid, wherein the washing liquid can be used for preparing the leaching agent and diluting the leaching mixed liquid.
In order that the details and operation of the above embodiments of the present application may be clearly understood by those skilled in the art, and that the advanced performance of the extraction method of valuable metals in solid lithium-containing materials of the embodiments of the present application may be significantly embodied, the above technical solutions are exemplified by a plurality of embodiments below.
Example 1
1) Grinding lepidolite, and sampling and detecting by using a 200-mesh screen to ensure that the 200-mesh passing rate of the ground lepidolite reaches more than 50%;
2) Mixing 100g of finely ground lepidolite, 19.4g of water, 110g of sulfuric acid and 10g of fluorite tailings, and carrying out pressure leaching reaction for 1.5h under the conditions that the reaction temperature is 160 ℃ and the reaction pressure is 0.5 MPa;
3) Adding 220g of water into the obtained leaching mixed solution for dilution after the leaching reaction is finished, cooling to below 80 ℃, and filtering to obtain valuable metal leaching solution and leaching residues;
wherein, the lithium element content in the valuable metal leaching solution is as follows: 3.4g/L, content of potassium element: 4.4g/L, aluminum element content: 23.0g/L, iron element content: 4.0g/L, rubidium element content: 1.0g/L, cesium element content: 0.3g/L and sodium element content of 1.0g/L; the leaching rates of lithium, potassium, aluminum, iron, rubidium and cesium reach 96.0%, 70.0%, 77.0%, 89.0%, 92.0% and 93.0% respectively;
4) Leaching residues are extracted, 300g of water is added for washing, and leaching residues with lithium oxide content lower than 0.05% and silicon dioxide content higher than 65% and washing liquid containing lithium are obtained, wherein the washing liquid can be returned to the step 2) for preparing a leaching agent and/or returned to the step 3) for diluting and leaching the mixed liquid;
5) Re-obtaining 100g of finely ground lepidolite, 30g of washing liquid, 110g of sulfuric acid and 10g of fluorite tailings, mixing, and carrying out pressure leaching reaction for 1.5h under the conditions that the reaction temperature is 160 ℃ and the reaction pressure is 0.5 MPa;
6) Adding 220g of washing liquid to dilute after the leaching reaction is finished, cooling to below 80 ℃, and filtering to obtain valuable metal leaching liquid and leaching slag;
wherein, the lithium element content in the valuable metal leaching solution is as follows: 3.6g/L, content of potassium element: 4.6g/L, aluminum element content: 23.2g/L, iron element content: 4.2g/L, rubidium element content: 1.2g/L, cesium element content: 0.5g/L and sodium element content of 1.2g/L; the leaching rates of lithium, potassium, aluminum, iron, rubidium and cesium respectively reach 97.0%, 71.0%, 78.0%, 90.0%, 93.0% and 94.0%.
Example 2
1) Grinding the waste lithium-containing glass material, and sampling and detecting by using a 200-mesh screen to ensure that the 200-mesh passing rate of the ground waste lithium-containing glass material reaches more than 50%;
2) Mixing 100g of ground waste lithium-containing glass frit, 20g of water, 80g of sulfuric acid and 20g of fluorite tailings, and carrying out pressure leaching reaction for 0.5h under the conditions that the reaction temperature is 190 ℃ and the reaction pressure is 0.7 MPa;
3) Adding 220g of water into the obtained leaching mixed solution for dilution after the leaching reaction is finished, cooling to below 80 ℃, and filtering to obtain valuable metal leaching solution and leaching residues;
wherein, the lithium element content in the valuable metal leaching solution is as follows: 4.1g/L, content of potassium element: 0.4g/L, aluminum element content: 10.8g/L, iron element content: 1.9g/L; the leaching rates of lithium, potassium, aluminum and iron respectively reach 95.0%, 70.0%, 77.0% and 90.0%;
4) Leaching residues are extracted, 300g of water is added for washing, and leaching residues with lithium oxide content lower than 0.05% and silicon dioxide content higher than 70% and washing liquid containing lithium are obtained, wherein the washing liquid can be returned to the step 2) for preparing leaching agents and/or returned to the step 3) for diluting and leaching mixed liquid;
5) Mixing 100g of ground waste lithium-containing glass frit, 20g of washing liquid, 80g of sulfuric acid and 20g of fluorite tailings, and carrying out pressure leaching reaction for 0.5h under the conditions that the reaction temperature is 190 ℃ and the reaction pressure is 0.7 MPa;
6) Adding 220g of washing liquid to dilute after the leaching reaction is finished, cooling to below 80 ℃, and filtering to obtain valuable metal leaching liquid and leaching slag;
wherein, the lithium element content in the valuable metal leaching solution is as follows: 4.3g/L, content of potassium element: 0.6g/L, aluminum element content: 11.0g/L, iron element content: 2.1g/L; the leaching rates of lithium, potassium, aluminum and iron respectively reach 96.0%, 71.0%, 80.0% and 92.0%.
Example 3
1) Grinding the waste aluminum electrolyte, and sampling and detecting by using a 200-mesh screen to ensure that the 200-mesh passing rate of the ground waste aluminum electrolyte reaches more than 50%;
2) Mixing 100g of ground waste aluminum electrolyte, 40g of water, 160g of sulfuric acid and 50g of fluorite tailings, and carrying out pressure leaching reaction for 2h under the conditions that the reaction temperature is 190 ℃ and the reaction pressure is 0.2 MPa;
3) Adding 220g of water into the obtained leaching mixed solution for dilution after the leaching reaction is finished, cooling to below 80 ℃, and filtering to obtain valuable metal leaching solution and leaching residues;
wherein, the lithium element content in the valuable metal leaching solution is as follows: 4.9g/L, content of potassium element: 0.6g/L, aluminum element content: 26.8g/L, iron element content: 1.7g/L; the leaching rates of lithium, potassium, aluminum and iron respectively reach 96.0%, 72.0%, 84.0% and 93.0%;
4) Leaching residues are extracted, 300g of water is added for washing, and leaching residues with lithium oxide content lower than 0.05% and silicon dioxide content higher than 70% and washing liquid containing lithium are obtained, wherein the washing liquid can be returned to the step 2) for preparing leaching agents and/or returned to the step 3) for diluting and leaching mixed liquid;
5) Mixing 100g of ground waste aluminum electrolyte, 60g of washing liquid, 140g of sulfuric acid and 50g of fluorite tailings, and carrying out pressure leaching reaction for 2h under the conditions that the reaction temperature is 190 ℃ and the reaction pressure is 0.2 MPa;
6) Adding 220g of washing liquid to dilute after the leaching reaction is finished, cooling to below 80 ℃, and filtering to obtain valuable metal leaching liquid and leaching slag;
wherein, the lithium element content in the valuable metal leaching solution is as follows: 5.1g/L, content of potassium element: 0.8g/L, aluminum element content: 27.0g/L, iron element content: 1.9g/L; the leaching rates of lithium, potassium, aluminum and iron respectively reach 98.0%, 73.0%, 85.0% and 94.0%.
Example 4
1) Grinding the lithium feldspar, and sampling and detecting by using a 200-mesh screen to ensure that the 200-mesh passing rate of the ground lithium feldspar reaches more than 50%;
2) Mixing 100g of ground lithium feldspar, 20g of water, 110g of sulfuric acid and 30g of fluorite tailings, and carrying out pressure leaching reaction for 3 hours under the conditions that the reaction temperature is 150 ℃ and the reaction pressure is 0.8 MPa;
3) Adding 220g of water for dilution after the leaching reaction is finished, cooling to below 80 ℃, and filtering to obtain valuable metal leaching liquid and leaching slag;
wherein, the content of lithium element in the leaching solution is as follows: 3.6g/L, content of potassium element: 4.0g/L, aluminum element content: 23.0g/L, iron element content: 1.4g/L; the leaching rates of lithium, potassium, aluminum and iron reach 95.0%, 70.0%, 77.0% and 89.0% respectively;
4) Leaching residues are extracted, 300g of water is added for washing, and leaching residues with lithium oxide content lower than 0.06% and silicon dioxide content higher than 70% and washing liquid containing lithium are obtained, wherein the washing liquid can be returned to the step 2) for preparing a leaching agent and/or returned to the step 3) for diluting and leaching the mixed liquid;
5) Mixing 100g of ground lithium feldspar, 20g of leaching solution, 110g of sulfuric acid and 30g of fluorite tailings, and carrying out pressure leaching reaction for 3 hours under the conditions that the reaction temperature is 150 ℃ and the reaction pressure is 0.8 MPa;
6) Adding 220g of leaching solution after the leaching reaction is finished, diluting, cooling to below 80 ℃, and filtering to obtain valuable metal leaching solution and leaching residues;
wherein, the content of lithium element in the leaching solution is as follows: 3.8g/L, content of potassium element: 4.2g/L, aluminum element content: 23.2g/L, iron element content: 1.6g/L; the leaching rates of lithium, potassium, aluminum and iron respectively reach 96.0%, 71.0%, 78.0% and 90.0%.
Comparative example 1
The experimental procedure and raw material ratios were the same as in example 1, except that: the leaching reaction pressure in steps 2) and 5) was 0.05MPa and the leaching reaction time was 6h.
Through the steps, the leaching rates of lithium, potassium, aluminum, iron, rubidium and cesium are respectively only: 85.0%, 60.1%, 68.3%, 84.6%, 84.8%, 85.6%.
Comparative example 2
The experimental procedure and raw material ratios were the same as in example 2, except that: and (3) no fluorite tailings are added in the steps 2) and 5).
Through the steps, the leaching rates of lithium, potassium, aluminum and iron are respectively only as follows: 60.0%, 50.6%, 70.0%, 82.6%.
According to the above examples 1 to 4 and comparative examples 1 to 2, the extraction method of valuable metals in the solid lithium-containing material of the present application has a larger improvement in the leaching rate of valuable metals than that of comparative examples 1 to 2; the pressurizing and leaching auxiliary agent is utilized to promote leaching reaction, so that the processing adaptability to solid lithium-containing materials is improved, the leaching time is shortened, and the extraction efficiency of valuable metals is improved; the full wet process is adopted, so that the problems of sulfuric acid decomposition and tail gas treatment required in the conventional high-temperature roasting process are avoided, the energy consumption is reduced, the process cost is greatly reduced, better economic benefits can be obtained for extracting lithium and other valuable metals from low-grade lithium-containing materials, and the method has better adaptability to processing raw materials.
The foregoing is merely a preferred embodiment of the present application and is not intended to limit the scope of the patent application, but rather, various modifications and variations can be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the scope of the patent protection of the present application.
Claims (10)
1. The extraction method of the valuable metal in the solid lithium-containing material is characterized by comprising the following steps of:
mixing the solid lithium-containing material with a leaching agent and a leaching auxiliary agent, and carrying out pressure leaching to obtain a leaching mixed solution;
and carrying out solid-liquid separation on the leaching mixed liquid to obtain valuable metal leaching liquid.
2. The method for extracting valuable metals from solid lithium-containing materials according to claim 1, wherein the mass ratio of the solid lithium-containing materials, the leaching agent and the leaching aid is 1 (1-2): 0.1-0.5.
3. The method for extracting valuable metals from solid lithium-containing materials according to claim 1 or 2, wherein the leaching aid comprises: a fluorite tailings having a lithium content of greater than or equal to 0.3wt.%.
4. The method for extracting valuable metals from solid lithium-containing materials according to claim 1 or 2, wherein the leaching agent comprises: sulfuric acid.
5. The method for extracting valuable metals from solid lithium-containing materials as claimed in claim 4, wherein the sulfuric acid in the leaching agent is 70-85 wt.%.
6. The method for extracting valuable metals from solid lithium-containing materials as claimed in claim 4, further comprising, after the step of obtaining the valuable metal leaching solution after the solid-liquid separation:
collecting leaching residues after the solid-liquid separation, and adding water to wash the leaching residues to obtain washing liquid;
the leaching agent is prepared by the washing liquid.
7. The method of extracting metal values from a solid lithium-containing material of claim 6, wherein said wash solution is used to dilute said leaching mixture prior to solid-liquid separation of said leaching mixture.
8. The method for extracting valuable metals from solid lithium-containing materials as claimed in claim 1, wherein the leaching temperature of the pressure leaching is: the leaching pressure is 150-190 ℃, and the leaching pressure is: the leaching time is 0.2-0.8 Mpa: 0.5-3h.
9. The method for extracting valuable metals from a solid lithium-containing material according to claim 1, wherein the solid lithium-containing material comprises: one or more of lepidolite, beta-phase spodumene, lithange, petalite, waste aluminum electrolyte, waste lithium-containing glass frit and waste polishing powder.
10. The method of extracting metal values from a solid lithium-containing material of claim 1 or 9, wherein the solid lithium-containing material is a finely ground lithium-containing material, and wherein more than 200 mesh particles in the particle size distribution of the solid lithium-containing material are greater than 50%.
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