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CN-121988300-A - Fluorine doped ion sieve precursor Li1.6Mn1.6O4Is used for synthesizing and adsorbing lithium

CN121988300ACN 121988300 ACN121988300 ACN 121988300ACN-121988300-A

Abstract

The invention provides synthesis and adsorption lithium extraction application of a fluorine doped ion sieve precursor Li 1.6 Mn 1.6 O 4 , and belongs to the technical field of lithium extraction by adsorbent brine. The synthesis method comprises the steps of placing ionic sieve precursor Li 1.6 Mn 1.6 O 4 and fluorine-containing ionic liquid in water, uniformly stirring, naturally cooling after thermal reaction, carrying out suction filtration and washing, and finally carrying out vacuum drying to obtain fluorine-doped ionic sieve precursor Li 1.6 Mn 1.6 O 4 , wherein the mass ratio of fluorine to manganese is (0.05-0.8): 1. The synthesis method of the fluorine doped ion sieve precursor Li 1.6 Mn 1.6 O 4 has the advantages of wide raw materials, simple and controllable doping process, recyclable doping raw materials, lower energy consumption and greener environmental protection, and the fluorine doped ion sieve H 1.6 Mn 1.6 O 4 prepared from the precursor has stable performance and has great significance in reducing manganese dissolution loss and improving the brine lithium extraction process.

Inventors

  • XU HUI
  • CAI KE
  • BAI XIAOLIANG
  • JIN QUAN
  • CHEN ZHIXIN

Assignees

  • 中国石油天然气集团有限公司
  • 中国石油集团工程材料研究院有限公司

Dates

Publication Date
20260508
Application Date
20241108

Claims (11)

  1. 1. The synthesis method of the fluorine doped ion sieve precursor Li 1.6 Mn 1.6 O 4 is characterized by comprising the following steps of: Placing the ionic sieve precursor Li 1.6 Mn 1.6 O 4 and the fluorine-containing ionic liquid in water, uniformly stirring, naturally cooling after thermal reaction, filtering, washing, and finally drying in vacuum to obtain a fluorine-doped ionic sieve precursor Li 1.6 Mn 1.6 O 4 ; wherein, in terms of the mass ratio of fluorine in the fluorine-containing ionic liquid to manganese in the ionic sieve precursor Li 1.6 Mn 1.6 O 4 , fluorine is manganese= (0.05-0.8): 1.
  2. 2. The synthetic method according to claim 1, wherein the fluorine-containing ionic liquid is selected from any one of 1-butyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole hexafluorophosphate, and 1-ethyl-3-methylimidazole bistrifluoromethane sulfonimide salt.
  3. 3. The synthetic method of claim 1 wherein the thermal reaction is at a temperature of 150-220 ℃ and the thermal reaction is for a time of 0.2-28 hours.
  4. 4. The method of claim 1, wherein the vacuum drying is performed at a temperature of 60-120 ℃ for a time of 12-24 hours.
  5. 5. The synthesis method according to claim 1, wherein the ionic sieve precursor Li 1.6 Mn 1.6 O 4 is prepared by: Uniformly mixing a lithium source and a manganese source, fully grinding, heating for two sections under a pressurizing range, and then vacuum drying to obtain an ion sieve precursor Li 1.6 Mn 1.6 O 4 , wherein the mass ratio of the lithium source to the manganese of the manganese source is (1.05-1.15): 1.
  6. 6. The method of claim 5, wherein the lithium source is selected from any one of LiOH H 2 O、Li 2 CO 3 、LiI、LiNO 3 .
  7. 7. The method according to claim 5, wherein the manganese source is selected from any one of manganese carbonate, manganese acetate, manganese oxalate, and manganese lactate.
  8. 8. A fluorine doped ion sieve precursor Li 1.6 Mn 1.6 O 4 , characterized in that it is obtained by the synthesis method according to any one of claims 1-7.
  9. 9. A method for preparing a fluorine doped ion sieve H 1.6 Mn 1.6 O 4 , which is characterized in that the fluorine doped ion sieve precursor Li 1.6 Mn 1.6 O 4 obtained in claim 8 is subjected to acid washing, then a suspension is filtered, and the product is washed to be neutral and dried in vacuum to obtain the fluorine doped ion sieve H 1.6 Mn 1.6 O 4 .
  10. 10. A fluorine-doped ion sieve H 1.6 Mn 1.6 O 4 , obtainable by the process of claim 9.
  11. 11. An application of fluorine doped ion sieve H 1.6 Mn 1.6 O 4 in the adsorption lithium extraction technology.

Description

Synthesis and adsorption lithium extraction application of fluorine doped ion sieve precursor Li 1.6Mn1.6O4 Technical Field The invention belongs to the technical field of extracting lithium from adsorbent brine, and particularly relates to synthesis and adsorption lithium extraction application of a fluorine doped ion sieve precursor Li 1.6Mn1.6O4. Background The strategic position of liquid lithium resources is increasingly highlighted, the lithium reserves in salt lake brine are rich, and at present, one of the brine lithium extraction methods with industrial application prospect is to adopt an inorganic adsorbent. The ion sieve adsorbent method is the most promising brine lithium extraction method currently acknowledged, and the ion sieve precursor is the key of the ion sieve preparation process, and the quality of the ion sieve precursor directly influences the quality of the ion sieve. Among the inorganic adsorbents, the manganese-based lithium ion sieve H 1.6Mn1.6O4 has great advantages in the aspect of extracting lithium from brine, and concretely comprises large lithium adsorption capacity, good selectivity and the like, but the manganese adsorption and desorption process has a certain manganese dissolution loss, so that the stability of the adsorbent is poor. Therefore, a new manganese series lithium ion sieve is researched to reduce manganese dissolution loss, improve the brine lithium extraction process and improve the lithium recovery rate, and has great significance for relieving the lithium resource market supply relation and promoting the energy form conversion. Disclosure of Invention Aiming at the defects of the prior art, the invention provides the following technical scheme: In a first aspect, the invention provides a method for synthesizing a fluorine doped ion sieve precursor Li 1.6Mn1.6O4, comprising the following steps: Placing the ionic sieve precursor Li 1.6Mn1.6O4 and the fluorine-containing ionic liquid in water, uniformly stirring, naturally cooling after thermal reaction, carrying out suction filtration, washing and finally carrying out vacuum drying to obtain the fluorine-doped ionic sieve precursor Li 1.6Mn1.6O4, wherein the fluorine is manganese= (0.05-0.8) 1 in terms of the mass ratio of fluorine in the fluorine-containing ionic liquid to manganese in the ionic sieve precursor Li 1.6Mn1.6O4. Further, the fluorine-containing ionic liquid is selected from any one of 1-butyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole hexafluorophosphate and 1-ethyl-3-methylimidazole bis-trifluoromethanesulfonyl imide salt. Further, the temperature of the thermal reaction is 150-220 ℃, and the time of the thermal reaction is 0.2-28h. Further, the temperature of the vacuum drying is 60-120 ℃, and the time of the vacuum drying is 12-24 hours. Further, the ion sieve precursor Li 1.6Mn1.6O4 is prepared by the following steps: Uniformly mixing and fully grinding a lithium source and a manganese source, placing the mixture in a pressure range of 10-100kPa, heating for two sections, and then vacuum drying to obtain an ion sieve precursor Li 1.6Mn1.6O4, wherein the mass ratio of lithium of the lithium source to manganese of the manganese source is (1.05-1.15): 1. Further, the two-stage heating is that the first stage heating is performed at a temperature of 100-120 ℃ for 24-48 hours, the second stage heating is performed at a temperature of 350-450 ℃ for 4-8 hours, wherein the temperature is controlled to 350-450 ℃ because impurities such as Li 2MnO3 can appear when the temperature of the second stage heating exceeds 450 ℃. Further, the first section heating and the second section heating are connected through a connecting pipe, and the material after the first section heating is ground until no obvious block exists. Further, the lithium source is selected from any one of lioh·h 2O、Li2CO3、LiI、LiNO3. Further, the manganese source is selected from any one of manganese carbonate MnCO 3, manganese acetate (CH 3COO)2 Mn, manganese oxalate MnC 2O4 and manganese lactate C 6H10MnO6). Further, the manganese source is subjected to calcination treatment before being mixed with the lithium source, the temperature of the calcination treatment is 750-850 ℃, and the time of the calcination treatment is 5-10 hours. In a second aspect, the present invention provides a fluorine doped ion sieve precursor Li 1.6Mn1.6O4, obtained by the above synthesis method. In a third aspect, the invention provides a preparation method of a fluorine doped ion sieve H 1.6Mn1.6O4, wherein the synthesized fluorine doped ion sieve precursor Li 1.6Mn1.6O4 is subjected to acid washing and then is subjected to suction filtration to obtain a suspension, and a product is washed to be neutral and is dried in vacuum at 60-120 ℃ for 12-24 hours to obtain the fluorine doped ion sieve H 1.6Mn1.6O4; Further, the acid used for pickling is any one of hydrochloric acid, sulfuric acid and nitric acid; further, the concentration of hydr