CN115161496A - Method for extracting lithium from lithium clay - Google Patents
Method for extracting lithium from lithium clay Download PDFInfo
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- CN115161496A CN115161496A CN202210741423.3A CN202210741423A CN115161496A CN 115161496 A CN115161496 A CN 115161496A CN 202210741423 A CN202210741423 A CN 202210741423A CN 115161496 A CN115161496 A CN 115161496A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 226
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 219
- 238000000034 method Methods 0.000 title claims abstract description 76
- 239000004927 clay Substances 0.000 title claims abstract description 69
- 238000002386 leaching Methods 0.000 claims abstract description 181
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 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 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011591 potassium Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 62
- 239000011780 sodium chloride Substances 0.000 claims description 31
- 239000002734 clay mineral Substances 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 238000005342 ion exchange Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 25
- 239000000203 mixture Substances 0.000 description 14
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 229910003251 Na K Inorganic materials 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000009616 inductively coupled plasma Methods 0.000 description 7
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 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 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052629 lepidolite Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910052642 spodumene Inorganic materials 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- -1 fluorine ions Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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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
-
- 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
-
- 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
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for extracting lithium from lithium clay, which comprises the steps of roasting lithium clay powder, grinding roasted clinker, mixing the grinded roasted clinker with a leaching agent and water, leaching at the temperature of 150-300 ℃ and under the pressure of 1.4-2.5MPa, carrying out solid-liquid separation to obtain a lithium-containing solution and leaching residues, wherein the leaching agent is at least one of sodium hydroxide, potassium hydroxide, a strong acid salt of sodium or a strong acid salt of potassium, adding a proper amount of the leaching agent into the lithium-containing solution, returning the lithium-containing solution to step S2 for cyclic leaching, and carrying out cyclic leaching for a plurality of times according to the process to obtain a lithium-rich solution. The invention is based on Li in lithium clay ore under high temperature and high pressure + In the same leaching agent as Na + /K + The selective leaching of lithium in the lithium clay is realized by the ion exchange effect between the two, and meanwhile, certain inert ore types in the clay ore are subjected to crystal form conversion by high-temperature roasting, so that the compatibility of the process is improved, and the leached lithium liquidThe recycling of the lithium ion battery is beneficial to improving the lithium concentration and reducing the dosage of the leaching agent.
Description
Technical Field
The invention belongs to the technical field of lithium extraction from lithium ore, and particularly relates to a method for extracting lithium from lithium clay.
Background
With the rapid popularization of lithium ion batteries, lithium is increasingly receiving industrial attention as a key element in the lithium ion batteries, and lithium salt products represented by lithium carbonate and lithium hydroxide are already in short supply and short supply in the market and are high in price. Therefore, further development of lithium resources is urgently required.
At present, lithium salt products in the market mainly come from spodumene lithium extraction, lepidolite lithium extraction, salt lake lithium extraction and lithium recovery in retired lithium ion batteries, lithium clay is neglected once because of low lithium oxide grade, and along with the deep development of mineral exploration work in recent years, many large-scale lithium clay minerals are found at home and abroad, the equivalent weight of lithium carbonate is more than megaton grade, and the reserve is very considerable. Compared with the spodumene and lepidolite ores which are very limited, gradually exhausted and high in price, the clay ore has development prospect in mining and smelting.
Aiming at the recovery of lithium in lithium clay, the related lithium extraction technology in China is very limited at present. Patent CN 110358931A discloses a method for extracting lithium in carbonate clay type lithium ore by an ion exchange method, which realizes leaching of lithium by ferric iron salt and roasted clay clinker in an ion exchange mode at 85 ℃, but the leaching rate is low, the consumption of iron salt is high, and the industrialization difficulty is high; patent CN202010684178.8 discloses a method for extracting lithium from lithium-containing clay, which comprises roasting ball-milled lithium clay, calcium carbonate, sodium sulfate and potassium sulfate in a certain proportion, crushing and leaching to obtain a lithium-containing solution, wherein a large amount of calcium-silicon waste residues are generated by the method and are difficult to process, the content of lithium oxide in the residues reaches 0.2%, and the method is only suitable for clay ores with high lithium oxide grade; patent CN201410098348.9 discloses a method for extracting lithium from low-grade lithium-containing clay ore, which provides a new process of 'modified roasting-dump leaching', but calcium fluoride is introduced in the roasting process, fluorine ions have high corrosivity on equipment, and the generated hydrogen fluoride also has pollution on the atmosphere.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. Therefore, the invention provides a method for extracting lithium from lithium clay, which has the advantages of simple process, high leaching rate of lithium and wide application prospect.
According to one aspect of the invention, a method for extracting lithium from lithium clay is provided, which comprises the following steps:
s1: roasting the lithium clay powder to obtain roasted clinker;
s2: grinding the roasted clinker, mixing the ground roasted clinker with a leaching agent and water, leaching at the temperature of 150-300 ℃ and under the pressure of 1.4-2.5MPa, and performing solid-liquid separation to obtain a lithium-containing solution and leaching residues; the leaching agent is at least one of sodium hydroxide, potassium hydroxide, sodium strong acid salt or potassium strong acid salt;
s3: and adding a proper amount of the leaching agent into the lithium-containing solution, then returning to the step S2 for circular leaching, and circularly leaching for a plurality of times according to the process to obtain a lithium-rich solution.
In some embodiments of the present invention, in step S1, the lithium content of the lithium clay powder is 0.1 to 0.5wt%.
In some embodiments of the invention, in step S1, the lithium clay powder comprises at least one of carbonate type clay mineral, volcanic type clay mineral, or Gu Daer lithium boron mineral.
In some embodiments of the present invention, in step S1, the particle size of the lithium clay powder is 50-400 mesh. Preferably, the particle size of the lithium clay powder is 100-200 meshes.
In some embodiments of the invention, the temperature of the firing in step S1 is 400 to 1200 ℃. Preferably, the temperature of the roasting is 500-800 ℃.
In some embodiments of the present invention, in step S1, the calcination time is 1 to 5 hours. Preferably, the roasting time is 2-3h.
In some embodiments of the invention, in step S2, the molar ratio of the metallic element in the leaching agent to the lithium in the roasting clinker is (1-10): 1. preferably, the molar ratio of the metal element in the leaching agent to the lithium in the roasting clinker is (2-5): 1.
in some embodiments of the invention, in step S2, the strong acid salt of sodium is selected from at least one of sodium sulfate or sodium chloride; the strong acid salt of potassium is at least one of potassium sulfate or potassium chloride.
In some preferred embodiments of the present invention, in step S2, the temperature of the leaching is 200 to 250 ℃ and the pressure is 1.8 to 2.2MPa.
In some embodiments of the invention, the leaching time in step S2 is 1-12h. Preferably, the leaching time is 2-6h.
In some embodiments of the invention, in step S2, the solid-to-liquid ratio of the clinker to water is 1: (2-10) g/L. Preferably, the solid-to-liquid ratio of the roasting clinker to water is 1: (2-4) g/L.
In some embodiments of the invention, the number of cycles of leaching in step S3 is 2-5 (first from the start of the first leaching).
In some embodiments of the invention, in step S3, the concentration of lithium in the lithium-rich solution is 0.5 to 10g/L.
According to a preferred embodiment of the invention, at least the following advantages are achieved:
1. the invention is based on Li in lithium clay ore under high temperature and high pressure + In the same leaching agent as Na + /K + The ion exchange effect between the two components realizes the selective leaching of lithium in the lithium clay, a solid-liquid reaction system is adopted under high pressure, the reaction kinetics is high, the ion exchange process of the roasted lithium clay and sodium/potassium salt can be directly realized, and experiments prove that the invention can realize more than 90 percent of the ion exchange process at the temperature of 150-300 ℃ and the pressure of 1.4-2.5MPaAnd (4) leaching rate of lithium. Meanwhile, through high-temperature roasting, certain inert ore types in the clay ore are subjected to crystal form conversion, the compatibility of the process is improved, the granularity of the materials is effectively reduced through grinding the roasted clinker, the reaction rate in the high-pressure leaching process is favorably improved, the leached lithium liquid is recycled, the concentration of lithium is favorably improved, and the using amount of a leaching agent is reduced. In general, the method for extracting lithium from lithium-containing clay at high temperature and high pressure, which is provided by the invention, has the advantages of simple process, strong compatibility, higher leaching rate of lithium and application prospect.
2. According to the invention, sodium/potassium hydroxide or sodium/potassium strong acid salt is used as a leaching agent, compared with Ca and Mg, the ionic radii of Na and K are smaller, the ion exchange kinetics is higher, the difficulty of subsequent lithium solution recovery caused by the introduction of Ca and Mg is avoided, and the subsequent impurity removal cost is reduced. Compared with weak acid salt, the strong acid salt is easy to dissolve, and the safety risk caused by hydrolysis and decomposition of the leaching agent under high temperature and high pressure is avoided.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a process flow diagram of example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts are within the protection scope of the present invention based on the embodiments of the present invention.
Example 1
A method for extracting lithium from lithium clay, referring to fig. 1, the specific process is as follows:
s1: crushing lithium-containing clay to 100 meshes by using a crusher (raw ore components are shown in table 1);
s2: roasting the obtained crushed material at 500 ℃ for 3h;
s3: grinding the obtained roasting clinker by using a ball mill, taking 500g of ground powder, adding water and sodium chloride, wherein the liquid-solid ratio of the water to the roasting clinker is 3:1L/g, the dosage of sodium chloride is as follows: li =3:1, and reacting for 4 hours in a high-temperature high-pressure reaction kettle at 200 ℃ and the reaction pressure of 1.6-2.0MPa;
s4: and (3) performing solid-liquid separation on the reacted slurry to obtain a lithium-containing solution and leaching residues, wherein the lithium solution leached for the first time is named as a primary lithium leaching solution, and the primary lithium leaching solution is prepared according to the proportion of Na: and Li =3:1 supplemented with sodium chloride is returned to the step S3 for circular leaching, and lithium-rich leachate is obtained after three times of circulation.
The lithium clay composition, the leaching residue and the leaching solution of the invention were detected by an inductively coupled plasma emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer, and the detection results are shown in table 1. Wherein the one-time leaching rate of lithium = (volume of leaching solution: lithium concentration)/(mass of leaching material: lithium content) × 100%, the multiple-time leaching rate = (volume of leaching solution) (lithium concentration-lithium concentration of circulating solution)/(mass of leaching material) × 100%, the leaching rate of lithium in the one-time leaching process can be calculated to obtain 92%, the leaching rate of lithium in the circulating leaching process is basically not influenced and can reach 90%, the concentration of lithium in the one-time leaching process is 981ppm, and the concentration of lithium in the three-time circulating process is increased to 2879ppm.
Table 1 example 1 lithium clay material and leachate composition
| Element(s) | Li | Na | K | Mg | Ca | Al | Si |
| Raw material wt% of lithium clay | 0.32 | 1.21 | 1.03 | 0.35 | 0.27 | 18.35 | 19.52 |
| Primary leach liquor/ppm | 981 | 5415 | 62 | 136 | 389 | 27 | 236 |
| Second leach liquor/ppm | 1952 | 10923 | 79 | 251 | 765 | 46 | 239 |
| Third leach liquor/ppm | 2879 | 16378 | 92 | 276 | 796 | 56 | 241 |
Example 2
A method for extracting lithium from lithium clay comprises the following specific processes:
s1: crushing lithium-containing clay to 100 meshes by using a crusher (the raw ore components are shown in a table 2);
s2: roasting the obtained crushed material at 600 ℃ for 2h;
s3: grinding the obtained roasting clinker by using a ball mill, taking 500g of ground powder, adding water and sodium chloride, wherein the liquid-solid ratio of the water to the roasting clinker is 3:1L/g, the dosage of sodium chloride is as follows: li =2:1, and reacting for 4 hours in a high-temperature high-pressure reaction kettle at 200 ℃ and the reaction pressure of 1.6-2.0MPa;
s4: and (3) carrying out solid-liquid separation on the reacted slurry to obtain a lithium-containing solution and leaching residues, wherein the lithium solution leached for the first time is named as a primary lithium leaching solution, and the primary lithium leaching solution is prepared according to the ratio of Na: and (3) replenishing sodium chloride to the Li =2:1, returning the sodium chloride to the step S3 for circulating leaching, and circulating the sodium chloride for three times to obtain a lithium-rich leaching solution.
The lithium clay composition, the leaching residue and the leaching solution of the invention were detected by an inductively coupled plasma emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer, and the detection results are shown in table 2. Wherein the first leaching rate of lithium = (volume of leaching solution x lithium concentration)/(mass of leaching material x lithium content) × 100%, the multiple leaching rate = (volume of leaching solution) × (lithium concentration-lithium concentration of circulating solution)/(mass of leaching material x lithium content) × 100%, the leaching rate of lithium in the first leaching process can be calculated to obtain 95.3%, the leaching rate of lithium in the circulating leaching process is basically not influenced and can reach 94.1%, the concentration of lithium in the first leaching process is 731ppm, and the concentration of lithium in the third leaching process is increased to 2163ppm.
Table 2 example 2 lithium clay material and leachate composition
| Element(s) | Li | Na | K | Mg | Ca | Al | Si |
| Raw material wt% of lithium clay | 0.23 | 1.05 | 1.31 | 0.24 | 0.29 | 23.75 | 18.23 |
| Primary leach solution/ppm | 731 | 3911 | 72 | 119 | 395 | 234 | 189 |
| Second leach liquor/ppm | 1451 | 7834 | 132 | 212 | 783 | 45 | 264 |
| Third leach liquor/ppm | 2163 | 11923 | 147 | 269 | 832 | 62 | 305 |
Example 3
A method for extracting lithium from lithium clay comprises the following specific processes:
s1: crushing lithium-containing clay to 100 meshes by using a crusher (the raw ore components are shown in a table 3);
s2: roasting the obtained crushed material at 700 ℃, wherein the roasting time is 2 hours;
s3: grinding the obtained roasting clinker by using a ball mill, taking 500g of ground powder, adding water and sodium chloride, wherein the liquid-solid ratio of the water to the roasting clinker is 3:1L/g, the dosage of sodium chloride is as follows: li =2:1, reacting for 4 hours in a high-temperature high-pressure reaction kettle at 250 ℃, wherein the reaction pressure is 1.6-2.2MPa;
s4: and (3) carrying out solid-liquid separation on the reacted slurry to obtain a lithium-containing solution and leaching residues, wherein the lithium solution leached for the first time is named as a primary lithium leaching solution, and the primary lithium leaching solution is prepared according to the ratio of Na: and (3) replenishing sodium chloride to the Li =3:1, returning the sodium chloride to the step S3 for circulating leaching, and circulating the sodium chloride for three times to obtain a lithium-rich leaching solution.
The lithium clay composition, the leaching residue and the leaching solution of the invention were detected by an inductively coupled plasma emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer, and the detection results are shown in table 3. Wherein the first leaching rate of lithium = (volume of leaching solution x lithium concentration)/(mass of leaching material x lithium content) × 100%, the multiple leaching rate = (volume of leaching solution) × (lithium concentration-lithium concentration of circulating solution)/(mass of leaching material x lithium content) × 100%, the leaching rate of lithium in the first leaching process can be calculated to obtain 94.7%, the leaching rate of lithium in the circulating leaching process is basically not influenced and can reach 93.9%, the concentration of lithium in the first leaching process is 1326ppm, and the concentration of lithium is increased to 3945ppm after three times of circulation.
Table 3 example 3 clay feed and leachate composition
| Element(s) | Li | Na | K | Mg | Ca | Al | Si |
| Raw material wt% of lithium clay | 0.42 | 1.17 | 1.25 | 0.31 | 0.29 | 19.62 | 18.31 |
| Primary leach solution/ppm | 1326 | 6712 | 76 | 196 | 368 | 25 | 325 |
| Second leach liquor/ppm | 2639 | 13425 | 142 | 242 | 690 | 48 | 365 |
| Third leach liquor/ppm | 3945 | 20136 | 197 | 312 | 712 | 59 | 372 |
Example 4
A method for extracting lithium from lithium clay comprises the following specific processes:
s1: crushing lithium-containing clay to 100 meshes by using a crusher (the raw ore components are shown in a table 4);
s2: roasting the obtained crushed material at 800 ℃ for 2h;
s3: grinding the obtained roasting clinker by using a ball mill, taking 500g of ground powder, adding water and sodium chloride, wherein the liquid-solid ratio of the water to the roasting clinker is 3:1L/g, the dosage of sodium chloride is as follows: li =3:1, and reacting for 4 hours in a high-temperature high-pressure reaction kettle at 200 ℃ and the reaction pressure of 1.4-2.0MPa;
s4: and (3) carrying out solid-liquid separation on the reacted slurry to obtain a lithium-containing solution and leaching residues, wherein the lithium solution leached for the first time is named as a primary lithium leaching solution, and the primary lithium leaching solution is prepared according to the ratio of Na: and (3) replenishing sodium chloride to the Li =3:1, returning the sodium chloride to the step S3 for circulating leaching, and circulating the sodium chloride for three times to obtain a lithium-rich leaching solution.
The compositions of the lithium clay, the leaching residues and the leaching solution of the invention are detected by an inductively coupled plasma emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer, and the detection results are shown in Table 4. Wherein the first leaching rate of lithium = (volume of leaching solution lithium concentration)/(mass of leaching material lithium content) × 100%, the multiple leaching rate = (volume of leaching solution) × (lithium concentration-lithium concentration of circulating solution)/(mass of leaching material) × 100%, the leaching rate of lithium in the first leaching process can be calculated to obtain 95.8%, the leaching rate of lithium in the circulating leaching process is basically not influenced and can reach 94.8%, the concentration of lithium in the first leaching process is 1022pm, and the concentration of lithium is increased to 3037ppm after three times of circulation.
Table 4 example 4 lithium clay feedstock and leachate composition
| Element(s) | Li | Na | K | Mg | Ca | Al | Si |
| Raw material wt% of lithium clay | 0.32 | 0.95 | 1.35 | 0.23 | 0.69 | 28.56 | 16.32 |
| Primary leach solution/ppm | 1022 | 10623 | 85 | 132 | 831 | 34 | 232 |
| Second leach liquor/ppm | 2035 | 21254 | 158 | 232 | 865 | 58 | 247 |
| Third leach liquor/ppm | 3037 | 31879 | 225 | 346 | 894 | 89 | 256 |
Comparative example 1
The method for extracting lithium from lithium clay is different from the method in example 1 in that the leaching reaction conditions are different, and the specific process is as follows:
s1: crushing lithium-containing clay to 100 meshes by using a crusher (the raw ore components are shown in table 5);
s2: roasting the obtained crushed material at 500 ℃ for 3h;
s3: grinding the obtained roasting clinker by using a ball mill, taking 500g of ground powder, adding water and sodium chloride, wherein the liquid-solid ratio of the water to the roasting clinker is 3:1L/g, the dosage of sodium chloride is as follows: li =3:1, reacting for 4 hours at 130 ℃ in a high-temperature high-pressure reaction kettle, wherein the reaction pressure is 0.2-0.6MPa;
s4: and (3) carrying out solid-liquid separation on the reacted slurry to obtain a lithium-containing solution and leaching residues, wherein the lithium solution leached for the first time is named as a primary lithium leaching solution, and the primary lithium leaching solution is prepared according to the ratio of Na: and (3) replenishing sodium chloride to the Li =3:1, returning the sodium chloride to the step S3 for circulating leaching, and circulating the sodium chloride for three times to obtain a lithium-rich leaching solution.
The compositions of the lithium clay, the leaching residue and the leaching solution of the invention were detected by an inductively coupled plasma emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer, and the detection results are shown in table 5. Wherein the first leaching rate of lithium = (volume of leaching solution x lithium concentration)/(mass of leaching material x lithium content) × 100%, the multiple leaching rate = (volume of leaching solution) × (lithium concentration-lithium concentration of circulating solution)/(mass of leaching material x lithium content) × 100%, the leaching rate of lithium in the first leaching process is only 37.2% by calculation, the leaching rate of lithium in the circulating leaching process is basically not influenced and is about 36.2%, the concentration of lithium in the first leaching process is 335ppm, and the concentration of lithium is increased to 978ppm after three times of circulation. This comparative example shows that temperature and pressure have a great influence on the lithium leaching effect, and that the lithium leaching rate is very low when the temperature and pressure are insufficient.
Table 5 comparative example 1 lithium clay feedstock and leachate composition
| Element(s) | Li | Na | K | Mg | Ca | Al | Si |
| Raw material wt% of lithium clay | 0.27 | 1.02 | 0.98 | 0.19 | 0.78 | 23.56 | 17.63 |
| Primary leach liquor/ppm | 335 | 9948 | 76 | 95 | 768 | 31 | 256 |
| Second leach liquor/ppm | 365 | 19876 | 149 | 185 | 782 | 56 | 263 |
| Third leach liquor/ppm | 978 | 29344 | 212 | 279 | 803 | 86 | 269 |
Comparative example 2
The method for extracting lithium from lithium clay is different from the method in the embodiment 2 in that magnesium chloride is used as a leaching agent, and the specific process is as follows:
s1: crushing lithium-containing clay to 100 meshes by using a crusher (raw ore components are shown in table 6);
s2: roasting the obtained crushed material at 600 ℃, wherein the roasting time is 2h;
s3: grinding the obtained roasting clinker by using a ball mill, taking 500g of ground powder, adding water and sodium chloride, wherein the liquid-solid ratio of the water to the roasting clinker is 3:1L/g, the dosage of magnesium chloride is as follows: li =2:1, reacting for 4 hours in a high-temperature high-pressure reaction kettle at 200 ℃, wherein the reaction pressure is 1.6-2.0MPa;
s4: and (3) carrying out solid-liquid separation on the reacted slurry to obtain a lithium-containing solution and leaching residues, wherein the lithium solution leached for the first time is named as a primary lithium leaching solution, and the primary lithium leaching solution is prepared according to the ratio of Mg: and (3) replenishing magnesium chloride to the Li =2:1, returning the magnesium chloride to the step S3 for circulating leaching, and circulating the magnesium chloride for three times to obtain a lithium-rich leaching solution.
The compositions of the lithium clay, the leaching residue and the leaching solution of the invention were measured by an inductively coupled plasma emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer, and the results are shown in table 6. Wherein the first leaching rate of lithium = (volume of leaching solution x lithium concentration)/(mass of leaching material x lithium content) × 100%, the multiple leaching rate = (volume of leaching solution) × (lithium concentration-lithium concentration of circulating solution)/(mass of leaching material x lithium content) × 100%, the leaching rate of lithium in the first leaching process is only 27.9% by calculation, the leaching rate of lithium in the circulating leaching process is basically not influenced, about 26.5%, the concentration of lithium in the first leaching process is 326ppm, and the concentration of lithium in the third leaching process is increased to 978ppm. In the comparative example, magnesium salt is used as a leaching agent, so that the leaching rate is low, a large amount of magnesium exists in the leaching solution, and the burden of subsequent impurity removal is increased.
Table 6 comparative example 2 lithium clay feed and leachate composition
| Element(s) | Li | Na | K | Mg | Ca | Al | Si |
| Raw material wt% of lithium clay | 0.35 | 1.11 | 1.03 | 0.29 | 0.35 | 26.78 | 17.59 |
| Primary leach solution/ppm | 326 | 92 | 83 | 12213 | 356 | 32 | 153 |
| Secondary leach liquor/ppm | 657 | 179 | 156 | 24418 | 695 | 57 | 296 |
| Third leach liquor/ppm | 978 | 268 | 219 | 36629 | 987 | 83 | 448 |
Comparative example 3
The method for extracting lithium from lithium clay is different from the method in the embodiment 3 in that the roasting treatment in the step S2 is not performed, and the specific process is as follows:
s1: crushing a lithium-containing clay to 100 meshes by using a crusher (the raw ore components are shown in a table 7);
s2: and grinding the obtained crushed material by using a ball mill, taking 500g of ground powder, adding water and sodium chloride, wherein the liquid-solid ratio of the water to the crushed material is 3:1L/g, the dosage of sodium chloride is as follows: li =2:1, and reacting for 4 hours in a high-temperature high-pressure reaction kettle at 250 ℃ and the reaction pressure of 1.6-2.2MPa;
s3: and (3) performing solid-liquid separation on the reacted slurry to obtain a lithium-containing solution and leaching residues, wherein the lithium solution leached for the first time is named as a primary lithium leaching solution, and the primary lithium leaching solution is prepared according to the proportion of Na: and (3) replenishing sodium chloride to the Li =3:1, returning the sodium chloride to the step S3 for circulating leaching, and circulating the sodium chloride for three times to obtain a lithium-rich leaching solution.
The compositions of the lithium clay, the leaching residue and the leaching solution of the invention were measured by an inductively coupled plasma emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer, and the results are shown in table 7. Wherein the leaching rate of lithium at one time = (volume of leaching solution: lithium concentration)/(mass of leaching material: lithium content) × 100%, the leaching rate of multiple times = (volume of leaching solution) (lithium concentration-lithium concentration of circulating solution)/(mass of leaching material) × 100%, the leaching rate of lithium at one leaching process is only 36.8% by calculation, the leaching rate of lithium at the circulating leaching process is basically not influenced, about 34.8%, the lithium concentration at one leaching process is 454ppm, and the lithium concentration is increased to 1291ppm after three times of circulation. According to the comparative example, the lithium clay raw ore is not roasted to convert the crystal form, more inert ore types exist in the raw material, the ion exchange process is difficult to carry out, and the leaching rate is low.
Table 7 comparative example 3 lithium clay feed and leachate composition
| Element(s) | Li | Na | K | Mg | Ca | Al | Si |
| Raw material wt% of lithium clay | 0.37 | 1.21 | 0.89 | 0.48 | 0.32 | 28.36 | 17.56 |
| Primary leach solution/ppm | 454 | 10721 | 56 | 78 | 356 | 42 | 225 |
| Second leach liquor/ppm | 827 | 21435 | 108 | 146 | 376 | 58 | 236 |
| Third leach liquor/ppm | 1291 | 32153 | 145 | 198 | 385 | 86 | 254 |
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A method for extracting lithium from lithium clay is characterized by comprising the following steps:
s1: roasting the lithium clay powder to obtain roasted clinker;
s2: grinding the roasted clinker, mixing the ground roasted clinker with a leaching agent and water, leaching at the temperature of 150-300 ℃ and under the pressure of 1.4-2.5MPa, and performing solid-liquid separation to obtain a lithium-containing solution and leaching residues; the leaching agent is at least one of sodium hydroxide, potassium hydroxide, sodium strong acid salt or potassium strong acid salt;
s3: and adding a proper amount of the leaching agent into the lithium-containing solution, then returning to the step S2 for circular leaching, and circularly leaching for a plurality of times according to the process to obtain a lithium-rich solution.
2. The method according to claim 1, wherein in step S1, the lithium clay powder is at least one of carbonate type clay mineral, volcanic type clay mineral, or Gu Daer lithium boron mineral.
3. The method of claim 1, wherein in step S1, the particle size of the lithium clay powder is 50-400 mesh.
4. The method of claim 1, wherein the temperature of the roasting in step S1 is 400-1200 ℃.
5. The method of claim 1, wherein in step S1, the roasting time is 1-5h.
6. The method according to claim 1, wherein in step S2, the molar ratio of the metallic element in the leaching agent to the lithium in the roasting clinker is (1-10): 1.
7. the method according to claim 1, wherein in step S2, the strong acid salt of sodium is selected from at least one of sodium sulfate or sodium chloride; the strong acid salt of potassium is at least one of potassium sulfate or potassium chloride.
8. The method according to claim 1, wherein in step S2, the leaching time is 1-12h.
9. The method according to claim 1, wherein in step S2, the solid-to-liquid ratio of the roasting clinker to water is 1: (2-10) g/L.
10. The method according to claim 1, wherein in step S3, the concentration of lithium in the lithium-rich solution is 0.5-10g/L.
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| CN116002736A (en) * | 2022-12-29 | 2023-04-25 | 四川顺应锂材料科技有限公司 | Method for preparing aluminum hydroxide by pressure leaching and separating aluminum and lithium from clay lithium ore |
| CN116829745A (en) * | 2023-04-19 | 2023-09-29 | 广东邦普循环科技有限公司 | Method for selectively extracting lithium from sedimentary type lean lithium clay and application thereof |
| CN117265288A (en) * | 2023-08-31 | 2023-12-22 | 中国科学院青海盐湖研究所 | Method for obtaining solution high in rubidium and cesium from salt lake sediment based on acid treatment |
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| CN107815557A (en) * | 2017-10-16 | 2018-03-20 | 福州大学 | A kind of spodumene pipe reaction puies forward lithium technique |
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| CN107089674A (en) * | 2017-07-03 | 2017-08-25 | 福州大学 | A kind of spodumene sodium sulphate pressure leaching puies forward lithium technique |
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| WO2021146768A1 (en) * | 2020-01-20 | 2021-07-29 | Tianqi Lithium Kwinana Pty Ltd | A process for producing alumina and a lithium salt |
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| CN116829745A (en) * | 2023-04-19 | 2023-09-29 | 广东邦普循环科技有限公司 | Method for selectively extracting lithium from sedimentary type lean lithium clay and application thereof |
| CN116829745B (en) * | 2023-04-19 | 2024-04-09 | 广东邦普循环科技有限公司 | Method for selectively extracting lithium from sedimentary type lean lithium clay and application thereof |
| CN117265288A (en) * | 2023-08-31 | 2023-12-22 | 中国科学院青海盐湖研究所 | Method for obtaining solution high in rubidium and cesium from salt lake sediment based on acid treatment |
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