CN115786732A - Method for extracting lithium resource from clay type lithium ore - Google Patents
Method for extracting lithium resource from clay type lithium ore Download PDFInfo
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- CN115786732A CN115786732A CN202211415191.9A CN202211415191A CN115786732A CN 115786732 A CN115786732 A CN 115786732A CN 202211415191 A CN202211415191 A CN 202211415191A CN 115786732 A CN115786732 A CN 115786732A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 131
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000004927 clay Substances 0.000 title claims abstract description 22
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 70
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000002386 leaching Methods 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012045 crude solution Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 34
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 30
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 30
- 239000003463 adsorbent Substances 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 15
- 238000000108 ultra-filtration Methods 0.000 claims description 13
- 238000001728 nano-filtration Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 238000001223 reverse osmosis Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000011001 backwashing Methods 0.000 claims description 6
- 238000010981 drying operation Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 238000000605 extraction Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 22
- 238000005374 membrane filtration Methods 0.000 description 22
- 238000012360 testing method Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- -1 iron ion Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001234 light alloy Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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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
- 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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Abstract
The invention relates to the technical field of lithium extraction, and discloses a method for extracting lithium resources from clay type lithium ores, which comprises the following steps: step S1: sequentially carrying out crushing operation and ball milling operation on the clay type lithium ore to obtain ore powder; the particle size of the ore powder is 50-300 meshes; step S2: mixing and stirring the ore powder and concentrated sulfuric acid at the temperature of 250-300 ℃, and keeping for 1-3 hours to obtain a lithium sulfate mixture; the mass ratio of the ore powder to the concentrated sulfuric acid is (1; and step S3: and (3) sequentially carrying out water washing operation and filtering operation on the mixture to obtain a dilute lithium sulfate crude solution. The method is simpler to operate, more environment-friendly, lower in cost, higher in lithium leaching rate and higher in lithium yield.
Description
Technical Field
The invention relates to the technical field of lithium extraction, in particular to a method for extracting lithium resources from clay type lithium ores.
Background
Lithium is a typical, new century green energy and ideal material of light alloy, and the application field is wide. With the rapid increase of the consumption of lithium ion batteries in industries such as new technology and new energy automobiles, the consumption of lithium in the new technology industry is increasing at a high speed, and the trend puts new requirements on the supply of lithium ore resources and low-cost lithium extraction methods all around the world. In recent years, a large amount of clay type lithium ore resources are discovered in southwest areas of China, and the clay type lithium ores are also called as sedimentary lithium ores or unconventional lithium ores and have the characteristics of wide distribution and large reserves, but the average Li 2 The grade of O is low, generally 0.3-0.8%, and the enrichment and recovery of lithium cannot be realized by adopting the conventional beneficiation method.
The concentrated sulfuric acid leaching method is the method for extracting lithium resources from clay type lithium ores, which is the lowest in cost, the simplest in operation and high in leaching rate at present. For example, chinese patent CN202010472603.7 discloses a method for efficiently leaching lithium from lithium-containing claystone. Crushing raw ores, adding the crushed raw ores into a rod mill, grinding, filtering, drying, scattering, uniformly mixing according to the ratio of a sample to concentrated sulfuric acid, putting the mixture into a muffle furnace for heat preservation, taking out the sample, naturally cooling, scattering, stirring and leaching according to the ratio of the sample to water, and filtering after stirring to obtain a leaching solution. However, the adding amount of concentrated sulfuric acid adopted by the method is 60-80% of the total amount of raw ore, the discharge amount of concentrated sulfuric acid waste water is large, the requirement on corrosion resistance of equipment is high, and the environmental protection pressure is large; and the obtained leachate has low lithium content and contains a large amount of impurities such as aluminum, magnesium, potassium and the like.
Therefore, there is a need to improve the existing concentrated sulfuric acid leaching method to obtain a method for extracting lithium resources from clay-type lithium ores, which is simpler in operation, more environment-friendly, lower in cost, higher in lithium leaching rate and higher in lithium yield.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for extracting lithium resources from clay type lithium ores, which is simpler to operate, more environment-friendly, lower in cost, higher in lithium leaching rate and higher in lithium yield.
The purpose of the invention is realized by the following technical scheme:
a method for extracting lithium resources from clay type lithium ores comprises the following steps:
step S1: sequentially carrying out crushing operation and ball milling operation on clay type lithium ore to obtain ore powder; the particle size of the ore powder is 50-300 meshes.
Through research and test, the inventor finds that when the particle size of the ore powder is 50-300 meshes, the leaching rate of lithium and the comprehensive yield of lithium are high; increasing the particle size of the ore powder decreases the leaching rate of lithium and the overall yield of lithium.
Step S2: mixing and stirring the ore powder and concentrated sulfuric acid at the temperature of 250-300 ℃, and keeping for 1-3 hours to obtain a lithium sulfate mixture; the mass ratio of the ore powder to the concentrated sulfuric acid is (1. The concentrated sulfuric acid is concentrated sulfuric acid with the concentration of 98%. At this time, the lithium oxide in the ore powder is converted into lithium sulfate which is soluble in water under the condition of heating by strong acid, and the reaction equation is as follows:
Li 2 O+H 2 SO 4 →Li 2 SO 4 +H 2 O
through research and test, the inventor finds that when the adding amount of concentrated sulfuric acid is 25-35% of the total amount of the ore powder, and the reaction temperature is 250-300 ℃, the leaching rate of lithium and the comprehensive yield of lithium are high; if the adding amount of concentrated sulfuric acid is continuously reduced, the leaching rate of lithium and the comprehensive yield of lithium are obviously reduced; if the reaction temperature is further lowered, the leaching rate of lithium and the overall yield of lithium are also significantly lowered.
And step S3: and (3) sequentially carrying out water washing operation and filtering operation on the mixture to obtain a dilute lithium sulfate crude solution.
In one embodiment, the water washing operation in step S3 includes the following steps: according to the lithium sulfate mixture: pure water = (1:2) - (1:5) by mass, putting the lithium sulfate mixture into pure water, stirring for 1-3 h, and filtering to obtain dilute lithium sulfate crude solution and filter residue; filtering residues: pure water = (1:1) - (1:3) by mass ratio, and washing was performed with stirring to obtain washing water.
In one embodiment, the method further includes step S4: and adjusting the pH value of the dilute lithium sulfate crude solution to 6-9 by adopting a sodium hydroxide solution, and circularly adsorbing by adopting a lithium adsorbent until the lithium adsorbent is saturated.
In one embodiment, the method further includes step S5: and (5) backwashing the lithium adsorbent by adopting the washing water obtained in the step (S3) to obtain a primary lithium sulfate solution.
Through research and test, the inventor finds that the lithium yield can be improved by carrying out backwashing operation on the lithium adsorbent by using the washing water in the step S3.
In one embodiment, the method further includes step S6: and sequentially filtering the preliminary lithium sulfate solution by using an ultrafiltration membrane, a reverse osmosis membrane and a nanofiltration membrane to obtain a refined lithium sulfate solution. Wherein, the ultrafiltration membrane filtration is mainly used for removing solid impurity particles in the primary lithium sulfate solution; the reverse osmosis membrane filtration is mainly used for removing macromolecular impurity ions in the preliminary lithium sulfate solution and improving the lithium concentration; the nanofiltration membrane filtration is mainly used for removing divalent and trivalent metal impurity ions in the primary lithium sulfate solution: calcium ion, magnesium ion, iron ion, aluminum ion, and the like.
The inventor discovers through research and test that the ultrafiltration membrane filtration, the reverse osmosis membrane filtration and the nanofiltration membrane filtration are sequentially adopted for the preliminary lithium sulfate solution according to the method in the step S6, the filtration and purification effects are better than those of the ultrafiltration membrane filtration, the reverse osmosis membrane filtration or the nanofiltration membrane filtration which are independently adopted, and the filtration and purification effects are better than those of any two filtration and purification effects which are used in combination.
In one embodiment, the method further includes step S7: evaporating and concentrating the refined lithium sulfate solution until the concentration of lithium sulfate is 10-20%, keeping the temperature at 90-100 ℃, and mixing the lithium sulfate: sodium carbonate = (1; the reaction equation is as follows:
2Li + +Na 2 CO 3 →Li 2 CO 3 ↓+2Na +
in one embodiment, the method further includes step S8: separating the lithium carbonate mixture by using a centrifugal machine to obtain lithium carbonate precipitate; and sequentially carrying out hot pure water leaching operation and drying operation on the lithium carbonate precipitate to obtain a lithium carbonate product meeting the national standard.
Compared with the prior art, the invention has at least the following advantages:
the invention provides a method for extracting lithium resources from clay type lithium ores, which is simpler to operate and lower in cost; the consumption of strong acid is less, the corrosivity to equipment is reduced, the discharge of strong acid wastewater is reduced, the environment is protected, and the environment pollution is avoided; the purification effect is good, and a lithium carbonate product meeting the national standard can be obtained; the extraction rate of the lithium element is up to more than 95%, the comprehensive yield of the lithium element is up to more than 85%, the waste of lithium resources is reduced, and the economic benefit is high.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a process flow chart of a method for extracting lithium resources from clay-type lithium ores according to example 1.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete. All the raw materials and reagents used in the present invention are commercially available raw materials and reagents, unless otherwise specified. In the examples, the amounts of the components are g and mL in parts by mass and volume.
Example 1
A method for extracting lithium resources from clay type lithium ores comprises the following steps:
step S1: sequentially carrying out crushing operation and ball milling operation on the clay type lithium ore to obtain ore powder; the particle size of the mineral powder is 50 meshes.
Step S2: mixing and stirring the ore powder and 98% concentrated sulfuric acid at the temperature of 250 ℃, and keeping for 1h to obtain a lithium sulfate mixture; the mass ratio of the ore powder to the concentrated sulfuric acid is 1.
And step S3: and (3) sequentially carrying out water washing operation and filtering operation on the mixture to obtain a dilute lithium sulfate crude solution. The water washing operation in step S3 includes the steps of: according to the lithium sulfate mixture: pure water =1:2, the lithium sulfate mixture is put into pure water, stirred for 1 hour and filtered to obtain dilute lithium sulfate crude solution and filter residue; filtering residues: pure water =1:3 by mass ratio, and washing was performed with stirring to obtain washing water.
And step S4: and adjusting the pH value of the dilute lithium sulfate crude solution to 6 by using a sodium hydroxide solution, and circularly adsorbing by using a lithium adsorbent until the lithium adsorbent is saturated. Wherein, lithium adsorbent manufacturer: lan Xiao technology, lithium adsorbent model: seplite @ LX-Li, introduction of lithium adsorbent: the material is prepared by sintering high-activity alumina and nano lithium materials, and has high selectivity on lithium ions. Can selectively adsorb lithium ions in a low-concentration solution (the lithium ions can be adsorbed when the concentration is more than 50 ppm). The lithium adsorption capacity can reach 3mg/g, the lithium can be desorbed by water washing after adsorption saturation, diluted acid is not needed, and the method is environment-friendly and pollution-free. The annual loss is less than 10 percent, and the method has extremely high economic benefit.
Step S5: and (5) backwashing the lithium adsorbent by adopting the washing water obtained in the step (S3) to obtain a primary lithium sulfate solution.
Step S6: and sequentially filtering the preliminary lithium sulfate solution by using an ultrafiltration membrane, a reverse osmosis membrane and a nanofiltration membrane to obtain a refined lithium sulfate solution.
Step S7: evaporating and concentrating the refined lithium sulfate solution until the concentration of lithium sulfate is 10%, keeping the temperature at 90 ℃, and mixing the lithium sulfate: sodium carbonate = 1.1, and the sodium carbonate solution was added and stirred for 2h to obtain a lithium carbonate mixture.
Step S8: separating the lithium carbonate mixture by using a centrifugal machine to obtain lithium carbonate precipitate; and sequentially carrying out hot pure water leaching operation and drying operation on the lithium carbonate precipitate to obtain a lithium carbonate product.
And (3) testing results: the lithium content of the dilute lithium sulfate crude solution obtained in the step S3 of the embodiment 1 is measured, the leaching rate of lithium is calculated, the leaching rate of lithium in the embodiment is calculated to be more than 95%, the comprehensive yield of lithium in the whole process is more than 85%, and the purity of the lithium carbonate product obtained in the step S8 is more than 99%.
Example 2
A method for extracting lithium resources from clay type lithium ores comprises the following steps:
step S1: sequentially carrying out crushing operation and ball milling operation on the clay type lithium ore to obtain ore powder; the particle size of the mineral powder is 300 meshes.
Step S2: mixing and stirring the ore powder and 98% concentrated sulfuric acid at the temperature of 300 ℃, and keeping for 3 hours to obtain a lithium sulfate mixture; the mass ratio of the ore powder to the concentrated sulfuric acid is 1.
And step S3: and (3) sequentially carrying out water washing operation and filtering operation on the mixture to obtain a dilute lithium sulfate crude solution. The water washing operation in step S3 includes the steps of: according to the lithium sulfate mixture: pure water =1:5, the lithium sulfate mixture is put into pure water, stirred for 3 hours and filtered to obtain dilute lithium sulfate crude solution and filter residue; filtering residues: pure water =1:1 by mass ratio, and washing was performed with stirring to obtain washing water.
And step S4: and adjusting the pH value of the dilute lithium sulfate crude solution to 9 by using a sodium hydroxide solution, and circularly adsorbing by using a lithium adsorbent until the lithium adsorbent is saturated.
Step S5: and (5) backwashing the lithium adsorbent by adopting the washing water obtained in the step (S3) to obtain a primary lithium sulfate solution.
Step S6: and sequentially filtering the preliminary lithium sulfate solution by using an ultrafiltration membrane, a reverse osmosis membrane and a nanofiltration membrane to obtain a refined lithium sulfate solution.
Step S7: evaporating and concentrating the refined lithium sulfate solution until the concentration of lithium sulfate is 20%, keeping the temperature at 100 ℃, and mixing the lithium sulfate: sodium carbonate = 1.3, and the sodium carbonate solution was added and stirred for 0.5h to obtain a lithium carbonate mixture.
Step S8: separating the lithium carbonate mixture by using a centrifugal machine to obtain lithium carbonate precipitate; and sequentially carrying out hot pure water leaching operation and drying operation on the lithium carbonate precipitate to obtain a lithium carbonate product.
And (3) testing results: the lithium content of the dilute lithium sulfate crude solution obtained in step S3 of example 2 is measured, and the leaching rate of lithium is calculated, so that the leaching rate of lithium in the present embodiment is calculated to be more than 95%, the comprehensive yield of lithium in the whole process is more than 85%, and the purity of the lithium carbonate product obtained in step S8 is more than 99%.
Example 3
A method for extracting lithium resources from clay type lithium ores comprises the following steps:
step S1: sequentially carrying out crushing operation and ball milling operation on the clay type lithium ore to obtain ore powder; the particle size of the mineral powder is 180 meshes.
Step S2: mixing and stirring the ore powder and 98% concentrated sulfuric acid at the temperature of 280 ℃, and keeping for 2 hours to obtain a lithium sulfate mixture; the mass ratio of the ore powder to the concentrated sulfuric acid is 1.
And step S3: and (3) sequentially carrying out water washing operation and filtering operation on the mixture to obtain a dilute lithium sulfate crude solution. The water washing operation in step S3 includes the steps of: according to the lithium sulfate mixture: pure water =1, 3.5, adding the lithium sulfate mixture into pure water, stirring for 2 hours, and filtering to obtain a dilute lithium sulfate crude solution and filter residue; filtering residues: pure water =1:2 by mass ratio, and washing was performed with stirring to obtain washing water.
And step S4: and adjusting the pH value of the dilute lithium sulfate crude solution to 7.5 by using a sodium hydroxide solution, and circularly adsorbing by using a lithium adsorbent until the lithium adsorbent is saturated.
Step S5: and (5) backwashing the lithium adsorbent by adopting the washing water obtained in the step (S3) to obtain a primary lithium sulfate solution.
Step S6: and sequentially filtering the preliminary lithium sulfate solution by using an ultrafiltration membrane, a reverse osmosis membrane and a nanofiltration membrane to obtain a refined lithium sulfate solution.
Step S7: evaporating and concentrating the refined lithium sulfate solution until the concentration of lithium sulfate is 15%, keeping the temperature at 95 ℃, and mixing the lithium sulfate: sodium carbonate = 1.2 molar ratio sodium carbonate solution was added and stirred for 1h to obtain a lithium carbonate mixture.
Step S8: separating the lithium carbonate mixture by using a centrifugal machine to obtain lithium carbonate precipitate; and sequentially carrying out hot pure water leaching operation and drying operation on the lithium carbonate precipitate to obtain a lithium carbonate product.
And (3) testing results: the lithium content of the dilute lithium sulfate crude solution obtained in step S3 of example 3 is measured, and the leaching rate of lithium is calculated, so that the leaching rate of lithium in the present embodiment is calculated to be more than 95%, the comprehensive yield of lithium in the whole process is more than 85%, and the purity of the lithium carbonate product obtained in step S8 is more than 99%.
Comparative example 1
Comparative example 1 is different from example 3 in that the ore powder in the S1 step has a particle size of 400 mesh.
And (3) testing results: in the comparative example 1, the leaching rate of lithium is reduced by 15.2%, and the comprehensive yield of lithium in the whole process is reduced by 13.6%.
Comparative example 2
Comparative example 2 is different from example 3 in that the lithium adsorbent is backwashed with pure water.
And (3) testing results: comparative example 2 the overall yield of lithium in the full run was reduced by 4.9%.
Comparative example 3
Comparative example 3 differs from example 3 in that concentrated sulfuric acid is added in an amount of 20% by mass of the ore powder in step S2.
And (3) testing results: in comparative example 3, the leaching rate of lithium is reduced by 14.8%, and the comprehensive yield of lithium in the whole process is reduced by 13.4%.
Comparative example 4
Comparative example 4 differs from example 3 in that the temperature in step S2 is 200 ℃.
And (3) testing results: in comparative example 4, the leaching rate of lithium is reduced by 10.7%, and the comprehensive yield of lithium in the whole process is reduced by 9.3%.
Comparative example 5
Comparative example 5 is different from example 3 in that step S6 employs only ultrafiltration membrane filtration and reverse osmosis membrane filtration.
And (3) testing results: the purity of the lithium carbonate product of step S8 in comparative example 5 decreased by 11.5%.
Comparative example 6
Comparative example 6 differs from example 3 in that step S6 employs only ultrafiltration membrane filtration and nanofiltration membrane filtration.
And (3) testing results: the purity of the lithium carbonate product of step S8 in comparative example 6 decreased by 3.2%.
To sum up, the test results were analyzed: according to the test results, the leaching rate of lithium in the clay type lithium ore can reach more than 95%, the comprehensive yield of lithium in the whole process can reach more than 85%, the purity of the obtained lithium carbonate product can reach more than 99%, the good extraction and recovery of lithium resources in the clay type lithium ore are realized, the waste of the lithium resources is reduced, and the economic benefit is high.
However, according to comparative example 1, the leaching rate of lithium and the overall yield of lithium were significantly reduced by increasing the particle size of the ore powder as compared with example 3. According to comparative example 2, the lithium adsorbent is backwashed using the washing water of step S3, and the yield of lithium can be improved, compared to example 3. Compared with the example 3 according to the comparative examples 3 and 4, if the adding amount of concentrated sulfuric acid is reduced, the leaching rate of lithium and the comprehensive yield of lithium are obviously reduced; when the reaction temperature is lowered, the leaching rate of lithium and the overall yield of lithium are also remarkably lowered. Compared with the embodiment 3 according to the comparative examples 5 and 6, the combined use of the ultrafiltration membrane filtration, the reverse osmosis membrane filtration and the nanofiltration membrane filtration has better purification effect than the combined use of any two of the ultrafiltration membrane filtration, the reverse osmosis membrane filtration and the nanofiltration membrane filtration, and the ultrafiltration membrane filtration, the reverse osmosis membrane filtration and the nanofiltration membrane filtration have good synergistic effect.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (7)
1. A method for extracting lithium resources from clay type lithium ores is characterized by comprising the following steps:
step S1: sequentially carrying out crushing operation and ball milling operation on the clay type lithium ore to obtain ore powder; the particle size of the ore powder is 50-300 meshes;
step S2: mixing and stirring the ore powder and concentrated sulfuric acid at the temperature of 250-300 ℃, and keeping for 1-3 hours to obtain a lithium sulfate mixture; the mass ratio of the ore powder to the concentrated sulfuric acid is (1;
and step S3: and (3) sequentially carrying out water washing operation and filtering operation on the mixture to obtain a dilute lithium sulfate crude solution.
2. The method for extracting lithium resources from clay-type lithium ores as claimed in claim 1, wherein the water washing operation in the step S3 comprises the steps of: according to the lithium sulfate mixture: pure water = (1:2) - (1:5) by mass, putting the lithium sulfate mixture into pure water, stirring for 1-3 h, and filtering to obtain dilute lithium sulfate crude solution and filter residue; filtering residues: pure water = (1:1) - (1:3) by mass ratio, and washing was performed with stirring to obtain washing water.
3. The method for extracting lithium resources from clay-type lithium ores as claimed in claim 2, further comprising the step S4: and adjusting the pH value of the dilute lithium sulfate crude solution to 6-9, and circularly adsorbing by using a lithium adsorbent until the lithium adsorbent is saturated.
4. The method of claim 3, further comprising the step S5: and (5) backwashing the lithium adsorbent by adopting the washing water obtained in the step (S3) to obtain a primary lithium sulfate solution.
5. The method for extracting lithium resources from clay-type lithium ores as claimed in claim 4, further comprising the step S6: and sequentially filtering the preliminary lithium sulfate solution by using an ultrafiltration membrane, a reverse osmosis membrane and a nanofiltration membrane to obtain a refined lithium sulfate solution.
6. The method for extracting lithium resources from clay-type lithium ores as claimed in claim 5, further comprising the step S7: evaporating and concentrating the refined lithium sulfate solution until the concentration of lithium sulfate is 10-20%, keeping the temperature at 90-100 ℃, and mixing the lithium sulfate: sodium carbonate = (1.
7. The method of claim 6, further comprising the step S8: separating the lithium carbonate mixture by using a centrifugal machine to obtain lithium carbonate precipitate; and sequentially carrying out hot pure water leaching operation and drying operation on the lithium carbonate precipitate to obtain a lithium carbonate product.
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