WO2024000883A1 - Method for extracting lithium from lithium clay - Google Patents

Method for extracting lithium from lithium clay Download PDF

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WO2024000883A1
WO2024000883A1 PCT/CN2022/122264 CN2022122264W WO2024000883A1 WO 2024000883 A1 WO2024000883 A1 WO 2024000883A1 CN 2022122264 W CN2022122264 W CN 2022122264W WO 2024000883 A1 WO2024000883 A1 WO 2024000883A1
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lithium
clay
leaching
microwave
extracting
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PCT/CN2022/122264
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French (fr)
Chinese (zh)
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苗耀文
李长东
乔延超
李波
陈若葵
阮丁山
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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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
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • 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

Definitions

  • the present invention relates to the technical field of lithium extraction from lithium resources, in particular to a method for extracting lithium from lithium clay.
  • lithium-ion batteries As a key element in lithium-ion batteries, lithium has attracted more and more attention from the industry. Lithium salt products represented by lithium carbonate and lithium hydroxide are already in short supply in the market and prices remain high. Therefore, the further development of lithium resources is very urgent.
  • lithium salt products on the market mainly come from lithium extraction from spodumene, lithium extraction from lepidolite, lithium extraction from salt lakes, and lithium recovery from retired lithium-ion batteries.
  • lithium clay was once ignored due to the low grade of lithium oxide.
  • Patent CN202010684178.8 discloses a method for extracting lithium from lithium-containing clay. This method produces a large amount of calcium-silicon waste residue, which is difficult to process.
  • the lithium oxide content in the residue reaches 0.2%, and is only suitable for clay ores with higher lithium oxide grades; the patent CN201410098348.9 published a method for extracting lithium from low-grade lithium-containing clay ores.
  • This method proposed a new process of "modified roasting-heap leaching", but the roasting process introduced calcium fluoride, and fluoride ions caused damage to the equipment. It is highly corrosive and the hydrogen fluoride produced also pollutes the atmosphere.
  • the object of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a method for extracting lithium from lithium clay.
  • the present invention provides a method for extracting lithium from lithium clay.
  • the microwave roasting method is used to extract lithium from clay-type lithium resources. This method raises the temperature in a relatively short period of time, and then adds a certain amount of Water leaching and leaching agents are cheap and the lithium extraction rate is extremely high.
  • the technical solution adopted by the present invention is: a method for extracting lithium from lithium clay, which includes the following steps:
  • step (1) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material;
  • the microwave power in microwave roasting is 1-3kw, and the temperature of microwave roasting is 650-750°C;
  • step (3) Mix the crushed material in step (2) with water, stir, and leach, and filter to obtain a lithium-containing leachate.
  • the lithium clay contains hectorite, and lithium is present in hectorite.
  • FIG. 1 is an XRD quantitative analysis chart of the composition of lithium clay.
  • Lithium in lithium clay mainly exists in lithium chlorite.
  • Lithium in clay-type lithium resources The content is generally not more than 0.4%.
  • Lithium element is mainly present in lithium in the form of lithium chlorite.
  • Lithium chlorite is a layered aluminum silicate clay mineral close to dioctahedron. By controlling the roasting process, it can be completely The hydroxyl groups in its layered structure are removed to improve the activity of the mineral. In addition, the distribution of the main impurity silicon atoms can remain in its original state.
  • the microwave roasting method used in this invention extracts lithium from lithium clay.
  • the temperature of the sample cannot reach 600°C even if it exceeds 70min; when the microwave power is increased to 1.0kW, the peak temperature of the sample can be within 30min. It can reach above 1200°C within 10 minutes; at 2.5kw or higher power, it can reach 1200°C within 10 minutes.
  • the inventor found in actual experiments that if the microwave power is higher than 3kW, the heating rate is extremely fast and the reaction temperature cannot be controlled.
  • the lithium clay pretreatment method is: crush the lithium clay, mix it with the leaching agent and then ball mill; wherein, the diameter of the crushed lithium clay is 2-5mm, and the pretreatment obtained after ball milling is The diameter of the material is 50-150 ⁇ m.
  • the present invention adopts microwave roasting and heating method, which has a fast heating rate. It is aimed at clay-type lithium resources where lithium is contained in lithium chlorite.
  • the lithium chlorite has strong absorption of microwaves.
  • the leaching agent selected in the present invention is a mixture of sulfate and calcium oxide. The inventor found that, first, calcium oxide solidifies SiO 2 in the lithium chlorite, destroys the crystal lattice, and generates calcium silicate to realize the synchronization of metal ions in the sulfate. Lithium is ion exchanged, and the exchanged lithium exists in the form of sulfate. The lithium in the lithium clay is deeply extracted, which greatly improves the lithium extraction rate.
  • the method adopts microwave roasting, which is fast, has low energy consumption and has no greenhouse gas emissions.
  • the recovery rate of Fe, Na, Ca, Al and Si during the leaching process is low, and has advantages in the downstream purification process.
  • the inventor found that during the actual test, if calcium carbonate is used for solidification, the roasting temperature during microwave roasting is about 850°C, and the lithium chlorite mineral structure is completely destroyed, resulting in the inability to effectively leach lithium element.
  • the leaching agent is a mixture of sulfate and calcium oxide.
  • the sulfate is at least one of potassium sulfate and sodium sulfate.
  • the microwave frequency is 2450 MHz; the heat preservation time is 1-4 h, cooled to 20-35°C, and ground to 50-200 ⁇ m.
  • the temperature of microwave roasting is 700-750°C. Further preferably, the temperature of microwave roasting is 730°C.
  • the present invention provides a method for extracting lithium from clay-type lithium resources.
  • the microwave roasting method is used to extract lithium from clay-type lithium resources. Lithium, this method heats up in a short period of time, and then adds a certain amount of water for leaching.
  • the leaching agent is cheap and the lithium extraction rate is extremely high.
  • Figure 1 shows the XRD quantitative analysis chart of lithium clay composition.
  • the experimental methods used are conventional methods unless otherwise specified, and the materials and reagents used can be obtained from commercial sources unless otherwise specified.
  • the lithium clay used in the embodiments of the present invention comes from a clay mine in Guizhou.
  • the lithium content in the lithium clay is 0.21%.
  • the method of extracting lithium from the lithium clay of the present invention is not limited to the use of the above-mentioned lithium clay.
  • the leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide.
  • the pretreated material obtained after ball milling The diameter is 50-150 ⁇ m; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent 5:3;
  • step (2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 700°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200 ⁇ m;
  • step (3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution.
  • the temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
  • the leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide.
  • the pretreated material obtained after ball milling The diameter is 50-150 ⁇ m; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent 5:3;
  • step (2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 700°C, the microwave power in microwave roasting is 1kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200 ⁇ m;
  • step (3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution.
  • the temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
  • the leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide.
  • the pretreated material obtained after ball milling The diameter is 50-150 ⁇ m; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent 5:3;
  • step (2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 700°C, the microwave power in microwave roasting is 3kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200 ⁇ m;
  • step (3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution.
  • the temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
  • the leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide.
  • the pretreated material obtained after ball milling The diameter is 50-150 ⁇ m; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent 5:3;
  • step (2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 730°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200 ⁇ m;
  • step (3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution.
  • the temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
  • the leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide.
  • the pretreated material obtained after ball milling The diameter is 50-150 ⁇ m; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent 5:3;
  • step (2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 750°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200 ⁇ m;
  • step (3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution.
  • the temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
  • the leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide.
  • the pretreated material obtained after ball milling The diameter is 50-150 ⁇ m; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent 5:3;
  • step (2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 650°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200 ⁇ m;
  • step (3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution.
  • the temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
  • the leaching agent is a mixture of potassium sulfate and calcium oxide.
  • step (2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 700°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 4h, cool to room temperature, and grind to 50-200 ⁇ m;
  • step (3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leachate.
  • the temperature for mixing, stirring and leaching is 85°C. , the leaching time is 2h.
  • the leaching agent is a mixture of sodium sulfate and calcium oxide.
  • step (2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 700°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 3h, cool to room temperature, and grind to 50-200 ⁇ m;
  • step (3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leach solution.
  • the temperature for mixing, stirring and leaching is 60°C. , the leaching time is 1h.
  • Comparative Example 1 is compared with Example 1. Only the power and temperature of microwave roasting in step (2) are different.
  • the method for extracting lithium from lithium clay in Comparative Example 1 includes the following steps:
  • the leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide.
  • the pretreated material obtained after ball milling The diameter is 50-150 ⁇ m; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent 5:3;
  • step (2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material;
  • the temperature of microwave roasting is 550°C
  • the microwave power in microwave roasting is 0.5kw
  • the microwave frequency is 2450MHz;
  • the heat preservation time is 1 hour, cool to room temperature, and grind to 50-200 ⁇ m;
  • step (3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution.
  • the temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
  • Comparative Example 2 is compared with Example 1. Only the power and temperature of microwave roasting in step (2) are different.
  • the method of extracting lithium from lithium clay in Comparative Example 2 includes the following steps:
  • the leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide.
  • the pretreated material obtained after ball milling The diameter is 50-150 ⁇ m; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent 5:3;
  • step (2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 600°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200 ⁇ m;
  • step (3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution.
  • the temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
  • Comparative Example 3 is compared with Example 1. Only the power and temperature of microwave roasting in step (2) are different.
  • the method of extracting lithium from lithium clay in Comparative Example 3 includes the following steps:
  • the leaching agent is a mixture of potassium sulfate, sodium sulfate, and calcium oxide.
  • step (2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 800°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200 ⁇ m;
  • step (3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution.
  • the temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
  • Comparative Example 4 is a single comparison with Example 1, only the selection of the leaching agent in step (1) is different.
  • the method of extracting lithium from lithium clay in Comparative Example 4 includes the following steps:
  • the leaching agent is a mixture of potassium sulfate and sodium sulfate.
  • step (2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 700°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200 ⁇ m;
  • step (3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution.
  • the temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
  • Example 1 700 2 14 Example 2 700 1 16 Example 3 700 3 11 Example 4 730 2 14.5 Example 5 750 2 15 Example 6 650 2 13 Example 7 700 2 14
  • the lithium leaching rate (volume of lithium-containing leach solution * lithium concentration in the leach solution) / (mass of lithium clay * percentage of lithium in the lithium clay), where the lithium content in the lithium clay is 0.21%; during the actual experimental process of the present invention, The lithium leachate is slightly lost during the leaching process.
  • Specific examples and comparative examples contain lithium leachate volumes as shown in Table 2 below;
  • the methods for extracting lithium from lithium clay in Examples 1-8 of the present invention use microwave roasting to extract lithium from clay-type lithium resources. This method heats up in a relatively short time, and the final lithium leaching rate is 95%. above. It can be seen from the comparison between Example 1 and Examples 4-6 that when the microwave power is 1-3kw and the roasting temperature is 700-750°C, the final lithium leaching rate is more than 96%; when the roasting temperature is 730°C, The lithium leaching rate reaches the optimal level, with a leaching rate of over 98%.
  • Comparative Example 1 has low microwave roasting power.
  • the maximum temperature reached by heating lithium clay at 0.5kw is about 550°C, and the heating time is long, requiring about 80 minutes.
  • the final lithium leaching rate is 72.1%, which is significantly lower than the implementation of the present invention.
  • the microwave roasting power is 2kw
  • the microwave roasting temperature is 600°C, which is lower than the microwave roasting temperature limited by the present invention
  • the final lithium leaching rate is significantly lower than the final lithium leaching rate of the embodiment of the present invention.
  • the microwave roasting power is 2kw
  • the microwave roasting temperature is 800°C, which is higher than the microwave roasting temperature limited by the present invention
  • the final lithium leaching rate is significantly lower than the final lithium leaching rate of the embodiments of the present invention.
  • the leaching agent in Comparative Example 4 does not contain calcium oxide. It is difficult for potassium salt or sodium salt to directly react with the silica in the lithium chlorite. Calcium oxide needs to be added to solidify SiO 2 to destroy the crystal lattice and generate calcium silicate to achieve sodium/potassium. For ion exchange with lithium, calcium oxide was not added to destroy the crystal lattice in this comparative example, and lithium could not effectively carry out replacement reaction with Na/K, resulting in a low lithium leaching rate.

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Abstract

A method for extracting lithium from lithium clay, which relates to the technical field of extraction of lithium from lithium resources. The method for extracting lithium from lithium clay comprises the following steps: (1) pretreating lithium clay to obtain a pretreated material; (2) subjecting the pretreated material in step (1) to microwave roasting, heat preservation, cooling and grinding to obtain a crushed material, wherein the microwave power of the microwave roasting is 1-3 kw, and the temperature of the microwave roasting is 650-750°C; and (3) mixing and stirring the crushed material in step (2) with water for leaching, and then filtering same to obtain a lithium-containing leachate. A method for extracting lithium from a clay-type lithium resource. Aiming at the specific technical difficulty of a clay-type lithium resource, a microwave roasting method is used in the present method to extract lithium from the clay-type lithium resource. By means of the method, the temperature rises in a short time, and a certain amount of water is then added for leaching. The leaching agent has a low price and the lithium extraction rate is extremely high.

Description

一种从锂黏土中提取锂的方法A method for extracting lithium from lithium clay 技术领域Technical field
本发明涉及锂资源提锂技术领域，尤其是一种从锂黏土中提取锂的方法。The present invention relates to the technical field of lithium extraction from lithium resources, in particular to a method for extracting lithium from lithium clay.
背景技术Background technique
随着石油等传统能源的日益紧缺，新能源的发展越来越受到重视，特别是对锂电池的需求量在不断急剧增。锂作为锂离子电池中的关键元素，愈发受到行业关注，以碳酸锂和氢氧化锂为代表的锂盐产品，市场已经供不应求，价格高居不下。所以，锂资源的进一步开发显得十分迫切。With the increasing shortage of traditional energy sources such as oil, the development of new energy sources has received more and more attention, especially the demand for lithium batteries, which continues to increase rapidly. As a key element in lithium-ion batteries, lithium has attracted more and more attention from the industry. Lithium salt products represented by lithium carbonate and lithium hydroxide are already in short supply in the market and prices remain high. Therefore, the further development of lithium resources is very urgent.
目前，市场上的锂盐产品主要来源于锂辉石提锂、锂云母提锂、盐湖提锂以及退役锂离子电池中的锂回收，而锂黏土由于氧化锂品位较低一度被忽视，近年随着矿物勘探工作的深入开展，国内外均发现许多大型的锂黏土矿，其碳酸锂当量均在百万吨级以上，储量非常可观。针对锂黏土中锂的回收，目前国内相关提锂技术十分有限。专利CN202010684178.8公布了一种含锂黏土提锂的方法，该法产生大量的钙硅废渣，难以处理，渣中氧化锂含量达到0.2％，仅适用于氧化锂品位较高的黏土矿；专利CN201410098348.9公布了一种低品位含锂粘土矿提锂的方法，该法提出了一种“改性焙烧-堆浸”的新工艺，但焙烧过程引入了氟化钙，氟离子对设备的腐蚀性较大，产生的氟化氢也对大气存在污染。At present, lithium salt products on the market mainly come from lithium extraction from spodumene, lithium extraction from lepidolite, lithium extraction from salt lakes, and lithium recovery from retired lithium-ion batteries. However, lithium clay was once ignored due to the low grade of lithium oxide. In recent years, with the With the in-depth development of mineral exploration work, many large-scale lithium clay mines have been discovered at home and abroad, with lithium carbonate equivalents exceeding one million tons, and the reserves are very considerable. Regarding the recovery of lithium from lithium clay, the relevant domestic lithium extraction technology is currently very limited. Patent CN202010684178.8 discloses a method for extracting lithium from lithium-containing clay. This method produces a large amount of calcium-silicon waste residue, which is difficult to process. The lithium oxide content in the residue reaches 0.2%, and is only suitable for clay ores with higher lithium oxide grades; the patent CN201410098348.9 published a method for extracting lithium from low-grade lithium-containing clay ores. This method proposed a new process of "modified roasting-heap leaching", but the roasting process introduced calcium fluoride, and fluoride ions caused damage to the equipment. It is highly corrosive and the hydrogen fluoride produced also pollutes the atmosphere.
发明内容Contents of the invention
基于此，本发明的目的在于克服上述现有技术的不足之处而提供一种从锂黏土中提取锂的方法。本发明提供了一种从锂黏土中提取锂的方法，针对黏土型锂资源的特定技术难点，采用微波焙烧法从黏土型锂资源中提取锂，该方法在较短时间内升温，后加入一定量水浸出、浸出剂价格便宜且锂提取率极高。Based on this, the object of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a method for extracting lithium from lithium clay. The present invention provides a method for extracting lithium from lithium clay. In view of the specific technical difficulties of clay-type lithium resources, the microwave roasting method is used to extract lithium from clay-type lithium resources. This method raises the temperature in a relatively short period of time, and then adds a certain amount of Water leaching and leaching agents are cheap and the lithium extraction rate is extremely high.
为实现上述目的，本发明所采取的技术方案为：一种从锂黏土中提取锂的方法，包括以下步骤：In order to achieve the above object, the technical solution adopted by the present invention is: a method for extracting lithium from lithium clay, which includes the following steps:
(1)将锂黏土进行预处理，得到预处理料；(1) Pretreat lithium clay to obtain pretreated material;
(2)将步骤(1)中的预处理料进行微波焙烧、保温、冷却、研磨后，得到粉碎料；微波焙烧中微波功率为1-3kw，微波焙烧的温度为650-750℃；(2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the microwave power in microwave roasting is 1-3kw, and the temperature of microwave roasting is 650-750°C;
(3)将步骤(2)中的粉碎料和水混合搅拌浸出，过滤得到含锂浸出液。(3) Mix the crushed material in step (2) with water, stir, and leach, and filter to obtain a lithium-containing leachate.
优选地，所述步骤(1)中，锂黏土包含锂绿泥石，锂存在于锂绿泥石中。Preferably, in step (1), the lithium clay contains hectorite, and lithium is present in hectorite.
本发明从微观角度解释锂从锂黏土中提取锂，如图1所示，图1为锂黏土组成XRD定量分析图，锂黏土中的锂主要存在锂绿泥石中，黏土型锂资源中锂含量一般不大于0.4％，锂元素主要以锂绿泥石形式赋存于锂中，锂绿泥石是一种接近二八面体的层状铝硅酸盐粘土矿物，通过控制焙烧过程，能完全脱去其层状结构中的羟基，提高矿物的活性，另外，主要杂质硅原子的分布还能保持原有状态。The present invention explains the extraction of lithium from lithium clay from a microscopic perspective, as shown in Figure 1. Figure 1 is an XRD quantitative analysis chart of the composition of lithium clay. Lithium in lithium clay mainly exists in lithium chlorite. Lithium in clay-type lithium resources The content is generally not more than 0.4%. Lithium element is mainly present in lithium in the form of lithium chlorite. Lithium chlorite is a layered aluminum silicate clay mineral close to dioctahedron. By controlling the roasting process, it can be completely The hydroxyl groups in its layered structure are removed to improve the activity of the mineral. In addition, the distribution of the main impurity silicon atoms can remain in its original state.
发明人发现，焙烧温度低于650℃，锂绿泥石层状结构中的羟基未完全脱除，高活性的非晶态结构尚未形成，锂元素就无法有效浸出；焙烧温度高于750℃，锂绿泥石矿物结构被完全破坏，会逐渐形成莫来石，主要杂质硅的晶型也会发生变化，对锂元素进行重新包裹，导致锂元素也无法有效浸出。常规煅烧方法很难实现锂绿泥石的处理，锂不能完全从锂绿泥石中释放出来。本发明采用的微波焙烧法从锂黏土中提取锂，通过研究发现在0.5kW时，样品的温度甚至超过70min也不能达到600℃；当微波功率提高到1.0kW时，样品的峰值温度可以在30min内达到1200℃以上；在2.5kw或者是更高功率，10min内就能达到1200℃。发明人在实际实验中发现，倘若微波功率高于3kW，升温速率极快，无法控制反应温度。The inventor found that when the roasting temperature is lower than 650°C, the hydroxyl groups in the lithium chlorite layered structure are not completely removed, and the highly active amorphous structure has not yet formed, so the lithium element cannot be effectively leached; when the roasting temperature is higher than 750°C, When the mineral structure of lithium chlorite is completely destroyed, mullite will gradually form, and the crystal form of the main impurity silicon will also change, re-coating the lithium element, resulting in the inability to effectively leach the lithium element. Conventional calcination method is difficult to achieve the treatment of lithium chlorite, and lithium cannot be completely released from lithium chlorite. The microwave roasting method used in this invention extracts lithium from lithium clay. Through research, it is found that at 0.5kW, the temperature of the sample cannot reach 600°C even if it exceeds 70min; when the microwave power is increased to 1.0kW, the peak temperature of the sample can be within 30min. It can reach above 1200℃ within 10 minutes; at 2.5kw or higher power, it can reach 1200℃ within 10 minutes. The inventor found in actual experiments that if the microwave power is higher than 3kW, the heating rate is extremely fast and the reaction temperature cannot be controlled.
优选地，所述步骤(1)中，锂黏土预处理的方法为：将锂黏土破碎，与浸出剂混合后球磨；其中，破碎后锂黏土的直径为2-5mm，球磨后得到的预处理料的直径为50-150μm。Preferably, in the step (1), the lithium clay pretreatment method is: crush the lithium clay, mix it with the leaching agent and then ball mill; wherein, the diameter of the crushed lithium clay is 2-5mm, and the pretreatment obtained after ball milling is The diameter of the material is 50-150μm.
本发明采用微波焙烧加热法，升温速率快，针对锂赋存在锂绿泥石中的黏土型锂资源，锂绿泥石对微波有很强的吸收。本发明选用的浸出剂为硫酸盐、氧化钙的混合物，发明人发现，首先，氧化钙固化锂绿泥石中的SiO 2，破坏晶格，生成硅酸钙从而实现硫酸盐中的金属离子同锂的进行离子交换，交换后的锂以硫酸盐的方式存在，深度提取锂黏土中的锂，大大提高了提锂率。本发明采用微波焙烧，速度快、能耗低、无温室气体排放，浸出过程中Fe、Na、Ca、Al、Si的回收率较低，在下游净化过程中具有优势。发明人发现，在实际试验过程中，如果采用碳酸钙固化，则微波焙烧过程中的焙烧温度为850℃左右，锂绿泥石矿物结构被完全破坏，导致锂元素无法有效浸出。 The present invention adopts microwave roasting and heating method, which has a fast heating rate. It is aimed at clay-type lithium resources where lithium is contained in lithium chlorite. The lithium chlorite has strong absorption of microwaves. The leaching agent selected in the present invention is a mixture of sulfate and calcium oxide. The inventor found that, first, calcium oxide solidifies SiO 2 in the lithium chlorite, destroys the crystal lattice, and generates calcium silicate to realize the synchronization of metal ions in the sulfate. Lithium is ion exchanged, and the exchanged lithium exists in the form of sulfate. The lithium in the lithium clay is deeply extracted, which greatly improves the lithium extraction rate. The method adopts microwave roasting, which is fast, has low energy consumption and has no greenhouse gas emissions. The recovery rate of Fe, Na, Ca, Al and Si during the leaching process is low, and has advantages in the downstream purification process. The inventor found that during the actual test, if calcium carbonate is used for solidification, the roasting temperature during microwave roasting is about 850°C, and the lithium chlorite mineral structure is completely destroyed, resulting in the inability to effectively leach lithium element.
优选地，所述步骤(1)中，锂黏土和浸出剂的质量比为：锂黏土：浸出剂＝5：(1-4)。Preferably, in the step (1), the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent = 5: (1-4).
优选地，所述浸出剂为硫酸盐和氧化钙的混合物。进一步优选地，所述硫酸盐为硫酸钾、硫酸钠中的至少一种。Preferably, the leaching agent is a mixture of sulfate and calcium oxide. Further preferably, the sulfate is at least one of potassium sulfate and sodium sulfate.
优选地，硫酸盐、氧化钙的质量比为：硫酸盐：氧化钙＝(1-2)：1。Preferably, the mass ratio of sulfate and calcium oxide is: sulfate:calcium oxide=(1-2):1.
优选地，所述步骤(2)中，微波频率为2450MHz；保温的时间为1-4h，冷却至20-35℃，研磨至50-200μm。Preferably, in step (2), the microwave frequency is 2450 MHz; the heat preservation time is 1-4 h, cooled to 20-35°C, and ground to 50-200 μm.
优选地，所述步骤(2)中，微波焙烧的温度为700-750℃。进一步优选地，微波焙烧的温度为730℃。Preferably, in step (2), the temperature of microwave roasting is 700-750°C. Further preferably, the temperature of microwave roasting is 730°C.
优选地，所述步骤(3)中，粉碎料和水的质量比为：粉碎料：水＝1：(3-5)，混合搅拌浸出的温度为60-85℃，浸出时间为1-2h。Preferably, in the step (3), the mass ratio of pulverized material and water is: pulverized material: water = 1: (3-5), the temperature of mixing, stirring and leaching is 60-85°C, and the leaching time is 1-2h. .
相对于现有技术，本发明的有益效果为：本发明提供一种从黏土型锂资源中提锂的方法，针对黏土型锂资源的特定技术难点，采用微波焙烧法从黏土型锂资源中提取锂，该方法在较短时间内升温，后加入一定量水浸出、浸出剂价格便宜且锂提取率极高。Compared with the existing technology, the beneficial effects of the present invention are: the present invention provides a method for extracting lithium from clay-type lithium resources. In view of the specific technical difficulties of clay-type lithium resources, the microwave roasting method is used to extract lithium from clay-type lithium resources. Lithium, this method heats up in a short period of time, and then adds a certain amount of water for leaching. The leaching agent is cheap and the lithium extraction rate is extremely high.
附图说明Description of drawings
图1为锂黏土组成XRD定量分析图。Figure 1 shows the XRD quantitative analysis chart of lithium clay composition.
具体实施方式Detailed ways
为更好的说明本发明的目的、技术方案和优点，下面将结合附图和具体实施例对本发明作进一步说明。In order to better explain the purpose, technical solutions and advantages of the present invention, the present invention will be further described below with reference to the drawings and specific embodiments.
实施例中，所使用的实验方法如无特殊说明，均为常规方法，所用的材料、试剂等，如无特殊说明，均可从商业途径得到。In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials and reagents used can be obtained from commercial sources unless otherwise specified.
本发明实施例中所用锂黏土来自贵州某黏土矿，锂黏土中锂含量为0.21％，本发明从锂黏土中提取锂的方法，不限于使用上述锂黏土。The lithium clay used in the embodiments of the present invention comes from a clay mine in Guizhou. The lithium content in the lithium clay is 0.21%. The method of extracting lithium from the lithium clay of the present invention is not limited to the use of the above-mentioned lithium clay.
实施例1-8和对比例1-4Examples 1-8 and Comparative Examples 1-4
实施例1Example 1
本发明实施例的一种从锂黏土中提取锂的方法，包括以下步骤：A method for extracting lithium from lithium clay according to an embodiment of the present invention includes the following steps:
(1)将500克锂黏土进行预处理，得到预处理料；锂黏土预处理的方法为：将锂黏土破碎，与浸出剂混合后球磨；其中，破碎后锂黏土的直径为2-5mm，浸出剂为硫酸钾、硫酸钠和氧化钙的混合物，硫酸钾、硫酸钠、氧化钙的质量比为：硫酸钾：硫酸钠：氧化钙＝1:1：1，球磨后得到的预处理料的直径为50-150μm；锂黏土和浸出剂的质量比为：锂黏土：浸出剂＝5：3；(1) Pretreat 500 grams of lithium clay to obtain pretreated material; the lithium clay pretreatment method is: crush the lithium clay, mix it with the leaching agent and then ball mill; wherein, the diameter of the crushed lithium clay is 2-5mm, The leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide. The mass ratio of potassium sulfate, sodium sulfate and calcium oxide is: potassium sulfate: sodium sulfate: calcium oxide = 1:1:1. The pretreated material obtained after ball milling The diameter is 50-150 μm; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent = 5:3;
(2)将步骤(1)中的预处理料进行微波焙烧、保温、冷却、研磨后，得到粉碎料；微波焙烧的温度为700℃，微波焙烧中微波功率为2kw，微波频率为2450MHz；保温的时间为 1h，冷却至室温，研磨至50-200μm；(2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 700°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200μm;
(3)将步骤(2)中的粉碎料和水混合搅拌浸出，过滤得到含锂浸出液，粉碎料和水的质量比为：粉碎料：水＝1：3，混合搅拌浸出的温度为80℃，浸出时间为1h。(3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution. The mass ratio of the pulverized material and water is: pulverized material: water = 1:3. The temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
实施例2Example 2
本发明实施例的一种从锂黏土中提取锂的方法，包括以下步骤：A method for extracting lithium from lithium clay according to an embodiment of the present invention includes the following steps:
(1)将500克锂黏土进行预处理，得到预处理料；锂黏土预处理的方法为：将锂黏土破碎，与浸出剂混合后球磨；其中，破碎后锂黏土的直径为2-5mm，浸出剂为硫酸钾、硫酸钠和氧化钙的混合物，硫酸钾、硫酸钠、氧化钙的质量比为：硫酸钾：硫酸钠：氧化钙＝1:1：1，球磨后得到的预处理料的直径为50-150μm；锂黏土和浸出剂的质量比为：锂黏土：浸出剂＝5：3；(1) Pretreat 500 grams of lithium clay to obtain pretreated material; the lithium clay pretreatment method is: crush the lithium clay, mix it with the leaching agent and then ball mill; wherein, the diameter of the crushed lithium clay is 2-5mm, The leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide. The mass ratio of potassium sulfate, sodium sulfate and calcium oxide is: potassium sulfate: sodium sulfate: calcium oxide = 1:1:1. The pretreated material obtained after ball milling The diameter is 50-150 μm; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent = 5:3;
(2)将步骤(1)中的预处理料进行微波焙烧、保温、冷却、研磨后，得到粉碎料；微波焙烧的温度为700℃，微波焙烧中微波功率为1kw，微波频率为2450MHz；保温的时间为1h，冷却至室温，研磨至50-200μm；(2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 700°C, the microwave power in microwave roasting is 1kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200μm;
(3)将步骤(2)中的粉碎料和水混合搅拌浸出，过滤得到含锂浸出液，粉碎料和水的质量比为：粉碎料：水＝1：3，混合搅拌浸出的温度为80℃，浸出时间为1h。(3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution. The mass ratio of the pulverized material and water is: pulverized material: water = 1:3. The temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
实施例3Example 3
本发明实施例的一种从锂黏土中提取锂的方法，包括以下步骤：A method for extracting lithium from lithium clay according to an embodiment of the present invention includes the following steps:
(1)将500克锂黏土进行预处理，得到预处理料；锂黏土预处理的方法为：将锂黏土破碎，与浸出剂混合后球磨；其中，破碎后锂黏土的直径为2-5mm，浸出剂为硫酸钾、硫酸钠和氧化钙的混合物，硫酸钾、硫酸钠、氧化钙的质量比为：硫酸钾：硫酸钠：氧化钙＝1：1：1，球磨后得到的预处理料的直径为50-150μm；锂黏土和浸出剂的质量比为：锂黏土：浸出剂＝5：3；(1) Pretreat 500 grams of lithium clay to obtain pretreated material; the lithium clay pretreatment method is: crush the lithium clay, mix it with the leaching agent and then ball mill; wherein, the diameter of the crushed lithium clay is 2-5mm, The leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide. The mass ratio of potassium sulfate, sodium sulfate and calcium oxide is: potassium sulfate: sodium sulfate: calcium oxide = 1:1:1. The pretreated material obtained after ball milling The diameter is 50-150 μm; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent = 5:3;
(2)将步骤(1)中的预处理料进行微波焙烧、保温、冷却、研磨后，得到粉碎料；微波焙烧的温度为700℃，微波焙烧中微波功率为3kw，微波频率为2450MHz；保温的时间为1h，冷却至室温，研磨至50-200μm；(2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 700°C, the microwave power in microwave roasting is 3kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200μm;
(3)将步骤(2)中的粉碎料和水混合搅拌浸出，过滤得到含锂浸出液，粉碎料和水的质量比为：粉碎料：水＝1：3，混合搅拌浸出的温度为80℃，浸出时间为1h。(3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution. The mass ratio of the pulverized material and water is: pulverized material: water = 1:3. The temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
实施例4Example 4
本发明实施例的一种从锂黏土中提取锂的方法，包括以下步骤：A method for extracting lithium from lithium clay according to an embodiment of the present invention includes the following steps:
(1)将500克锂黏土进行预处理，得到预处理料；锂黏土预处理的方法为：将锂黏土破碎，与浸出剂混合后球磨；其中，破碎后锂黏土的直径为2-5mm，浸出剂为硫酸钾、硫酸钠和氧化钙的混合物，硫酸钾、硫酸钠、氧化钙的质量比为：硫酸钾：硫酸钠：氧化钙＝1:1：1，球磨后得到的预处理料的直径为50-150μm；锂黏土和浸出剂的质量比为：锂黏土：浸出剂＝5：3；(1) Pretreat 500 grams of lithium clay to obtain pretreated material; the lithium clay pretreatment method is: crush the lithium clay, mix it with the leaching agent and then ball mill; wherein, the diameter of the crushed lithium clay is 2-5mm, The leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide. The mass ratio of potassium sulfate, sodium sulfate and calcium oxide is: potassium sulfate: sodium sulfate: calcium oxide = 1:1:1. The pretreated material obtained after ball milling The diameter is 50-150 μm; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent = 5:3;
(2)将步骤(1)中的预处理料进行微波焙烧、保温、冷却、研磨后，得到粉碎料；微波焙烧的温度为730℃，微波焙烧中微波功率为2kw，微波频率为2450MHz；保温的时间为1h，冷却至室温，研磨至50-200μm；(2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 730°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200μm;
(3)将步骤(2)中的粉碎料和水混合搅拌浸出，过滤得到含锂浸出液，粉碎料和水的质量比为：粉碎料：水＝1：3，混合搅拌浸出的温度为80℃，浸出时间为1h。(3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution. The mass ratio of the pulverized material and water is: pulverized material: water = 1:3. The temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
实施例5Example 5
本发明实施例的一种从锂黏土中提取锂的方法，包括以下步骤：A method for extracting lithium from lithium clay according to an embodiment of the present invention includes the following steps:
(1)将500克锂黏土进行预处理，得到预处理料；锂黏土预处理的方法为：将锂黏土破碎，与浸出剂混合后球磨；其中，破碎后锂黏土的直径为2-5mm，浸出剂为硫酸钾、硫酸钠和氧化钙的混合物，硫酸钾、硫酸钠、氧化钙的质量比为：硫酸钾：硫酸钠：氧化钙＝1:1：1，球磨后得到的预处理料的直径为50-150μm；锂黏土和浸出剂的质量比为：锂黏土：浸出剂＝5：3；(1) Pretreat 500 grams of lithium clay to obtain pretreated material; the lithium clay pretreatment method is: crush the lithium clay, mix it with the leaching agent and then ball mill; wherein, the diameter of the crushed lithium clay is 2-5mm, The leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide. The mass ratio of potassium sulfate, sodium sulfate and calcium oxide is: potassium sulfate: sodium sulfate: calcium oxide = 1:1:1. The pretreated material obtained after ball milling The diameter is 50-150 μm; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent = 5:3;
(2)将步骤(1)中的预处理料进行微波焙烧、保温、冷却、研磨后，得到粉碎料；微波焙烧的温度为750℃，微波焙烧中微波功率为2kw，微波频率为2450MHz；保温的时间为1h，冷却至室温，研磨至50-200μm；(2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 750°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200μm;
(3)将步骤(2)中的粉碎料和水混合搅拌浸出，过滤得到含锂浸出液，粉碎料和水的质量比为：粉碎料：水＝1：3，混合搅拌浸出的温度为80℃，浸出时间为1h。(3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution. The mass ratio of the pulverized material and water is: pulverized material: water = 1:3. The temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
实施例6Example 6
本发明实施例的一种从锂黏土中提取锂的方法，包括以下步骤：A method for extracting lithium from lithium clay according to an embodiment of the present invention includes the following steps:
(1)将500克锂黏土进行预处理，得到预处理料；锂黏土预处理的方法为：将锂黏土破碎，与浸出剂混合后球磨；其中，破碎后锂黏土的直径为2-5mm，浸出剂为硫酸钾、硫酸钠和氧化钙的混合物，硫酸钾、硫酸钠、氧化钙的质量比为：硫酸钾：硫酸钠：氧化钙＝1:1：1， 球磨后得到的预处理料的直径为50-150μm；锂黏土和浸出剂的质量比为：锂黏土：浸出剂＝5：3；(1) Pretreat 500 grams of lithium clay to obtain pretreated material; the lithium clay pretreatment method is: crush the lithium clay, mix it with the leaching agent and then ball mill; wherein, the diameter of the crushed lithium clay is 2-5mm, The leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide. The mass ratio of potassium sulfate, sodium sulfate and calcium oxide is: potassium sulfate: sodium sulfate: calcium oxide = 1:1:1. The pretreated material obtained after ball milling The diameter is 50-150 μm; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent = 5:3;
(2)将步骤(1)中的预处理料进行微波焙烧、保温、冷却、研磨后，得到粉碎料；微波焙烧的温度为650℃，微波焙烧中微波功率为2kw，微波频率为2450MHz；保温的时间为1h，冷却至室温，研磨至50-200μm；(2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 650°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200μm;
(3)将步骤(2)中的粉碎料和水混合搅拌浸出，过滤得到含锂浸出液，粉碎料和水的质量比为：粉碎料：水＝1：3，混合搅拌浸出的温度为80℃，浸出时间为1h。(3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution. The mass ratio of the pulverized material and water is: pulverized material: water = 1:3. The temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
实施例7Example 7
本发明实施例的一种从锂黏土中提取锂的方法，包括以下步骤：A method for extracting lithium from lithium clay according to an embodiment of the present invention includes the following steps:
(1)将500克锂黏土进行预处理，得到预处理料；锂黏土预处理的方法为：将锂黏土破碎，与浸出剂混合后球磨；其中，破碎后锂黏土的直径为2-5mm，浸出剂为硫酸钾和氧化钙的混合物，硫酸钾、氧化钙的质量比为：硫酸钾：氧化钙＝1：1，球磨后得到的预处理料的直径为50-150μm；锂黏土和浸出剂的质量比为：锂黏土：浸出剂＝5：1；(1) Pretreat 500 grams of lithium clay to obtain pretreated material; the lithium clay pretreatment method is: crush the lithium clay, mix it with the leaching agent and then ball mill; wherein, the diameter of the crushed lithium clay is 2-5mm, The leaching agent is a mixture of potassium sulfate and calcium oxide. The mass ratio of potassium sulfate and calcium oxide is: potassium sulfate: calcium oxide = 1:1. The diameter of the pretreated material obtained after ball milling is 50-150 μm; lithium clay and leaching agent The mass ratio is: lithium clay: leaching agent = 5:1;
(2)将步骤(1)中的预处理料进行微波焙烧、保温、冷却、研磨后，得到粉碎料；微波焙烧的温度为700℃，微波焙烧中微波功率为2kw，微波频率为2450MHz；保温的时间为4h，冷却至室温，研磨至50-200μm；(2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 700°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 4h, cool to room temperature, and grind to 50-200μm;
(3)将步骤(2)中的粉碎料和水混合搅拌浸出，过滤得到含锂浸出液，粉碎料和水的质量比为：粉碎料：水＝1：5，混合搅拌浸出的温度为85℃，浸出时间为2h。(3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leachate. The mass ratio of the pulverized material and water is: pulverized material: water = 1:5. The temperature for mixing, stirring and leaching is 85°C. , the leaching time is 2h.
实施例8Example 8
本发明实施例的一种从锂黏土中提取锂的方法，包括以下步骤：A method for extracting lithium from lithium clay according to an embodiment of the present invention includes the following steps:
(1)将500克锂黏土进行预处理，得到预处理料；锂黏土预处理的方法为：将锂黏土破碎，与浸出剂混合后球磨；其中，破碎后锂黏土的直径为2-5mm，浸出剂为硫酸钠和氧化钙的混合物，硫酸钠、氧化钙的质量比为：硫酸钠：氧化钙＝2：1，球磨后得到的预处理料的直径为50-150μm；锂黏土和浸出剂的质量比为：锂黏土：浸出剂＝5：4；(1) Pretreat 500 grams of lithium clay to obtain pretreated material; the lithium clay pretreatment method is: crush the lithium clay, mix it with the leaching agent and then ball mill; wherein, the diameter of the crushed lithium clay is 2-5mm, The leaching agent is a mixture of sodium sulfate and calcium oxide. The mass ratio of sodium sulfate and calcium oxide is: sodium sulfate: calcium oxide = 2:1. The diameter of the pretreated material obtained after ball milling is 50-150 μm; lithium clay and leaching agent The mass ratio is: lithium clay: leaching agent = 5:4;
(2)将步骤(1)中的预处理料进行微波焙烧、保温、冷却、研磨后，得到粉碎料；微波焙烧的温度为700℃，微波焙烧中微波功率为2kw，微波频率为2450MHz；保温的时间为3h，冷却至室温，研磨至50-200μm；(2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 700°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 3h, cool to room temperature, and grind to 50-200μm;
(3)将步骤(2)中的粉碎料和水混合搅拌浸出，过滤得到含锂浸出液，粉碎料和水的 质量比为：粉碎料：水＝1：3，混合搅拌浸出的温度为60℃，浸出时间为1h。(3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leach solution. The mass ratio of the pulverized material and water is: pulverized material: water = 1:3. The temperature for mixing, stirring and leaching is 60°C. , the leaching time is 1h.
对比例1Comparative example 1
对比例1与实施例1进行单一对比，仅步骤(2)微波焙烧的功率和温度不同。Comparative Example 1 is compared with Example 1. Only the power and temperature of microwave roasting in step (2) are different.
具体地，对比例1的从锂黏土中提取锂的方法，包括以下步骤：Specifically, the method for extracting lithium from lithium clay in Comparative Example 1 includes the following steps:
(1)将500克锂黏土进行预处理，得到预处理料；锂黏土预处理的方法为：将锂黏土破碎，与浸出剂混合后球磨；其中，破碎后锂黏土的直径为2-5mm，浸出剂为硫酸钾、硫酸钠和氧化钙的混合物，硫酸钾、硫酸钠、氧化钙的质量比为：硫酸钾：硫酸钠：氧化钙＝1:1：1，球磨后得到的预处理料的直径为50-150μm；锂黏土和浸出剂的质量比为：锂黏土：浸出剂＝5：3；(1) Pretreat 500 grams of lithium clay to obtain pretreated material; the lithium clay pretreatment method is: crush the lithium clay, mix it with the leaching agent and then ball mill; wherein, the diameter of the crushed lithium clay is 2-5mm, The leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide. The mass ratio of potassium sulfate, sodium sulfate and calcium oxide is: potassium sulfate: sodium sulfate: calcium oxide = 1:1:1. The pretreated material obtained after ball milling The diameter is 50-150 μm; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent = 5:3;
(2)将步骤(1)中的预处理料进行微波焙烧、保温、冷却、研磨后，得到粉碎料；微波焙烧的温度为550℃，微波焙烧中微波功率为0.5kw，微波频率为2450MHz；保温的时间为1h，冷却至室温，研磨至50-200μm；(2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 550°C, the microwave power in microwave roasting is 0.5kw, and the microwave frequency is 2450MHz; The heat preservation time is 1 hour, cool to room temperature, and grind to 50-200 μm;
(3)将步骤(2)中的粉碎料和水混合搅拌浸出，过滤得到含锂浸出液，粉碎料和水的质量比为：粉碎料：水＝1：3，混合搅拌浸出的温度为80℃，浸出时间为1h。(3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution. The mass ratio of the pulverized material and water is: pulverized material: water = 1:3. The temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
对比例2Comparative example 2
对比例2与实施例1进行单一对比，仅步骤(2)微波焙烧的功率和温度不同。Comparative Example 2 is compared with Example 1. Only the power and temperature of microwave roasting in step (2) are different.
具体地，对比例2的从锂黏土中提取锂的方法，包括以下步骤：Specifically, the method of extracting lithium from lithium clay in Comparative Example 2 includes the following steps:
(1)将500克锂黏土进行预处理，得到预处理料；锂黏土预处理的方法为：将锂黏土破碎，与浸出剂混合后球磨；其中，破碎后锂黏土的直径为2-5mm，浸出剂为硫酸钾、硫酸钠和氧化钙的混合物，硫酸钾、硫酸钠、氧化钙的质量比为：硫酸钾：硫酸钠：氧化钙＝1:1：1，球磨后得到的预处理料的直径为50-150μm；锂黏土和浸出剂的质量比为：锂黏土：浸出剂＝5：3；(1) Pretreat 500 grams of lithium clay to obtain pretreated material; the lithium clay pretreatment method is: crush the lithium clay, mix it with the leaching agent and then ball mill; wherein, the diameter of the crushed lithium clay is 2-5mm, The leaching agent is a mixture of potassium sulfate, sodium sulfate and calcium oxide. The mass ratio of potassium sulfate, sodium sulfate and calcium oxide is: potassium sulfate: sodium sulfate: calcium oxide = 1:1:1. The pretreated material obtained after ball milling The diameter is 50-150 μm; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent = 5:3;
(2)将步骤(1)中的预处理料进行微波焙烧、保温、冷却、研磨后，得到粉碎料；微波焙烧的温度为600℃，微波焙烧中微波功率为2kw，微波频率为2450MHz；保温的时间为1h，冷却至室温，研磨至50-200μm；(2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 600°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200μm;
(3)将步骤(2)中的粉碎料和水混合搅拌浸出，过滤得到含锂浸出液，粉碎料和水的质量比为：粉碎料：水＝1：3，混合搅拌浸出的温度为80℃，浸出时间为1h。(3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution. The mass ratio of the pulverized material and water is: pulverized material: water = 1:3. The temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
对比例3Comparative example 3
对比例3与实施例1进行单一对比，仅步骤(2)微波焙烧的功率和温度不同。Comparative Example 3 is compared with Example 1. Only the power and temperature of microwave roasting in step (2) are different.
具体地，对比例3的从锂黏土中提取锂的方法，包括以下步骤：Specifically, the method of extracting lithium from lithium clay in Comparative Example 3 includes the following steps:
(1)将500克锂黏土进行预处理，得到预处理料；锂黏土预处理的方法为：将锂黏土破碎，与浸出剂混合后球磨；其中，破碎后锂黏土的直径为2-5mm，浸出剂为硫酸钾、硫酸钠、氧化钙的混合物，硫酸钾、硫酸钠、氧化钙的质量比为：硫酸钾：硫酸钠：氧化钙＝1:1：1，球磨后得到的预处理料的直径为50-150μm；锂黏土和浸出剂的质量比为：锂黏土：浸出剂＝5：3；(1) Pretreat 500 grams of lithium clay to obtain pretreated material; the lithium clay pretreatment method is: crush the lithium clay, mix it with the leaching agent and then ball mill; wherein, the diameter of the crushed lithium clay is 2-5mm, The leaching agent is a mixture of potassium sulfate, sodium sulfate, and calcium oxide. The mass ratio of potassium sulfate, sodium sulfate, and calcium oxide is: potassium sulfate: sodium sulfate: calcium oxide = 1:1:1. The pretreated material obtained after ball milling The diameter is 50-150 μm; the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent = 5:3;
(2)将步骤(1)中的预处理料进行微波焙烧、保温、冷却、研磨后，得到粉碎料；微波焙烧的温度为800℃，微波焙烧中微波功率为2kw，微波频率为2450MHz；保温的时间为1h，冷却至室温，研磨至50-200μm；(2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 800°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200μm;
(3)将步骤(2)中的粉碎料和水混合搅拌浸出，过滤得到含锂浸出液，粉碎料和水的质量比为：粉碎料：水＝1：3，混合搅拌浸出的温度为80℃，浸出时间为1h。(3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution. The mass ratio of the pulverized material and water is: pulverized material: water = 1:3. The temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
对比例4Comparative example 4
对比例4与实施例1进行单一对比，仅步骤(1)浸出剂的选择不同.Comparative Example 4 is a single comparison with Example 1, only the selection of the leaching agent in step (1) is different.
具体地，对比例4的从锂黏土中提取锂的方法，包括以下步骤：Specifically, the method of extracting lithium from lithium clay in Comparative Example 4 includes the following steps:
(1)将500克锂黏土进行预处理，得到预处理料；锂黏土预处理的方法为：将锂黏土破碎，与浸出剂混合后球磨；其中，破碎后锂黏土的直径为2-5mm，浸出剂为硫酸钾和硫酸钠的混合物，硫酸钾和硫酸钠的质量比为：硫酸钾：硫酸钠＝1:1，球磨后得到的预处理料的直径为50-150μm；锂黏土和浸出剂的质量比为：锂黏土：浸出剂＝5：3；(1) Pretreat 500 grams of lithium clay to obtain pretreated material; the lithium clay pretreatment method is: crush the lithium clay, mix it with the leaching agent and then ball mill; wherein, the diameter of the crushed lithium clay is 2-5mm, The leaching agent is a mixture of potassium sulfate and sodium sulfate. The mass ratio of potassium sulfate and sodium sulfate is: potassium sulfate: sodium sulfate = 1:1. The diameter of the pretreated material obtained after ball milling is 50-150 μm; lithium clay and leaching agent The mass ratio is: lithium clay: leaching agent = 5:3;
(2)将步骤(1)中的预处理料进行微波焙烧、保温、冷却、研磨后，得到粉碎料；微波焙烧的温度为700℃，微波焙烧中微波功率为2kw，微波频率为2450MHz；保温的时间为1h，冷却至室温，研磨至50-200μm；(2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the temperature of microwave roasting is 700°C, the microwave power in microwave roasting is 2kw, and the microwave frequency is 2450MHz; heat preservation The time is 1h, cool to room temperature, and grind to 50-200μm;
(3)将步骤(2)中的粉碎料和水混合搅拌浸出，过滤得到含锂浸出液，粉碎料和水的质量比为：粉碎料：水＝1：3，混合搅拌浸出的温度为80℃，浸出时间为1h。(3) Mix and stir the pulverized material in step (2) with water for leaching, and filter to obtain the lithium-containing leaching solution. The mass ratio of the pulverized material and water is: pulverized material: water = 1:3. The temperature for mixing, stirring and leaching is 80°C. , the leaching time is 1h.
实施例1-8及对比例1-4从锂黏土中提取锂的方法中，不同功率升温到目标温度用时如表1所示：In the methods of extracting lithium from lithium clay in Examples 1-8 and Comparative Examples 1-4, the time it takes to heat up to the target temperature with different powers is as shown in Table 1:
表1Table 1
编号serial number 目标温度(℃)Target temperature(℃) 升温功率(kw)Heating power (kw) 升温时间(min)Heating time (min)
实施例1Example 1 700700 22 1414
实施例2Example 2 700700 11 1616
实施例3Example 3 700700 33 1111
实施例4Example 4 730730 22 14.514.5
实施例5Example 5 750750 22 1515
实施例6Example 6 650650 22 1313
实施例7Example 7 700700 22 1414
实施例8Example 8 700700 22 1414
对比例1Comparative example 1 550550 0.50.5 8080
对比例2Comparative example 2 600600 22 1212
对比例3Comparative example 3 800800 22 1616
对比例4Comparative example 4 700700 22 1414
性能测试Performance Testing
测试标准：采用原子吸收分光光度计检测，根据国标GB/T 15337-2008。其中锂浸出率＝(含锂浸出液体积*浸出液中锂浓度)/(锂黏土质量*锂黏土中锂百分含量)，其中锂黏土中锂含量为0.21％；本发明在实际实验过程中，含锂浸出液在浸出过程略有损失，具体实施例及对比例含锂浸出液体积如下表2所示；Testing standards: Detected using atomic absorption spectrophotometer, in accordance with national standard GB/T 15337-2008. The lithium leaching rate = (volume of lithium-containing leach solution * lithium concentration in the leach solution) / (mass of lithium clay * percentage of lithium in the lithium clay), where the lithium content in the lithium clay is 0.21%; during the actual experimental process of the present invention, The lithium leachate is slightly lost during the leaching process. Specific examples and comparative examples contain lithium leachate volumes as shown in Table 2 below;
测试结果：如表2所示；Test results: as shown in Table 2;
表2Table 2
Figure PCTCN2022122264-appb-000001
Figure PCTCN2022122264-appb-000001
Figure PCTCN2022122264-appb-000002
Figure PCTCN2022122264-appb-000002
Figure PCTCN2022122264-appb-000003
Figure PCTCN2022122264-appb-000003
由上表可知，本发明实施例1-8从锂黏土中提取锂的方法，采用微波焙烧法从黏土型锂资源中提取锂，该方法在较短时间内升温，最终锂浸出率为95％以上。由实施例1、实施例4-6对比可知，微波焙烧中微波功率为1-3kw，焙烧温度700-750℃时，最终锂浸出率为96％以上；当微波焙烧中焙烧温度730℃时，锂浸出率达到最佳，浸出率98％以上。As can be seen from the above table, the methods for extracting lithium from lithium clay in Examples 1-8 of the present invention use microwave roasting to extract lithium from clay-type lithium resources. This method heats up in a relatively short time, and the final lithium leaching rate is 95%. above. It can be seen from the comparison between Example 1 and Examples 4-6 that when the microwave power is 1-3kw and the roasting temperature is 700-750°C, the final lithium leaching rate is more than 96%; when the roasting temperature is 730°C, The lithium leaching rate reaches the optimal level, with a leaching rate of over 98%.
对比例1微波焙烧功率较低，在0.5kw下加热锂黏土达到的最高温度约为550℃，且加热时间较长，需要80min左右，且最终锂浸出率为72.1％，明显低于本发明实施例最终锂浸出率。对比例2中微波焙烧功率为2kw，微波焙烧的温度为600℃，低于本发明限定的微波焙烧温度，最终锂浸出率明显低于本发明实施例最终锂浸出率。对比例3微波焙烧功率为2kw，微波焙烧的温度为800℃，高于本发明限定的微波焙烧温度，最终锂浸出率明显低于本发明实施例最终锂浸出率。对比例4中浸出剂不含氧化钙，钾盐或钠盐难以直接和锂绿泥石中二氧化硅发生反应，需要加入氧化钙固化SiO 2破坏晶格，生成硅酸钙从而实现钠/钾同锂的进行离子交换，本对比例中未加入氧化钙破坏晶格，锂不能有效地与Na/K进行置换反应，导致锂浸出率较低。 Comparative Example 1 has low microwave roasting power. The maximum temperature reached by heating lithium clay at 0.5kw is about 550°C, and the heating time is long, requiring about 80 minutes. The final lithium leaching rate is 72.1%, which is significantly lower than the implementation of the present invention. Example final lithium leaching rate. In Comparative Example 2, the microwave roasting power is 2kw, the microwave roasting temperature is 600°C, which is lower than the microwave roasting temperature limited by the present invention, and the final lithium leaching rate is significantly lower than the final lithium leaching rate of the embodiment of the present invention. Comparative Example 3 The microwave roasting power is 2kw, the microwave roasting temperature is 800°C, which is higher than the microwave roasting temperature limited by the present invention, and the final lithium leaching rate is significantly lower than the final lithium leaching rate of the embodiments of the present invention. The leaching agent in Comparative Example 4 does not contain calcium oxide. It is difficult for potassium salt or sodium salt to directly react with the silica in the lithium chlorite. Calcium oxide needs to be added to solidify SiO 2 to destroy the crystal lattice and generate calcium silicate to achieve sodium/potassium. For ion exchange with lithium, calcium oxide was not added to destroy the crystal lattice in this comparative example, and lithium could not effectively carry out replacement reaction with Na/K, resulting in a low lithium leaching rate.
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and do not limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that The technical solution of the present invention may be modified or equivalently substituted without departing from the essence and scope of the technical solution of the present invention.

Claims (10)

  1. 一种从锂黏土中提取锂的方法，其特征在于，包括以下步骤：A method for extracting lithium from lithium clay, characterized by comprising the following steps:
    (1)将锂黏土进行预处理，得到预处理料；(1) Pretreat lithium clay to obtain pretreated material;
    (2)将步骤(1)中的预处理料进行微波焙烧、保温、冷却、研磨后，得到粉碎料；微波焙烧中微波功率为1-3kw，微波焙烧的温度为650-750℃；(2) The pretreated material in step (1) is subjected to microwave roasting, heat preservation, cooling and grinding to obtain pulverized material; the microwave power in microwave roasting is 1-3kw, and the temperature of microwave roasting is 650-750°C;
    (3)将步骤(2)中的粉碎料和水混合搅拌浸出，过滤得到含锂浸出液。(3) Mix the crushed material in step (2) with water, stir, and leach, and filter to obtain a lithium-containing leachate.
  2. 如权利要求1所述的从锂黏土中提取锂的方法，其特征在于，所述步骤(1)中，锂黏土预处理的方法为：将锂黏土破碎，与浸出剂混合后球磨；其中，破碎后锂黏土的直径为2-5mm，球磨后得到的预处理料的直径为50-150μm。The method of extracting lithium from lithium clay according to claim 1, characterized in that in the step (1), the lithium clay pretreatment method is: crushing the lithium clay, mixing it with a leaching agent and then ball milling; wherein, The diameter of the crushed lithium clay is 2-5mm, and the diameter of the pretreated material obtained after ball milling is 50-150μm.
  3. 如权利要求2所述的从锂黏土中提取锂的方法，其特征在于，所述步骤(1)中，锂黏土和浸出剂的质量比为：锂黏土：浸出剂＝5：(1-4)。The method for extracting lithium from lithium clay according to claim 2, characterized in that in the step (1), the mass ratio of lithium clay and leaching agent is: lithium clay: leaching agent = 5: (1-4 ).
  4. 如权利要求2所述的从锂黏土中提取锂的方法，其特征在于，所述浸出剂为硫酸盐和氧化钙的混合物。The method for extracting lithium from lithium clay according to claim 2, wherein the leaching agent is a mixture of sulfate and calcium oxide.
  5. 如权利要求4所述的从锂黏土中提取锂的方法，其特征在于，所述硫酸盐为硫酸钾、硫酸钠中的至少一种。The method for extracting lithium from lithium clay according to claim 4, wherein the sulfate is at least one of potassium sulfate and sodium sulfate.
  6. 如权利要求4所述的从锂黏土中提取锂的方法，其特征在于，所述步骤(1)中，硫酸盐和氧化钙的质量比为：硫酸盐：氧化钙＝(1-2)：1。The method for extracting lithium from lithium clay according to claim 4, wherein in step (1), the mass ratio of sulfate and calcium oxide is: sulfate:calcium oxide=(1-2): 1.
  7. 如权利要求1所述的从锂黏土中提取锂的方法，其特征在于，所述步骤(2)中，微波焙烧频率为2450MHz；保温的时间为1-4h，冷却至20-35℃，研磨至50-200μm。The method for extracting lithium from lithium clay according to claim 1, characterized in that in the step (2), the microwave roasting frequency is 2450MHz; the heat preservation time is 1-4h, cooled to 20-35°C, and ground to 50-200μm.
  8. 如权利要求1所述的从锂黏土中提取锂的方法，其特征在于，所述步骤(2)中，微波焙烧的温度为700-750℃。The method for extracting lithium from lithium clay according to claim 1, wherein in step (2), the temperature of microwave roasting is 700-750°C.
  9. 如权利要求8所述的从锂黏土中提取锂的方法，其特征在于，所述步骤(2)中，微波焙烧的温度为730℃。The method for extracting lithium from lithium clay according to claim 8, wherein in step (2), the temperature of microwave roasting is 730°C.
  10. 如权利要求1所述的从锂黏土中提取锂的方法，其特征在于，所述步骤(3)中，粉碎料和水的质量比为：粉碎料：水＝1：(3-5)，混合搅拌浸出的温度为60-85℃，浸出时间为1-2h。The method for extracting lithium from lithium clay according to claim 1, characterized in that in the step (3), the mass ratio of the crushed material and water is: crushed material: water=1: (3-5), The temperature of mixing, stirring and leaching is 60-85°C, and the leaching time is 1-2 hours.
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