WO2024254863A1 - Procédé de préparation de particules de tamis lithium-ion et utilisation de particules de tamis lithium-ion - Google Patents

Procédé de préparation de particules de tamis lithium-ion et utilisation de particules de tamis lithium-ion Download PDF

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Publication number
WO2024254863A1
WO2024254863A1 PCT/CN2023/100789 CN2023100789W WO2024254863A1 WO 2024254863 A1 WO2024254863 A1 WO 2024254863A1 CN 2023100789 W CN2023100789 W CN 2023100789W WO 2024254863 A1 WO2024254863 A1 WO 2024254863A1
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WIPO (PCT)
Prior art keywords
ion sieve
lithium ion
preparation
lithium
particles
Prior art date
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Ceased
Application number
PCT/CN2023/100789
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English (en)
Chinese (zh)
Inventor
李爱霞
余海军
谢英豪
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Original Assignee
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Application filed by Hunan Brunp Recycling Technology Co Ltd, Guangdong Brunp Recycling Technology Co Ltd filed Critical Hunan Brunp Recycling Technology Co Ltd
Priority to PCT/CN2023/100789 priority Critical patent/WO2024254863A1/fr
Priority to CN202380010020.4A priority patent/CN117015436B/zh
Priority to ARP240101207A priority patent/AR132670A1/es
Publication of WO2024254863A1 publication Critical patent/WO2024254863A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention belongs to the technical field of lithium extraction from salt lakes, and in particular relates to a preparation method of lithium ion sieve particles and application thereof.
  • Salt lake lithium resources account for more than 69% of the world's industrial lithium reserves.
  • the world's salt lake lithium resources are mainly distributed in South America, North America and Asia. Salt lake areas are often sparsely populated, with incomplete infrastructure and insufficient energy supply, which has brought serious constraints to the development and utilization of these lithium resources.
  • the main methods for extracting lithium from brine include evaporation crystallization, precipitation, extraction, adsorption, calcination, membrane separation and other methods.
  • the adsorption method is to separate and extract lithium using lithium selective adsorbents, which is particularly suitable for salt lake brine with high Mg/Li.
  • the key to this method lies in the selection of adsorbent materials.
  • adsorbent materials can be summarized into two categories: organic adsorbents and inorganic adsorbents.
  • Organic adsorbents usually use strong acidic cation exchange resins to selectively collect and recover lithium from lithium-containing solutions, mainly relying on Coulomb force to adsorb lithium ions into the resin, but this type of adsorbent has a low affinity for lithium ions and low selectivity for lithium ions, making it unsuitable for lithium extraction and recovery.
  • inorganic lithium adsorbents mainly relies on the unique memory effect and selectivity of inorganic lithium ion adsorbents for Li +. It has the advantages of low cost, good cycle stability and high selectivity, and has become the most promising adsorbent for adsorbing lithium ions from lithium-containing solutions. According to the classification of the main elements in inorganic lithium ion adsorbent materials, they mainly include aluminum salt adsorbents, antimony acid adsorbents, titanium oxide adsorbents and manganese oxide adsorbents.
  • lithium ion sieve materials Although these lithium ion sieve materials have the advantages of large adsorption capacity, high selectivity, and good cycle stability, they usually exist in powder form. They have poor fluidity, low cycle efficiency, and are easy to lose in industrial applications. In addition, powdered ion sieve materials can cause a large pressure drop, resulting in high energy consumption in column operations. They cannot be directly used to extract lithium from salt lake brine. These shortcomings are currently mainly overcome through the granulation molding technology of powder lithium ion sieve. The granulation method is to evenly mix the lithium ion sieve powder and the adhesive polymer together, and then form spherical particles through the polymerization reaction of the binder itself.
  • the powder ion sieve can have good mechanical strength, so that it can adapt to industrial column operations, effectively improving the recycling and permeability of the lithium ion sieve powder.
  • PVC, PVDF, etc. as the binder
  • the material mechanical properties of the agent are excellent, acid and alkali resistant, easy to shape and low cost, but compared with the powder adsorbent, the adsorption performance of the ion sieve particles after granulation will be significantly reduced. This is because PVC and PVDF binders are hydrophobic materials, which reduce the diffusion capacity of lithium ions.
  • binders containing hydrophilic groups such as agar, chitosan, polyacrylonitrile, and polyacrylamide are used to granulate powders to improve the permeability and wettability of adsorbed water and improve the adsorption performance, but hydrophilic binders have low stability in water and poor mechanical properties, which reduces the cycle performance of the adsorbent and is not suitable for long-term use.
  • the present disclosure aims to at least solve the technical problems existing in the above-mentioned prior art. To this end, the present disclosure provides a preparation method of lithium ion sieve particles and application thereof.
  • a method for preparing lithium ion sieve particles comprising the following steps:
  • the lithium ion sieve powder is a titanium-based lithium ion sieve, a manganese-based lithium ion sieve, or an aluminum-based lithium ion sieve.
  • the binder is at least one of PVDF, PVC or epoxy resin.
  • the pore-forming agent is at least one of ethanol, isopropanol or n-butanol.
  • the pore-forming agent is a volatile organic compound, and the high temperature environment accompanying the extrusion process allows the pore-forming agent to volatilize quickly and generate gas, so that the extruded particles have a porous structure, and the porous structure has strong liquid absorption.
  • step S1 the extrusion granulation is performed using an extruder, and the segmented temperature range of the extruder is 110-250°C.
  • step S1 the mass ratio of the lithium ion sieve powder to the pore-forming agent is 1:(0.1-0.2).
  • step S1 the mass ratio of the lithium ion sieve powder to the binder is 1:(0.15-0.3).
  • the porous particles in step S1, have a particle size of 1-5 mm.
  • the strong oxidizing solution is at least one of nitric acid, sodium hypochlorite, hydrogen peroxide, ammonium persulfate, acidic potassium permanganate, acidic potassium dichromate or potassium persulfate.
  • step S2 the temperature of the first heating treatment is 70-90° C. and the time is 3-6 hours.
  • step S2 the length of the carbon fiber filaments is 0.1-2 mm.
  • step S3 the temperature of the second heating treatment is 60-80° C. and the time is 2-4 hours.
  • step S3 the temperature of the third heating treatment is 90-110° C., and the time is 1-3 hours.
  • the silane coupling agent is at least one of 3-aminopropyltriethoxysilane or 3-aminopropyltrimethoxysilane.
  • step S3 the mass content of carbon fiber filaments in the lithium ion sieve particles is 1%-10%.
  • the present disclosure also provides application of the lithium ion sieve particles prepared by the preparation method in extracting lithium from salt lakes.
  • the present invention uses a strong oxidizing solution to oxidize and etch the surface of carbon fiber filaments, introduces oxygen-active functional groups (such as hydroxyl and carboxyl), can improve the hydrophilicity of carbon fiber filaments, reduce the surface tension of carbon fiber filaments, and make them easy to disperse evenly in the solution without attracting each other and affecting the processing performance.
  • oxygen-active functional groups such as hydroxyl and carboxyl
  • the oxidized carbon fiber is first combined with a silane coupling agent and then Branched to the surface of lithium ion sieve particles, silane coupling is used as a bridging agent between carbon fiber filaments and lithium ion sieve particles, and its silane alkoxy end reacts with the oxygen-active functional group of carbon fiber filaments, and the organic functional group end combines with the hydrophobic binder in the lithium ion sieve particles, so that there are covalent bonds, hydrogen bonds and multiple interface bonding effects in the interface area, which plays a good bridging role, thereby improving the interface strength between carbon fiber and lithium ion sieve particles.
  • the present disclosure is through the access of carbon fiber filaments on the surface of lithium ion sieve particles, the carbon fiber filaments can disturb the solution near the lithium ion sieve particles, enhance the convection mass transfer effect near the lithium ion sieve particles, and make the lithium-containing solution near the lithium ion sieve particles more smoothly and quickly enter the pores of the particles, improve the problem of hydrophobic binders reducing the diffusion capacity of lithium ions, and improve the diffusion capacity of lithium ions in the solution through the disturbance of carbon fiber filaments on the surface of particles, thereby improving the adsorption efficiency of lithium ion sieve particles.
  • hydrophobic binders Compared with hydrophilic binders, hydrophobic binders have higher stability in water and better mechanical properties, and are suitable for the recycling of lithium ion sieve particles.
  • the polar groups introduced into the carbon fiber after surface treatment enhance the hydrophilicity, which can further improve the permeability and wettability of the lithium ion sieve particles in the solution, thereby improving the adsorption efficiency.
  • This embodiment prepares a lithium ion sieve particle, and the specific process is as follows:
  • This embodiment prepares a lithium ion sieve particle, and the specific process is as follows:
  • Manganese lithium ion sieve powder MnO2 ⁇ 0.5H2O , PVDF, and isopropanol were mixed in a mass ratio of 1:0.15:0.15, and then extruded and granulated using a twin-screw extruder.
  • the first section temperature of the extruder was 130°C
  • the second section temperature was 170°C
  • the third section temperature was 190°C
  • the fourth section temperature was 210°C
  • the die head temperature was 230°C.
  • the extruded strips were pelletized using a pelletizer to obtain porous particles with a particle size D50 of 4.0 mm.
  • This embodiment prepares a lithium ion sieve particle, and the specific process is as follows:
  • This comparative example prepares a lithium ion sieve particle.
  • the difference from Example 1 is that only step (1) of Example 1 is performed, and the obtained porous particle is the lithium ion sieve particle of this comparative example.
  • the adsorption performance of the lithium ion sieve particles prepared in the above embodiments and comparative examples was tested.
  • the test method is as follows: 300 g of the lithium ion sieve particles of the embodiments and comparative examples were weighed and filled into an adsorption column, 10 kg of brine was weighed, and adsorption was performed through the column at a rate of 5 seconds per drop, the lithium content after passing through the column was tested, and the lithium adsorption capacity was calculated. The results are shown in Table 2.
  • adsorption capacity (lithium content in brine before adsorption - lithium content in brine after adsorption) * mass of brine passing through the column / mass of lithium ion sieve particles.

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  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention se rapporte au domaine technique de l'extraction de lithium à partir d'un lac salé. L'invention concerne un procédé de préparation de particules de tamis lithium-ion, et l'utilisation de particules de tamis lithium-ion. Le procédé comprend les étapes consistant à : mélanger une poudre de tamis lithium-ion, un liant et un agent porogène, puis extruder et granuler celle-ci, de façon à obtenir des particules poreuses ; placer des fibres de carbone dans une solution oxydante forte pour subir un premier traitement thermique, les retirer, et les nettoyer et les sécher, de façon à obtenir des fibres de carbone modifiées ; et placer les fibres de carbone modifiées dans une solution d'agent de couplage au silane pour subir un deuxième traitement thermique, de façon à obtenir un liquide trouble, ajouter les particules poreuses au liquide trouble, les mélanger jusqu'à ce qu'elles soient uniformes, les soumettre à un troisième traitement thermique, et filtrer et sécher celles-ci, de façon à obtenir des particules de tamis lithium-ion.
PCT/CN2023/100789 2023-06-16 2023-06-16 Procédé de préparation de particules de tamis lithium-ion et utilisation de particules de tamis lithium-ion Ceased WO2024254863A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/CN2023/100789 WO2024254863A1 (fr) 2023-06-16 2023-06-16 Procédé de préparation de particules de tamis lithium-ion et utilisation de particules de tamis lithium-ion
CN202380010020.4A CN117015436B (zh) 2023-06-16 2023-06-16 锂离子筛颗粒的制备方法及其应用
ARP240101207A AR132670A1 (es) 2023-06-16 2024-05-10 Método de preparación y uso de partículas de tamiz de iones de litio

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2023/100789 WO2024254863A1 (fr) 2023-06-16 2023-06-16 Procédé de préparation de particules de tamis lithium-ion et utilisation de particules de tamis lithium-ion

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CN117942954A (zh) * 2024-01-31 2024-04-30 广东邦普循环科技有限公司 一种凝胶态锂离子吸附剂及其制备方法与脱锂方法

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CN114345291B (zh) * 2021-11-15 2023-07-25 成都开飞高能化学工业有限公司 一种高吸附容量粒状钛基锂离子筛吸附剂的制备方法

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Publication number Priority date Publication date Assignee Title
JP2011060432A (ja) * 2009-09-04 2011-03-24 Ube Industries Ltd 微細な炭素繊維で覆われた粒子
CN103181004A (zh) * 2010-08-26 2013-06-26 宇部兴产株式会社 复合有细碳纤维的锂钛复合氧化物电极材料
CN104300133A (zh) * 2014-06-04 2015-01-21 中航锂电（洛阳）有限公司 一种碳纳米管包覆的钛酸锂材料及其制备方法
CN107376827A (zh) * 2017-09-08 2017-11-24 中南大学 一种二氧化锆包覆锰系锂离子筛及其制备方法和应用
CN109174049A (zh) * 2018-08-06 2019-01-11 江苏大学 印迹多孔吸附锂/铷离子材料的制备方法及应用
CN111250063A (zh) * 2020-03-06 2020-06-09 合肥工业大学 一种导电锰-钛锂离子筛/石墨烯复合水凝胶的制备及其在盐湖卤水提取锂中的应用
CN115775886A (zh) * 2022-12-26 2023-03-10 河北麦森钛白粉有限公司 一种磷酸铁锂/碳纤维复合材料的制备方法及应用

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AR132670A1 (es) 2025-07-16
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