WO2023226546A1 - Method for recycling lithium from lithium clay - Google Patents

Method for recycling lithium from lithium clay Download PDF

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Publication number
WO2023226546A1
WO2023226546A1 PCT/CN2023/081687 CN2023081687W WO2023226546A1 WO 2023226546 A1 WO2023226546 A1 WO 2023226546A1 CN 2023081687 W CN2023081687 W CN 2023081687W WO 2023226546 A1 WO2023226546 A1 WO 2023226546A1
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Prior art keywords
lithium
clay
roasting
leaching
acid
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PCT/CN2023/081687
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French (fr)
Chinese (zh)
Inventor
包冬莲
李长东
阮丁山
陈若葵
乔延超
李波
Original Assignee
广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
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Publication of WO2023226546A1 publication Critical patent/WO2023226546A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • 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
    • 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
    • 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 invention belongs to the technical field of lithium extraction from lithium ore, and specifically relates to a method for recovering lithium from lithium clay.
  • lithium as a key element in lithium-ion batteries, has attracted more and more attention from the industry.
  • Lithium salt products represented by lithium carbonate and lithium hydroxide are 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.
  • 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.
  • the mining and smelting of clay minerals has great development prospects.
  • Patent application CN110358931A discloses an ion exchange method for extracting lithium from carbonated clay lithium ore. This method uses ferric salt and roasted clay clinker to achieve lithium leaching in the form of ion exchange at 85°C, but the leaching rate is biased. Low, the consumption of iron salt is high, and industrialization is difficult; patent application CN111893318A discloses a method for extracting lithium from lithium-containing clay. This method roasts the ball-milled lithium clay with calcium carbonate, sodium sulfate, and potassium sulfate in a certain proportion. , crushed and leached to obtain a lithium-containing solution.
  • the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a method for recovering lithium from lithium clay. This method has simple process, high feasibility, low process energy consumption, and is suitable for low-grade lithium clay. Soil has a higher lithium leaching rate.
  • a method for recovering lithium from lithium clay including the following steps:
  • S1 Crush the lithium clay raw material to obtain lithium clay powder, and perform the first roasting of the lithium clay powder to obtain the primary roasting material;
  • S2 Mix the primary roasting material with an additive and then grind it to obtain a grinding material;
  • the additive is at least one of sodium salt, potassium salt, sodium hydroxide or potassium hydroxide;
  • the secondary roasting material is leached by adding a leaching agent, and solid-liquid separation is performed to obtain a leaching liquid.
  • step S1 the lithium content of the lithium clay raw material is 0.1-0.8 wt%.
  • the particle size of the lithium clay powder is 50-300 mesh.
  • the particle size of the lithium clay powder is 100-200 mesh.
  • the temperature of the first roasting is 600-1200°C.
  • the temperature of the first roasting is 600-900°C.
  • the first roasting time is 1-8 hours.
  • the first roasting time is 2-4 hours.
  • the additive in step S2, is at least one of NaOH, KOH, Na 2 CO 3 , K 2 CO 3 , CH 3 COONa, CH 3 COOK, NaHCO 3 or KHCO 3 .
  • Na and K have smaller ionic radii and higher ion exchange kinetics.
  • it avoids the introduction of Ca and Mg, which increases the difficulty of subsequent lithium solution recovery and reduces subsequent impurity removal costs.
  • the mass ratio of the additive to the primary roasting material is 1: (5-30).
  • the mass ratio of the additive to the primary roasting material is 1: (10-20).
  • the grinding speed is 100-1200 rpm.
  • the grinding speed is 500-800 rpm.
  • the grinding time is 1-12 hours. Preferably, the grinding time is 2-6 hours.
  • step S2 the grinding uses one of a planetary ball mill, a horizontal ball mill, a crusher or a vibrating ball mill.
  • the acid is at least one of hydrochloric acid, sulfuric acid or nitric acid.
  • the mass concentration of the acid is 2-50%. Preferably, the mass concentration of the acid is 5-10%.
  • the mass ratio of the acid to the abrasive is (0.2-2):1.
  • the mass ratio of the acid to the grinding material is (0.5-1):1.
  • the structure of lithium-containing clay minerals is complex, and there are various structures such as volcanic rock type and carbonate rock type. Considering process compatibility and cost, adding a small amount of acid and roasting at low temperature is beneficial to the leaching of residual lithium and is also beneficial to different lithium-containing structures. Extraction of lithium from clay minerals.
  • the temperature of the second roasting is 150-300°C.
  • the temperature of the second roasting is 200-250°C.
  • the second roasting time is 1-10 h.
  • the second roasting time is 2-4 hours.
  • step S4 the leachate is recycled as the leachant to enrich lithium.
  • the leaching agent is water, or at least one selected from sulfuric acid, hydrochloric acid, nitric acid or saturated carbonic acid solution. Further, the concentration of sulfuric acid, hydrochloric acid or nitric acid is 1-2mol/L.
  • the leaching agent is water.
  • the present invention realizes lithium extraction from lithium clay based on primary roasting, high-energy grinding and secondary acidification roasting.
  • the structural hydroxyl groups in the clay mineral are first removed through primary roasting, which increases the lattice spacing of the clay mineral and is conducive to the removal of lithium ions. Intercalation and exchange; then through high-energy grinding, local high-energy collision occurs between the material and the additive, which further destroys the structure of the clay mineral and provides the activation energy required for the reaction, causing ion exchange between Na + /K + and Li + in the clay mineral.
  • ground simultaneously The process reduces the particle size, which is beneficial to improving ion exchange kinetics.
  • the ground lithium exists in the form of carbonate/bicarbonate, etc.
  • This process can achieve the separation of most of the lattice lithium; and then through secondary acidification and roasting, Add a certain amount of acid to convert the detached lithium into easily soluble lithium salts.
  • the acid is used to deeply extract lithium from the clay ore during the roasting process.
  • the acidified and roasted materials are leached using a leaching agent.
  • the leached lithium solution can be Cyclic leaching achieves lithium enrichment. This process is suitable for leaching lithium from low-grade lithium clay ores, with high leaching rate, high lithium concentration in the leach solution, and strong process compatibility. It is suitable for the extraction of lithium from different lithium-containing clay ores and has great application prospects.
  • Figure 1 is a process flow diagram of the present invention.
  • a method of recovering lithium from lithium clay Refer to Figure 1. The specific process is:
  • the obtained secondary roasting material is leached by adding pure water at a liquid-to-solid ratio of 3:1 mL/g.
  • the leachate and leaching residue are separated to obtain the leachate.
  • the leachate is used as a leachant and circulated for three times to achieve lithium enrichment.
  • the enriched leachate is subjected to lithium Recycle.
  • the composition of the lithium clay, the leaching residue and the leaching liquid in this example an inductively coupled plasma emission spectrometer was used (ICP-OES) and atomic absorption spectrophotometer detection, the detection results are shown in Table 1.
  • the lithium leaching rate (leaching liquid volume * lithium concentration) / (leaching material mass * lithium content) * 100%.
  • the calculated lithium leaching rate in S5 is 90.5%.
  • the lithium concentration in the leaching liquid reaches 90.5% after three cycles of enrichment. 3095ppm.
  • a method for recovering lithium from lithium clay is:
  • the obtained secondary roasting material is leached by adding pure water at a liquid-to-solid ratio of 3:1 mL/g.
  • the solid-liquid separation is performed to obtain the leachate and leaching residue.
  • the leachate is used as a leachant and circulated for three times to achieve lithium enrichment.
  • the composition of the lithium clay, the leaching residue and the leaching liquid in this embodiment were detected using an inductively coupled plasma optical emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer.
  • ICP-OES inductively coupled plasma optical emission spectrometer
  • atomic absorption spectrophotometer atomic absorption spectrophotometer.
  • Table 2 The detection results are shown in Table 2.
  • the lithium leaching rate (leaching liquid volume * lithium concentration) / (leaching material mass * lithium content) * 100%
  • the calculated lithium leaching rate in S5 is 89.2%
  • the lithium concentration in the leach liquid reaches 89.2% after three cycles of enrichment. 3375 ppm.
  • a method for recovering lithium from lithium clay is:
  • the obtained secondary roasting material is leached by adding pure water at a liquid-to-solid ratio of 3:1 mL/g.
  • the solid-liquid separation is performed to obtain the leachate and leaching residue.
  • the leachate is used as a leachant and circulated for three times to achieve lithium enrichment.
  • the composition of the lithium clay, the leaching residue and the leaching liquid in this embodiment were detected using an inductively coupled plasma optical emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer.
  • ICP-OES inductively coupled plasma optical emission spectrometer
  • atomic absorption spectrophotometer atomic absorption spectrophotometer.
  • the calculated lithium leaching rate in S5 is 95.5%.
  • the lithium concentration in the leaching liquid reaches 95.5% after three cycles of enrichment. 3998ppm.
  • a method for recovering lithium from lithium clay is:
  • the obtained secondary roasting material is leached by adding pure water at a liquid-to-solid ratio of 3:1 mL/g.
  • the solid-liquid separation is performed to obtain the leachate and leaching residue.
  • the leachate is used as a leachant and circulated for three times to achieve lithium enrichment.
  • the composition of the lithium clay, the leaching residue and the leaching liquid in this embodiment were tested using an inductively coupled plasma optical emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer.
  • ICP-OES inductively coupled plasma optical emission spectrometer
  • atomic absorption spectrophotometer atomic absorption spectrophotometer.
  • the calculated lithium leaching rate in S5 is 97.5%.
  • the lithium concentration in the leaching liquid reaches 97.5% after three cycles of enrichment. 4025ppm.
  • a method for recovering lithium from lithium clay The difference from Example 1 is that no acid is added to the secondary roasting.
  • the specific process is:
  • the obtained secondary roasting mixture is leached with pure water at a liquid-to-solid ratio of 3:1 mL/g.
  • the solid-liquid separation is performed to obtain the leachate and leaching residue.
  • the leachate is used as a leachant and circulated for three times to achieve lithium enrichment.
  • the composition of the lithium clay as well as the leaching residue and leachate of this comparative example were tested using an inductively coupled plasma optical emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer.
  • ICP-OES inductively coupled plasma optical emission spectrometer
  • atomic absorption spectrophotometer atomic absorption spectrophotometer.
  • the calculated lithium leaching rate in S5 is 72.3%.
  • the lithium concentration in the leaching liquid reaches 72.3% after three cycles of enrichment. 2573ppm.
  • Comparative Example 1 has not been acidified and roasted. As can be seen from Table 5, the leaching rate of lithium is low. This is because Comparative Example 1 has only undergone high-energy ball milling. The ball milling process itself is a solid-phase reaction with limited reaction kinetics. The ball milling process alone is Lithium cannot be completely leached. Example: Adding a small amount of acid and performing acidification roasting at low temperature can deeply extract lithium from clay minerals and increase the lithium leaching rate.

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  • Engineering & Computer Science (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

A method for recycling lithium from lithium clay, comprising: roasting lithium clay powder for the first time, mixing the primary roasted material with an additive, grinding to obtain a ground material, mixing the ground material with acid, roasting for the second time, and adding a leaching agent into the secondary roasted material for leaching to obtain a leachate. Lithium extraction of the lithium clay is realized on the basis of primary roasting, high-energy grinding and secondary acidification roasting, and the structural hydroxyl in the clay ore is removed by means of one-time roasting, such that the lattice spacing of the clay ore is increased, and the deintercalation and exchange of lithium ions are facilitated; then the structure of the clay ore is further damaged by means of high-energy grinding, such that ion exchange occurs between Na+/K+ and Li+ in the clay ore; the separated lithium is converted into soluble lithium salt by means of secondary acidification roasting, and meanwhile, the acid is used for deeply extracting lithium in the clay ore in the roasting process, and the process is suitable for leaching lithium from low-grade lithium clay.

Description

一种从锂黏土中回收锂的方法A method for recovering lithium from lithium clay 技术领域Technical field
本发明属于锂矿石提锂技术领域，具体涉及一种从锂黏土中回收锂的方法。The invention belongs to the technical field of lithium extraction from lithium ore, and specifically relates to a method for recovering lithium from lithium clay.
背景技术Background technique
随着锂离子电池的迅速推广，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 rapid promotion of lithium-ion batteries, lithium, as a key element in lithium-ion batteries, has attracted more and more attention from the industry. Lithium salt products represented by lithium carbonate and lithium hydroxide are 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。相对于十分有限、日渐枯竭、价格高昂的锂辉石、锂云母矿，黏土矿的开采和冶炼十分具有发展前景。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. Compared with the very limited, increasingly depleted and expensive spodumene and lepidolite ores, the mining and smelting of clay minerals has great development prospects.
针对锂黏土中锂的回收，目前国内相关提锂技术十分有限。专利申请CN110358931A公布了一种离子交换法提取碳酸粘土型锂矿中锂的方法，该法通过三价铁盐和焙烧黏土熟料在85℃以离子交换的形式实现锂的浸出，但浸出率偏低，铁盐的消耗较高，工业化难度较大；专利申请CN111893318A公布了一种含锂黏土提锂的方法，该法将球磨后的锂黏土同碳酸钙、硫酸钠、硫酸钾按一定比例焙烧，粉碎后浸出得到含锂溶液，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CN103849761B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。Regarding the recovery of lithium from lithium clay, the relevant domestic lithium extraction technology is currently very limited. Patent application CN110358931A discloses an ion exchange method for extracting lithium from carbonated clay lithium ore. This method uses ferric salt and roasted clay clinker to achieve lithium leaching in the form of ion exchange at 85°C, but the leaching rate is biased. Low, the consumption of iron salt is high, and industrialization is difficult; patent application CN111893318A discloses a method for extracting lithium from lithium-containing clay. This method roasts the ball-milled lithium clay with calcium carbonate, sodium sulfate, and potassium sulfate in a certain proportion. , crushed and leached to obtain a lithium-containing solution. This method produces a large amount of calcium-silicon waste residue, which is difficult to handle. The lithium oxide content in the residue reaches 0.2%, and is only suitable for clay minerals with higher lithium oxide grades; patent CN103849761B publishes a low-grade A method for extracting lithium from lithium-containing clay ores. This method proposes a new process of "modified roasting-heap leaching". However, calcium fluoride is introduced during the roasting process. The fluoride ions are highly corrosive to the equipment, and the hydrogen fluoride produced is also There is pollution to the atmosphere.
发明内容Contents of the invention
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种从锂黏土中回收锂的方法，该方法工艺简单，可行性高，过程能耗低，对低品位的锂黏 土具有较高的锂浸出率。The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a method for recovering lithium from lithium clay. This method has simple process, high feasibility, low process energy consumption, and is suitable for low-grade lithium clay. Soil has a higher lithium leaching rate.
根据本发明的一个方面，提出了一种从锂黏土中回收锂的方法，包括以下步骤：According to one aspect of the present invention, a method for recovering lithium from lithium clay is proposed, including the following steps:
S1：将锂黏土原料进行破碎，得到锂黏土粉料，将所述锂黏土粉料进行第一次焙烧，得到一次焙烧料；S1: Crush the lithium clay raw material to obtain lithium clay powder, and perform the first roasting of the lithium clay powder to obtain the primary roasting material;
S2：将所述一次焙烧料与添加剂混合后进行研磨，得到研磨料；所述添加剂为钠盐、钾盐、氢氧化钠或氢氧化钾中的至少一种；S2: Mix the primary roasting material with an additive and then grind it to obtain a grinding material; the additive is at least one of sodium salt, potassium salt, sodium hydroxide or potassium hydroxide;
S3：将所述研磨料与酸混合后进行第二次焙烧，得到二次焙烧料；S3: Mix the grinding material with acid and then roast it for the second time to obtain the secondary roasting material;
S4：所述二次焙烧料加入浸出剂进行浸出，固液分离得到浸出液。S4: The secondary roasting material is leached by adding a leaching agent, and solid-liquid separation is performed to obtain a leaching liquid.
在本发明的一些实施方式中，步骤S1中，所述锂黏土原料的锂含量0.1-0.8wt％。In some embodiments of the present invention, in step S1, the lithium content of the lithium clay raw material is 0.1-0.8 wt%.
在本发明的一些实施方式中，步骤S1中，所述锂黏土粉料的粒径为50-300目。优选的，所述锂黏土粉料的粒径为100-200目。In some embodiments of the present invention, in step S1, the particle size of the lithium clay powder is 50-300 mesh. Preferably, the particle size of the lithium clay powder is 100-200 mesh.
在本发明的一些实施方式中，步骤S1中，所述第一次焙烧的温度为600-1200℃。优选的，所述第一次焙烧的温度为600-900℃。In some embodiments of the present invention, in step S1, the temperature of the first roasting is 600-1200°C. Preferably, the temperature of the first roasting is 600-900°C.
在本发明的一些实施方式中，步骤S1中，所述第一次焙烧的时间为1-8h。优选的，所述第一次焙烧的时间为2-4h。In some embodiments of the present invention, in step S1, the first roasting time is 1-8 hours. Preferably, the first roasting time is 2-4 hours.
在本发明的一些实施方式中，步骤S2中，所述添加剂为NaOH、KOH、Na2CO3、K2CO3、CH3COONa、CH3COOK、NaHCO3或KHCO3中的至少一种。与Ca、Mg相比，Na、K的离子半径较小，离子交换动力学较高，同时避免Ca、Mg的引入增加后续锂溶液回收的难度，降低后续除杂成本。In some embodiments of the present invention, in step S2, the additive is at least one of NaOH, KOH, Na 2 CO 3 , K 2 CO 3 , CH 3 COONa, CH 3 COOK, NaHCO 3 or KHCO 3 . Compared with Ca and Mg, Na and K have smaller ionic radii and higher ion exchange kinetics. At the same time, it avoids the introduction of Ca and Mg, which increases the difficulty of subsequent lithium solution recovery and reduces subsequent impurity removal costs.
在本发明的一些实施方式中，步骤S2中，所述添加剂与一次焙烧料的质量比为1：(5-30)。优选的，所述添加剂与一次焙烧料的质量比为1：(10-20)。In some embodiments of the present invention, in step S2, the mass ratio of the additive to the primary roasting material is 1: (5-30). Preferably, the mass ratio of the additive to the primary roasting material is 1: (10-20).
在本发明的一些实施方式中，步骤S2中，所述研磨的转速为100-1200rpm。优选的，所述研磨的转速为500-800rpm。In some embodiments of the present invention, in step S2, the grinding speed is 100-1200 rpm. Preferably, the grinding speed is 500-800 rpm.
在本发明的一些实施方式中，步骤S2中，所述研磨的时间为1-12h。优选的，所述研磨的时间为2-6h。 In some embodiments of the present invention, in step S2, the grinding time is 1-12 hours. Preferably, the grinding time is 2-6 hours.
在本发明的一些实施方式中，步骤S2中，所述研磨采用行星式球磨机、卧式球磨机、破碎机或振动球磨机中的一种。In some embodiments of the present invention, in step S2, the grinding uses one of a planetary ball mill, a horizontal ball mill, a crusher or a vibrating ball mill.
在本发明的一些实施方式中，步骤S3中，所述酸为盐酸、硫酸或硝酸中的至少一种。In some embodiments of the present invention, in step S3, the acid is at least one of hydrochloric acid, sulfuric acid or nitric acid.
在本发明的一些实施方式中，步骤S3中，所述酸的质量浓度为2-50％。优选的，所述酸的质量浓度为5-10％。In some embodiments of the present invention, in step S3, the mass concentration of the acid is 2-50%. Preferably, the mass concentration of the acid is 5-10%.
在本发明的一些实施方式中，步骤S3中，所述酸与所述研磨料的质量比为(0.2-2)：1。优选的，所述酸与所述研磨料的质量比为(0.5-1)：1。含锂黏土矿结构复杂，存在火山岩型、碳酸岩型等多种结构，考虑到工艺兼容性和成本，加少量的酸在低温下进行焙烧，有利于残锂的浸出，也有利于不同含锂黏土矿中锂的提取。In some embodiments of the present invention, in step S3, the mass ratio of the acid to the abrasive is (0.2-2):1. Preferably, the mass ratio of the acid to the grinding material is (0.5-1):1. The structure of lithium-containing clay minerals is complex, and there are various structures such as volcanic rock type and carbonate rock type. Considering process compatibility and cost, adding a small amount of acid and roasting at low temperature is beneficial to the leaching of residual lithium and is also beneficial to different lithium-containing structures. Extraction of lithium from clay minerals.
在本发明的一些实施方式中，步骤S3中，所述第二次焙烧的温度为150-300℃。优选的，所述第二次焙烧的温度为200-250℃。In some embodiments of the present invention, in step S3, the temperature of the second roasting is 150-300°C. Preferably, the temperature of the second roasting is 200-250°C.
在本发明的一些实施方式中，步骤S3中，所述第二次焙烧的时间为1-10h。优选的，所述第二次焙烧的时间为2-4h。In some embodiments of the present invention, in step S3, the second roasting time is 1-10 h. Preferably, the second roasting time is 2-4 hours.
在本发明的一些实施方式中，步骤S4中，所述浸出液作为所述浸出剂循环使用以富集锂。In some embodiments of the present invention, in step S4, the leachate is recycled as the leachant to enrich lithium.
在本发明的一些实施方式中，步骤S4中，所述浸出剂为水，或者选自的硫酸、盐酸、硝酸或饱和碳酸溶液中的至少一种。进一步的，所述硫酸、盐酸或硝酸的浓度为1-2mol/L。In some embodiments of the present invention, in step S4, the leaching agent is water, or at least one selected from sulfuric acid, hydrochloric acid, nitric acid or saturated carbonic acid solution. Further, the concentration of sulfuric acid, hydrochloric acid or nitric acid is 1-2mol/L.
在本发明的一些优选的实施方式中，步骤S4中，所述浸出剂为水。In some preferred embodiments of the present invention, in step S4, the leaching agent is water.
根据本发明的一种优选的实施方式，至少具有以下有益效果：According to a preferred embodiment of the present invention, it has at least the following beneficial effects:
本发明基于一次焙烧、高能研磨和二次酸化焙烧的方式实现锂黏土的锂提取，先通过一次焙烧脱除黏土矿中的结构羟基，致使黏土矿晶格间距增大，有利于锂离子的脱嵌和交换；再通过高能研磨使物料和添加剂之间发生局部高能碰撞，进一步破坏黏土矿的结构，提供反应所需活化能，使得Na+/K+同黏土矿中的Li+发生离子交换，同时研磨过 程减小颗粒尺寸，有利于提高离子交换动力学，研磨后的锂以碳酸盐/碳酸氢盐等形式存在，该过程能实现大部分的晶格锂的脱离；再通过二次酸化焙烧，加入一定量的酸，将脱离的锂转化为易溶解的锂盐，同时酸在焙烧过程中用于深度提取黏土矿中的锂，酸化焙烧后的物料利用浸出剂浸出，浸出的锂溶液可通过循环浸出实现锂的富集。该工艺适用于低品位锂黏土锂的浸出，浸出率高，浸出液锂浓度高，工艺兼容性强，适用于不同含锂黏土矿中锂的提取，极具应用前景。The present invention realizes lithium extraction from lithium clay based on primary roasting, high-energy grinding and secondary acidification roasting. The structural hydroxyl groups in the clay mineral are first removed through primary roasting, which increases the lattice spacing of the clay mineral and is conducive to the removal of lithium ions. Intercalation and exchange; then through high-energy grinding, local high-energy collision occurs between the material and the additive, which further destroys the structure of the clay mineral and provides the activation energy required for the reaction, causing ion exchange between Na + /K + and Li + in the clay mineral. ground simultaneously The process reduces the particle size, which is beneficial to improving ion exchange kinetics. The ground lithium exists in the form of carbonate/bicarbonate, etc. This process can achieve the separation of most of the lattice lithium; and then through secondary acidification and roasting, Add a certain amount of acid to convert the detached lithium into easily soluble lithium salts. At the same time, the acid is used to deeply extract lithium from the clay ore during the roasting process. The acidified and roasted materials are leached using a leaching agent. The leached lithium solution can be Cyclic leaching achieves lithium enrichment. This process is suitable for leaching lithium from low-grade lithium clay ores, with high leaching rate, high lithium concentration in the leach solution, and strong process compatibility. It is suitable for the extraction of lithium from different lithium-containing clay ores and has great application prospects.
附图说明Description of the drawings
下面结合附图和实施例对本发明做进一步的说明，其中：The present invention will be further described below in conjunction with the accompanying drawings and examples, wherein:
图1为本发明的工艺流程图。Figure 1 is a process flow diagram of the present invention.
具体实施方式Detailed ways
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。The concept of the present invention and the technical effects produced will be clearly and completely described below with reference to the embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without exerting creative efforts are all protection scope of the present invention.
实施例1Example 1
一种从锂黏土中回收锂的方法，参照图1，具体过程为：A method of recovering lithium from lithium clay. Refer to Figure 1. The specific process is:
S1：将含锂黏土破碎至100目；S1: Crush the lithium-containing clay to 100 mesh;
S2：将得到破碎混料在800℃下进行焙烧，焙烧时间为2h，得到一次焙烧料；S2: Roast the obtained crushed mixture at 800°C for 2 hours to obtain primary roasted material;
S3：取500g一次焙烧料与碳酸氢钠按15：1的质量比在行星式球磨机中进行混合球磨，转速设为800rpm，研磨4h；S3: Take 500g of the primary roasting material and sodium bicarbonate and mix them in a planetary ball mill at a mass ratio of 15:1. The rotation speed is set to 800rpm and grinded for 4 hours;
S4：将研磨后的混料按质量比1：2与10％的硫酸混合，混合均匀后在250℃下焙烧2h，得到二次焙烧料；S4: Mix the ground mixture with 10% sulfuric acid in a mass ratio of 1:2, mix evenly and roast at 250°C for 2 hours to obtain a secondary roasting material;
S5：得到的二次焙烧料按液固比3：1mL/g加入纯水进行浸出，分离得到浸出液与浸出渣，浸出液作为浸出剂循环浸出三次实现锂的富集，富集后的浸出液进行锂回收。S5: The obtained secondary roasting material is leached by adding pure water at a liquid-to-solid ratio of 3:1 mL/g. The leachate and leaching residue are separated to obtain the leachate. The leachate is used as a leachant and circulated for three times to achieve lithium enrichment. The enriched leachate is subjected to lithium Recycle.
对本实施例的锂黏土组成以及浸出渣和浸出液，采用电感耦合等离子体发射光谱仪 (ICP-OES)和原子吸收分光光度计检测，检测结果如表1所示。其中锂的浸出率＝(浸出液体积*锂浓度)/(浸出物料质量*锂含量)*100％，计算得到S5中锂的浸出率为90.5％，浸出液中的锂浓度经过三次循环富集后达到3095ppm。For the composition of the lithium clay, the leaching residue and the leaching liquid in this example, an inductively coupled plasma emission spectrometer was used (ICP-OES) and atomic absorption spectrophotometer detection, the detection results are shown in Table 1. Among them, the lithium leaching rate = (leaching liquid volume * lithium concentration) / (leaching material mass * lithium content) * 100%. The calculated lithium leaching rate in S5 is 90.5%. The lithium concentration in the leaching liquid reaches 90.5% after three cycles of enrichment. 3095ppm.
表1实施例1锂黏土原料及浸出液组成
Table 1 Example 1 Lithium clay raw materials and leachate composition
实施例2Example 2
一种从锂黏土中回收锂的方法，具体过程为：A method for recovering lithium from lithium clay. The specific process is:
S1：将含锂黏土破碎至100目；S1: Crush the lithium-containing clay to 100 mesh;
S2：将得到破碎混料在800℃下进行焙烧，焙烧时间为2h，得到一次焙烧料；S2: Roast the obtained crushed mixture at 800°C for 2 hours to obtain primary roasted material;
S3：取500g一次焙烧料与碳酸氢钾按15：1的质量比在行星式球磨机中进行混合球磨，转速设为800rpm，研磨4h；S3: Take 500g of the primary roasting material and potassium bicarbonate and mix them in a planetary ball mill at a mass ratio of 15:1. The rotation speed is set to 800rpm and grinded for 4 hours;
S4：将研磨后的混料按质量比1：2与10％的硫酸混合，混合均匀后在250℃下焙烧2h，得到二次焙烧料；S4: Mix the ground mixture with 10% sulfuric acid in a mass ratio of 1:2, mix evenly and roast at 250°C for 2 hours to obtain a secondary roasting material;
S5：得到的二次焙烧料按液固比3：1mL/g加入纯水进行浸出，固液分离得到浸出液与浸出渣，浸出液作为浸出剂循环浸出三次实现锂的富集。S5: The obtained secondary roasting material is leached by adding pure water at a liquid-to-solid ratio of 3:1 mL/g. The solid-liquid separation is performed to obtain the leachate and leaching residue. The leachate is used as a leachant and circulated for three times to achieve lithium enrichment.
对本实施例的锂黏土组成以及浸出渣和浸出液，采用电感耦合等离子体发射光谱仪(ICP-OES)和原子吸收分光光度计检测，检测结果如表2所示。其中锂的浸出率＝(浸出液体积*锂浓度)/(浸出物料质量*锂含量)*100％，计算得到S5中锂的浸出率为89.2％，浸出液中的锂浓度经过三次循环富集后达到3375ppm。The composition of the lithium clay, the leaching residue and the leaching liquid in this embodiment were detected using an inductively coupled plasma optical emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer. The detection results are shown in Table 2. Among them, the lithium leaching rate = (leaching liquid volume * lithium concentration) / (leaching material mass * lithium content) * 100%, the calculated lithium leaching rate in S5 is 89.2%, and the lithium concentration in the leach liquid reaches 89.2% after three cycles of enrichment. 3375 ppm.
表2实施例2锂黏土原料及浸出液组成

Table 2 Example 2 Lithium clay raw materials and leachate composition

实施例3Example 3
一种从锂黏土中回收锂的方法，具体过程为：A method for recovering lithium from lithium clay. The specific process is:
S1：将含锂黏土破碎至100目；S1: Crush the lithium-containing clay to 100 mesh;
S2：将得到破碎混料在800℃下进行焙烧，焙烧时间为2h，得到一次焙烧料；S2: Roast the obtained crushed mixture at 800°C for 2 hours to obtain primary roasted material;
S3：取500g一次焙烧料与碳酸氢钠按10：1的质量比在行星式球磨机中进行混合球磨，转速设为800rpm，研磨4h；S3: Take 500g of primary roasting material and sodium bicarbonate and mix them in a planetary ball mill at a mass ratio of 10:1. The rotation speed is set to 800rpm and grinded for 4 hours;
S4：将研磨后的混料按质量比1：2与10％的硫酸混合，混合均匀后在250℃下焙烧2h，得到二次焙烧料；S4: Mix the ground mixture with 10% sulfuric acid in a mass ratio of 1:2, mix evenly and roast at 250°C for 2 hours to obtain a secondary roasting material;
S5：得到的二次焙烧料按液固比3：1mL/g加入纯水进行浸出，固液分离得到浸出液与浸出渣，浸出液作为浸出剂循环浸出三次实现锂的富集。S5: The obtained secondary roasting material is leached by adding pure water at a liquid-to-solid ratio of 3:1 mL/g. The solid-liquid separation is performed to obtain the leachate and leaching residue. The leachate is used as a leachant and circulated for three times to achieve lithium enrichment.
对本实施例的锂黏土组成以及浸出渣和浸出液，采用电感耦合等离子体发射光谱仪(ICP-OES)和原子吸收分光光度计检测，检测结果如表3所示。其中锂的浸出率＝(浸出液体积*锂浓度)/(浸出物料质量*锂含量)*100％，计算得到S5中锂的浸出率为95.5％，浸出液中的锂浓度经过三次循环富集后达到3998ppm。The composition of the lithium clay, the leaching residue and the leaching liquid in this embodiment were detected using an inductively coupled plasma optical emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer. The detection results are shown in Table 3. Among them, the lithium leaching rate = (leaching liquid volume * lithium concentration) / (leaching material mass * lithium content) * 100%. The calculated lithium leaching rate in S5 is 95.5%. The lithium concentration in the leaching liquid reaches 95.5% after three cycles of enrichment. 3998ppm.
表3实施例3锂黏土原料及浸出液组成
Table 3 Example 3 Lithium clay raw materials and leachate composition
实施例4Example 4
一种从锂黏土中回收锂的方法，具体过程为：A method for recovering lithium from lithium clay. The specific process is:
S1：将含锂黏土破碎至100目；S1: Crush the lithium-containing clay to 100 mesh;
S2：将得到破碎混料在800℃下进行焙烧，焙烧时间为2h，得到一次焙烧料； S2: Roast the crushed mixture at 800°C for 2 hours to obtain primary roasting material;
S3：取500g一次焙烧料与碳酸氢钠按15：1的质量比在行星式球磨机中进行混合球磨，转速设为800rpm，研磨10h；S3: Take 500g of the primary roasting material and sodium bicarbonate and mix them in a planetary ball mill at a mass ratio of 15:1. The rotation speed is set to 800rpm and grinded for 10 hours;
S4：将研磨后的混料按质量比1：2与10％的硫酸混合，混合均匀后在250℃下焙烧2h，得到二次焙烧料；S4: Mix the ground mixture with 10% sulfuric acid in a mass ratio of 1:2, mix evenly and roast at 250°C for 2 hours to obtain a secondary roasting material;
S5：得到的二次焙烧料按液固比3：1mL/g加入纯水进行浸出，固液分离得到浸出液与浸出渣，浸出液作为浸出剂循环浸出三次实现锂的富集。S5: The obtained secondary roasting material is leached by adding pure water at a liquid-to-solid ratio of 3:1 mL/g. The solid-liquid separation is performed to obtain the leachate and leaching residue. The leachate is used as a leachant and circulated for three times to achieve lithium enrichment.
对本实施例的锂黏土组成以及浸出渣和浸出液，采用电感耦合等离子体发射光谱仪(ICP-OES)和原子吸收分光光度计检测，检测结果如表4所示。其中锂的浸出率＝(浸出液体积*锂浓度)/(浸出物料质量*锂含量)*100％，计算得到S5中锂的浸出率为97.5％，浸出液中的锂浓度经过三次循环富集后达到4025ppm。The composition of the lithium clay, the leaching residue and the leaching liquid in this embodiment were tested using an inductively coupled plasma optical emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer. The test results are shown in Table 4. Among them, the lithium leaching rate = (leaching liquid volume * lithium concentration) / (leaching material mass * lithium content) * 100%. The calculated lithium leaching rate in S5 is 97.5%. The lithium concentration in the leaching liquid reaches 97.5% after three cycles of enrichment. 4025ppm.
表4实施例4锂黏土原料及浸出液组成
Table 4 Example 4 lithium clay raw materials and leachate composition
对比例1Comparative example 1
一种从锂黏土中回收锂的方法，与实施例1的区别在于，二次焙烧未加入酸，具体过程为：A method for recovering lithium from lithium clay. The difference from Example 1 is that no acid is added to the secondary roasting. The specific process is:
S1：将含锂黏土破碎至100目；S1: Crush the lithium-containing clay to 100 mesh;
S2：将得到破碎混料在800℃下进行焙烧，焙烧时间为2h，得到一次焙烧料；S2: Roast the obtained crushed mixture at 800°C for 2 hours to obtain primary roasted material;
S3：取500g一次焙烧料与碳酸氢钠按质量比15：1的比例在行星式球磨机中进行混合球磨，转速设为800rpm，研磨4h。S3: Take 500g of primary roasting material and sodium bicarbonate and mix and ball mill them in a planetary ball mill at a mass ratio of 15:1. The rotation speed is set to 800 rpm and grinded for 4 hours.
S4：将研磨后的混料在250℃下焙烧2h，得到二次焙烧料；S4: Roast the ground mixture for 2 hours at 250°C to obtain secondary roasting material;
S5：得到的二次焙烧混料按液固比3：1mL/g加入纯水进行浸出，固液分离得到浸出液与浸出渣，浸出液作为浸出剂循环浸出三次实现锂的富集。 S5: The obtained secondary roasting mixture is leached with pure water at a liquid-to-solid ratio of 3:1 mL/g. The solid-liquid separation is performed to obtain the leachate and leaching residue. The leachate is used as a leachant and circulated for three times to achieve lithium enrichment.
对本对比例的锂黏土组成以及浸出渣和浸出液，采用电感耦合等离子体发射光谱仪(ICP-OES)和原子吸收分光光度计检测，检测结果如表1所示。其中锂的浸出率＝(浸出液体积*锂浓度)/(浸出物料质量*锂含量)*100％，计算得到S5中锂的浸出率为72.3％，浸出液中的锂浓度经过三次循环富集后达到2573ppm。The composition of the lithium clay as well as the leaching residue and leachate of this comparative example were tested using an inductively coupled plasma optical emission spectrometer (ICP-OES) and an atomic absorption spectrophotometer. The test results are shown in Table 1. Among them, the lithium leaching rate = (leaching liquid volume * lithium concentration) / (leaching material mass * lithium content) * 100%. The calculated lithium leaching rate in S5 is 72.3%. The lithium concentration in the leaching liquid reaches 72.3% after three cycles of enrichment. 2573ppm.
表5对比例1锂黏土原料及浸出液组成
Table 5 Comparative Example 1 Lithium Clay Raw Materials and Leachate Composition
对比例1未经过酸化焙烧，从表5可以看出，锂的浸出率较低，这是由于对比例1仅经过高能球磨，球磨过程本身属于固相反应，反应动力学有限，仅靠球磨过程不能使锂浸出彻底。实施例加少量的酸在低温下进行酸化焙烧，能够深度提取黏土矿中的锂，提高锂浸出率。Comparative Example 1 has not been acidified and roasted. As can be seen from Table 5, the leaching rate of lithium is low. This is because Comparative Example 1 has only undergone high-energy ball milling. The ball milling process itself is a solid-phase reaction with limited reaction kinetics. The ball milling process alone is Lithium cannot be completely leached. Example: Adding a small amount of acid and performing acidification roasting at low temperature can deeply extract lithium from clay minerals and increase the lithium leaching rate.
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。 The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those of ordinary skill in the art, various modifications can be made without departing from the purpose of the present invention. Variety. In addition, the embodiments of the present invention and the features in the embodiments may be combined with each other without conflict.

Claims (10)

  1. 一种从锂黏土中回收锂的方法，其特征在于，包括以下步骤：A method for recovering lithium from lithium clay, characterized by comprising the following steps:
    S1：将锂黏土原料进行破碎，得到锂黏土粉料，将所述锂黏土粉料进行第一次焙烧，得到一次焙烧料；S1: Crush the lithium clay raw material to obtain lithium clay powder, and perform the first roasting of the lithium clay powder to obtain the primary roasting material;
    S2：将所述一次焙烧料与添加剂混合后进行研磨，得到研磨料；所述添加剂为钠盐、钾盐、氢氧化钠或氢氧化钾中的至少一种；S2: Mix the primary roasting material with an additive and then grind it to obtain a grinding material; the additive is at least one of sodium salt, potassium salt, sodium hydroxide or potassium hydroxide;
    S3：将所述研磨料与酸混合后进行第二次焙烧，得到二次焙烧料；S3: Mix the grinding material with acid and then roast it for the second time to obtain the secondary roasting material;
    S4：所述二次焙烧料加入浸出剂进行浸出，固液分离，得到浸出液。S4: The secondary roasting material is leached by adding a leaching agent, and the solid and liquid are separated to obtain a leaching liquid.
  2. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述锂黏土粉料的粒径为50-300目。The method according to claim 1, characterized in that in step S1, the particle size of the lithium clay powder is 50-300 mesh.
  3. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述第一次焙烧的温度为600-1200℃。The method according to claim 1, characterized in that in step S1, the temperature of the first roasting is 600-1200°C.
  4. 根据权利要求1所述的方法，其特征在于，步骤S2中，所述添加剂为NaOH、KOH、Na2CO3、K2CO3、CH3COONa、CH3COOK、NaHCO3或KHCO3中的至少一种。The method according to claim 1, characterized in that in step S2, the additive is NaOH, KOH, Na 2 CO 3 , K 2 CO 3 , CH 3 COONa, CH 3 COOK, NaHCO 3 or KHCO 3 At least one.
  5. 根据权利要求1或4所述的方法，其特征在于，步骤S2中，所述添加剂与一次焙烧料的质量比为1：(5-30)。The method according to claim 1 or 4, characterized in that in step S2, the mass ratio of the additive to the primary roasting material is 1: (5-30).
  6. 根据权利要求1所述的方法，其特征在于，步骤S2中，所述研磨的转速为100-1200rpm。The method according to claim 1, characterized in that in step S2, the grinding speed is 100-1200 rpm.
  7. 根据权利要求1所述的方法，其特征在于，步骤S3中，所述酸为盐酸、硫酸或硝酸中的至少一种。The method of claim 1, wherein in step S3, the acid is at least one of hydrochloric acid, sulfuric acid or nitric acid.
  8. 根据权利要求1所述的方法，其特征在于，步骤S3中，所述第二次焙烧的温度为150-300℃。The method according to claim 1, characterized in that in step S3, the temperature of the second roasting is 150-300°C.
  9. 根据权利要求1所述的方法，其特征在于，步骤S4中，所述浸出液作为所述浸出剂循环使用以富集锂。The method according to claim 1, characterized in that, in step S4, the leachate is recycled as the leachant to enrich lithium.
  10. 根据权利要求1所述的方法，其特征在于，步骤S4中，所述浸出剂为水，或者选自硫酸、盐酸、硝酸、碳酸中的至少一种。 The method according to claim 1, characterized in that in step S4, the leaching agent is water, or at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid and carbonic acid.
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