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WO2017181759A1 - Procédé de fabrication de chlorure de lithium anhydre à l'aide d'eaux usées contenant du lithium - Google Patents

Procédé de fabrication de chlorure de lithium anhydre à l'aide d'eaux usées contenant du lithium Download PDF

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Publication number
WO2017181759A1
WO2017181759A1 PCT/CN2017/072970 CN2017072970W WO2017181759A1 WO 2017181759 A1 WO2017181759 A1 WO 2017181759A1 CN 2017072970 W CN2017072970 W CN 2017072970W WO 2017181759 A1 WO2017181759 A1 WO 2017181759A1
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WIPO (PCT)
Prior art keywords
lithium
chloride
waste liquid
containing waste
sodium
Prior art date
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Ceased
Application number
PCT/CN2017/072970
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English (en)
Chinese (zh)
Inventor
曹乃珍
高洁
肇巍
樊平
张炳元
杜明泽
赵莉
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Tianqi Lithium Corp
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Tianqi Lithium Corp
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Publication of WO2017181759A1 publication Critical patent/WO2017181759A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/04—Halides

Definitions

  • the present invention relates to the technical field of lithium chloride preparation, and more particularly to a method for preparing anhydrous lithium chloride using a lithium-containing waste liquid.
  • Lithium chloride is an important lithium salt product. In recent years, it has been widely used as a mutagen in pharmaceutical, food, environmental protection and other industries. It can be used to cultivate high-yield strains, synthetic pharmaceutical intermediates, and genetic modification of strains. It can also be used for the extraction and purification of isolated RNA and a small amount of plasmid DNA; it is also an important cationic additive in organic structure analysis; in medicine, it can be used for the treatment of diabetes and applied to genetic research; In the field of materials, it can be applied to the production of chitin. In addition, electrolytic production of lithium metal is the largest consumption of lithium chloride, and it is also the only industrial method for producing lithium metal. Metallic lithium and its alloys and compounds have a wide range of applications in many fields such as metallurgical industry, battery, ceramics, glass, chemical, aerospace, and atomic energy industries.
  • the preparation methods of lithium chloride mainly include solvent extraction method, ion exchange adsorption method, salting out method and conversion method, and the conversion method is generally divided into ore direct conversion method, lithium carbonate or lithium hydroxide conversion method, lithium sulfate conversion method and Lithium hydroxide direct chlorination method, in which lithium carbonate or lithium hydroxide conversion method is the most important industrial method, most of the lithium chloride in China is produced by this method.
  • the raw material cost is high and the impurity sodium and potassium are difficult to be separated.
  • the separation of sodium and potassium by solvent extraction or ion exchange has an ideal separation effect, but the production cost is high and economically unreasonable.
  • lithium-containing waste liquid produced in the production process of pharmaceutical intermediates as raw material to prepare anhydrous lithium chloride can greatly reduce the cost of raw materials and solve problems such as wastewater discharge and environmental pollution. Therefore, it is necessary to provide a method for preparing anhydrous lithium chloride by utilizing a lithium-containing waste liquid produced in the production process of a pharmaceutical intermediate.
  • an object of the present invention is to provide a method for preparing anhydrous lithium chloride using a lithium-containing waste liquid with a simple process, low production cost, high lithium recovery rate, and environmental friendliness.
  • the invention provides a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid containing at least lithium ions, calcium ions, magnesium ions, sodium ions, potassium ions, sulfate ions and chloride ions.
  • the method includes the following steps:
  • the refined mother liquid is concentrated by evaporation to precipitate sodium chloride and potassium chloride solids and filtered to remove the sodium chloride and potassium chloride solids to obtain a lithium chloride clear solution;
  • An embodiment of a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid according to the present invention wherein the lithium-containing waste liquid is a lithium-containing waste liquid produced in a production process of a pharmaceutical intermediate, wherein the lithium-containing waste liquid
  • the lithium ion concentration is 10 to 35 g/L
  • the chloride ion concentration is 80 to 200 g/L
  • the sodium ion concentration is 1 to 15 g/L
  • the sulfate ion concentration is 0.5 to 5 g/L
  • the magnesium ion concentration is 0.1 to 2 g/ L
  • the calcium ion concentration is 0.2 to 4 g/L
  • the potassium ion concentration is 0.01 to 0.2 g/L.
  • the hydrogen peroxide in the step A, has a mass concentration of 10 to 50% and a reaction time of 10 to 50 minutes.
  • step B An embodiment of a method for preparing anhydrous lithium chloride using a lithium-containing waste liquid according to the present invention, in step B
  • the concentration of the ruthenium chloride solution is 50 to 200 g/L, and the reaction time is 30 to 120 min.
  • a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid in the step C, the sodium carbonate solution has a concentration of 50 to 200 g/L, and the reaction temperature is 20 to 60 ° C, and the reaction time is It is 30 to 240 minutes.
  • the sodium ion concentration in the lithium chloride supernatant is less than 1 g/L, and the potassium ion concentration is less than 0.5. g/L.
  • the sodium fine preparation is Li 1.3 Zr 0.8 Ce 0.4 Si 0.5 Al 0.3 (PO 4 ) 3 and The sodium concentrate preparation is added in an amount of 25 to 30 times the mass of the sodium in the lithium chloride supernatant.
  • a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid in the step E, the reaction temperature is 40 to 95 ° C, the reaction time is 2 to 8 hours, and the pore diameter is 0.5 to 0.5 after the reaction.
  • a 1 ⁇ m microfiltration membrane was used for filtration.
  • the sodium ion concentration in the high-concentration lithium chloride solution is less than 0.02 g/L.
  • step F placing the high concentration lithium chloride solution in a titanium crucible and in an oven at 200 to 250 ° C Dry down.
  • the method for preparing anhydrous lithium chloride by using lithium-containing waste liquid has the following advantages: 1) simple process and low production cost; 2) high lithium recovery rate; 3) anhydrous water prepared Lithium chloride can reach the battery level standard; 4)
  • the raw material used is the lithium-containing waste liquid produced in the production process of the pharmaceutical intermediate, and the raw material cost is low; 5)
  • the method is environmentally friendly and the environmental protection pressure is small.
  • the present invention provides a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid, and the lithium-containing waste liquid produced in the production process of the pharmaceutical intermediate is removed from the residual organic phase by hydrogen peroxide, and then the ruthenium chloride is first removed.
  • Sulfate ion, sodium carbonate is added to the mother liquor, and a trace amount of calcium ions, magnesium ions and barium ions are removed by stirring, and the precipitate is filtered to obtain a refined mother liquid, which is concentrated by evaporation and filtered to remove sodium chloride and potassium chloride, and then heated.
  • the obtained lithium chloride clear solution is added to the sodium fine preparation and stirred and filtered to obtain a high concentration lithium chloride solution, which is dried to obtain a battery-grade anhydrous lithium chloride product.
  • the lithium-containing waste liquid according to the present invention contains at least lithium ions, calcium ions, magnesium ions, sodium ions, potassium ions, sulfate ions, and chloride ions. More preferably, the lithium-containing waste liquid is a lithium-containing waste liquid produced in the production process of a pharmaceutical intermediate.
  • the lithium-containing waste liquid has a lithium ion concentration of 10 to 35 g/L, a chloride ion concentration of 80 to 200 g/L, a sodium ion concentration of 1 to 15 g/L, and a sulfate ion concentration of 0.5 to 5 g/L, a magnesium ion concentration of 0.1 to 2 g/L, a calcium ion concentration of 0.2 to 4 g/L, and a potassium ion concentration of 0.01 to 0.2 g/L, but the present invention is not limited thereto.
  • the method of preparing anhydrous lithium chloride using a lithium-containing waste liquid includes the following multiple steps.
  • Hydrogen peroxide was added to the lithium-containing waste liquid to remove residual organic phase.
  • Hydrogen peroxide has strong oxidizing properties and can effectively decompose the organic phase remaining in the lithium-containing waste liquid.
  • the hydrogen peroxide has a mass concentration of 10 to 50% and a reaction time of 10 to 50 minutes.
  • the sulfate ion can be precipitated by adding a ruthenium chloride or ruthenium chloride solution, and the sulfate ion can be removed by filtration.
  • the concentration of the ruthenium chloride solution is from 50 to 200 g/L and the reaction time is from 30 to 120 min.
  • a sodium carbonate or sodium carbonate solution is added to the mother liquor and filtered to obtain a refined mother liquor.
  • the metal cation can be precipitated by adding sodium carbonate or sodium carbonate solution, and the purified mother liquid can be removed by filtration.
  • the sodium carbonate solution has a concentration of 50 to 200 g/L, a reaction temperature of 20 to 60 ° C, and a reaction time of 30 to 240 minutes.
  • the refined mother liquid is concentrated by evaporation to precipitate sodium chloride and potassium chloride solids, and the sodium chloride and potassium chloride solids are removed by filtration to obtain a lithium chloride clear solution;
  • sodium chloride and potassium chloride in the mother liquor can be precipitated, and a large amount of potassium ions and sodium ions can be removed by filtration.
  • the obtained lithium chloride supernatant has a sodium ion concentration of less than 1 g/L and a potassium ion concentration of less than 0.5 g/L.
  • a sodium concentrate preparation is added to the lithium chloride supernatant, and the reaction is stirred and filtered to obtain a high concentration lithium chloride solution.
  • the main function of the sodium concentrate preparation is to deeply remove the residual impurity sodium in the lithium chloride supernatant.
  • the sodium concentrate preparation may be Li 1.3 Zr 0.8 Ce 0.4 Si 0.5 Al 0.3 (PO 4 ) 3 , and the sodium concentrate preparation is added in an amount of 25 to 30 times the sodium mass in the lithium chloride supernatant.
  • the amount of sodium in the lithium chloride supernatant can be determined by ICP or the like before adding the sodium concentrate preparation, and then the amount of the sodium concentrate preparation added can be calculated.
  • the reaction temperature is controlled to be 40 to 95 ° C and the reaction time is 2 to 8 h.
  • the lithium chloride supernatant may be heated to the above reaction temperature, and then the sodium refined preparation is added for the reaction, and After the reaction, filtration was carried out using a microfiltration membrane having a pore diameter of 0.5 to 1 ⁇ m.
  • the sodium ion concentration in the obtained high-concentration lithium chloride solution is less than 0.02 g/L.
  • a high-concentration lithium chloride solution can be placed in a titanium crucible and dried in an oven at 200 to 250 ° C to obtain a battery-grade standard anhydrous lithium chloride.
  • lithium-containing waste liquid is a lithium-containing waste liquid produced in a production process of a pharmaceutical intermediate
  • the lithium ion concentration in the lithium-containing waste liquid is 25 g/L
  • the chloride ion concentration is 150 g. /L, sodium ion concentration 10 g / L, sulfate ion concentration 3 g / L, magnesium ion concentration 0.1 g / L, calcium ion concentration 0.2 g / L, potassium ion concentration 0.01 g / L.
  • lithium-containing waste liquid is a lithium-containing waste liquid produced in the production process of the pharmaceutical intermediate
  • the lithium ion concentration in the lithium-containing waste liquid is 30 g/L
  • the chloride ion concentration is 120 g. /L, sodium ion concentration 8 g / L, sulfate ion concentration 4 g / L, magnesium ion concentration 2 g / L, calcium ion concentration 0.5 g / L, potassium ion concentration 0.1 g / L.
  • lithium-containing waste liquid is a lithium-containing waste liquid produced in a production process of a pharmaceutical intermediate
  • the lithium ion concentration in the lithium-containing waste liquid is 20 g/L
  • the chloride ion concentration is 100 g. /L, sodium ion concentration 12g / L, sulfate ion concentration 2g / L, magnesium ion concentration of 0.5g / L, calcium ion concentrated
  • the degree was 4 g/L and the potassium ion concentration was 0.2 g/L.
  • the method for preparing anhydrous lithium chloride by using lithium-containing waste liquid has the following advantages: 1) simple process and low production cost; 2) high lithium recovery rate; 3) anhydrous chlorination prepared Lithium can reach the battery level standard; 4)
  • the raw materials used are lithium-containing waste liquid produced during the production of pharmaceutical intermediates, and the raw material cost is low; 5)
  • the method is environmentally friendly and has low environmental protection pressure.
  • the invention is not limited to the specific embodiments described above.
  • the invention extends to any new feature or any new combination disclosed in this specification, as well as any novel method or process steps or any new combination disclosed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

L'invention concerne un procédé de fabrication de chlorure de lithium anhydre à l'aide d'eaux usées contenant du lithium, les eaux usées contenant du lithium présentant au moins un ion lithium, un ion calcium, un ion magnésium, un ion sodium, un ion potassium, un ion sulfate et un ion chlorure. Le procédé comprend les étapes suivantes : A. l'ajout de peroxyde d'hydrogène aux eaux usées contenant du lithium pour éliminer une phase organique résiduelle ; B. l'ajout de chlorure de baryum ou de son solvant pour entraîner une réaction, puis le filtrage afin d'obtenir une liqueur mère ; C. l'ajout de carbonate de sodium ou de son solvant à la liqueur mère, puis le filtrage afin d'obtenir une liqueur mère raffinée ; D. la mise en œuvre de l'évapo-concentration de la liqueur mère raffinée pour précipiter le chlorure de sodium solide et le chlorure de potassium, puis l'élimination du chlorure de sodium solide et du chlorure de potassium afin d'obtenir une solution de chlorure de lithium purifiée ; E. l'ajout d'un agent de raffinage de sodium dans la solution de chlorure de lithium purifiée, le mélange et la réaction afin d'obtenir une solution de chlorure de lithium hautement concentrée ; F. et le séchage au four de la solution de chlorure de lithium hautement concentrée afin d'obtenir le chlorure de lithium anhydre. Le procédé présente des techniques simples, de faibles coûts de production, un taux élevé de récupération de lithium et est respectueux de l'environnement.
PCT/CN2017/072970 2016-04-22 2017-02-06 Procédé de fabrication de chlorure de lithium anhydre à l'aide d'eaux usées contenant du lithium Ceased WO2017181759A1 (fr)

Applications Claiming Priority (2)

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CN201610257026.3 2016-04-22
CN201610257026.3A CN105836767B (zh) 2016-04-22 2016-04-22 一种利用含锂废液制备无水氯化锂的方法

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CN118388066A (zh) * 2024-04-10 2024-07-26 珠海万锂新材料有限公司 一种离子交换法脱除沉锂母液中氯的方法

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CN105836767B (zh) * 2016-04-22 2017-10-31 天齐锂业股份有限公司 一种利用含锂废液制备无水氯化锂的方法
CN106565956B (zh) * 2016-10-21 2018-09-28 天津科技大学 一种聚苯硫醚生产过程中副产物浆料综合回收利用方法
CN108220625B (zh) * 2016-12-21 2020-08-14 天齐锂业股份有限公司 一种从含锂废液中回收锂的方法
CN107954455A (zh) * 2017-12-06 2018-04-24 天齐锂业股份有限公司 一种利用含锂废液制备电池级碳酸锂的方法
CN108264063B (zh) * 2018-01-13 2019-12-24 安徽金禾实业股份有限公司 一种麦芽酚生产中污水提盐的方法
CN109574047B (zh) * 2018-10-22 2021-03-12 天齐锂业（江苏）有限公司 从医药含锂废液中回收高纯度依法韦伦和氯化锂的方法
CN110304642B (zh) * 2019-08-15 2021-10-29 赣州有色冶金研究所有限公司 一种去除氯化锂中杂质钠的方法和电池级无水氯化锂的制备方法
CN111017965B (zh) * 2019-11-29 2022-06-10 湖北金泉新材料有限公司 工业级氯化锂制备方法
CN115465932A (zh) * 2022-10-24 2022-12-13 中化学朗正环保科技有限公司 一种去除钙盐浓缩液中硫酸根离子的方法

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CN118388066A (zh) * 2024-04-10 2024-07-26 珠海万锂新材料有限公司 一种离子交换法脱除沉锂母液中氯的方法

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