Search

CN-122011431-A - SDS micelle-mediated swelling enhanced adsorption lithium ion sieve HMO@PPSH hydrogel and preparation method and application thereof

CN122011431ACN 122011431 ACN122011431 ACN 122011431ACN-122011431-A

Abstract

The invention belongs to the technical field of preparation of high polymer materials, and provides a lithium ion sieve HMO@PPSH hydrogel for strengthening adsorption by SDS micelle-mediated swelling, and a preparation method and application thereof. Mixing MnCO 3 and Li 2 CO 3 according to the mole ratio of Li/Mn of 1.33:1.67, performing heat treatment for 4 hours in 500 ℃ air to obtain precursor LMO, preparing PVA solution and SDS solution, mixing the PVA solution, the SDS solution, AM, MBA and LMO, obtaining solution A after bubbles disappear, adding ammonium persulfate solution into the solution A, reacting for 6-8 hours at 60 ℃ to obtain LMO@PPSH, soaking the LMO@PPSH in HCl solution, and washing with deionized water to obtain the HMO@PPSH composite material. The adsorption content of 30% HMO@PPSH is up to 52.79 mg/g. The method has high selectivity, the extraction efficiency of Li + in natural seawater is up to 98.12%, and the adsorption capacity is high under 10 adsorption-desorption cycles.

Inventors

  • WANG MEILING
  • LI CHENYANG
  • ZHANG CHAOQUN
  • ZHANG JIAPENG

Assignees

  • 太原理工大学

Dates

Publication Date
20260512
Application Date
20260107

Claims (6)

  1. 1. A preparation method of a lithium ion sieve HMO@PPSH hydrogel with SDS micelle mediated swelling enhanced adsorption is characterized by mixing MnCO 3 and Li 2 CO 3 according to a molar ratio of Li/Mn of 1.33:1.67, performing heat treatment for 4 hours in air at 500 ℃ to obtain precursor lithium manganese oxide LMO, mixing a polyvinyl alcohol PVA solution, a sodium dodecyl sulfate SDS solution, acrylamide AM, methylene bisacrylamide MBA and LMO, obtaining a solution A after bubbles disappear, adding an ammonium persulfate APS solution into the solution A, reacting for 6-8 hours at 60 ℃ to obtain LMO@PPSH, and finally soaking the prepared LMO@PPSH in an HCl solution, and washing with deionized water to obtain the HMO@PPSH composite material.
  2. 2. The preparation method of claim 1, which is characterized by comprising the following steps: (1) Li 1.33 Mn 1.67 O 4 is prepared by mixing MnCO 3 and Li 2 CO 3 according to the mole ratio of Li/Mn of 1.33:1.67, and performing heat treatment on the mixture in 500 ℃ air for 4 hours to obtain a precursor lithium manganese oxide LMO; (2) Preparing an LMO@PPSH composite material, namely firstly preparing a 5% PVA solution, dissolving PVA in deionized water, swelling for 1h at 60 ℃, then dissolving for 1h at 90 ℃, taking 1.2-3.5g of 5wt% PVA, adding 0.0577-0.1154g of SDS, 0.25-0.5mL of water, stirring in a 50 ℃ water bath until no bubble exists, adding 0.5g of AM, 0.015-0.030g of MBA and 0.5-1mL of deionized water at room temperature, stirring for 1h at room temperature, and then adding the LMO obtained in the step (1) according to the mass ratio of the LMO/LMO composite hydrogel of 10%,20%,30%,40% and 50%, stirring at room temperature for 1h until the bubble disappears, thereby obtaining a solution A; 30-150mg of APS is dissolved in 0.5-2.5mL of deionized water to form solution B, the solution B is added into the solution A while stirring, the solution A is stirred for 1-2min at room temperature to be fully dissolved in the solution A, and the solution is reacted for 6-8h at 60 ℃ to obtain the LMO@PPSH composite material; (3) And (3) preparing the HMO@PPSH composite material, namely soaking the LMO@PPSH obtained in the step (3) in 0.5M HCl solution for 24 hours, and flushing with deionized water to obtain the HMO@PPSH composite material.
  3. 3. The preparation method of the composite hydrogel according to claim 2, wherein the mass ratio of the composite hydrogel in the step (2) is 30%, and the mass percentage of HMO to the HMO@PPSH in the HMO@PPSH prepared in the step (3) is 30%.
  4. 4. The lithium ion sieve hmo@ppsh hydrogel obtained by the method of any one of claims 1 to 3, wherein the SDS micelles mediate swelling to strengthen adsorption.
  5. 5. The application of the HMO@PPSH hydrogel in extracting lithium from seawater.
  6. 6. The method of claim 5, wherein the HMO@PPSH hydrogel is soaked in seawater, kept at a constant temperature of 25 ℃ and adsorbed under stirring at a rotating speed of 150rpm, and lithium ion concentration in the solution at different times is measured by an inductively coupled plasma emission spectrometer ICP-MS.

Description

SDS micelle-mediated swelling enhanced adsorption lithium ion sieve HMO@PPSH hydrogel and preparation method and application thereof Technical Field The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a lithium ion sieve HMO@PPSH hydrogel for strengthening adsorption by SDS micelle-mediated swelling, and a preparation method and application thereof. More particularly relates to a lithium ion sieve hydrogel with sodium dodecyl sulfate micelle-mediated swelling and enhanced adsorption. Aiming at a seawater complex natural solution system, the invention provides a porous HMO@PPSH composite material with high swelling capacity and enhanced lithium ion adsorption, which is prepared by selecting different substrate materials by taking Li 1.33Mn1.67O4 as a Li + imprinting site and adopting a simple synthesis method. Background In recent years, lithium has been widely used in the fields of ceramics, glass, rechargeable lithium batteries, nuclear fusion fuels, energy storage materials, and the like. However, as demand increases, meeting the provision of lithium resources becomes an important challenge. According to related researches, lithium resources are mainly derived from ores, salt lake seawater and seawater, wherein the seawater has high Li + content and low concentration, and meanwhile, the seawater also contains a large amount of coexisting alkali metal ions (Na +、K+、Ca2+、Mg2+), which brings great difficulty to extracting Li +. The HMO-based lithium ion sieve is one of the most popular lithium adsorbents because of its advantages such as excellent lithium selectivity and high lithium adsorption capacity. Although HMO shows excellent selectivity to Li +, the method has some problems restricting practical application when extracting lithium by a physical method, such as (1) more Mn dissolution loss during acid leaching, (2) easy powder loss during adsorption, (3) longer adsorption time, and (4) capacity reduction caused by embedding of powder agglomeration adsorption sites. Disclosure of Invention The invention provides a lithium ion sieve HMO@PPSH hydrogel for enhancing adsorption by SDS micelle-mediated swelling, and a preparation method and application thereof, and aims to solve the problems that the existing lithium ion sieve is in a powdery state and is not easy to recover, and adsorption capacity is reduced due to embedding of powder agglomeration adsorption sites. The composite material (HMO@PPSH) of H 1.33Mn1.67O4 is coated by the hydrogel doped with the dodecyl sodium sulfate SDS anionic surfactant micelle, and the continuous swelling capacity of the lithium ion sieve hydrogel in the adsorption process is enhanced by the surfactant modification, so that the exposure of an H 1.33Mn1.67O4 active site is promoted, and the adsorption performance of the lithium ion sieve hydrogel on lithium ions is finally improved. The preparation method of the lithium ion sieve HMO@PPSH hydrogel comprises the following steps of mixing MnCO 3 and Li 2CO3 according to a molar ratio of Li/Mn of 1.33:1.67, performing heat treatment for 4 hours in 500 ℃ air to obtain precursor lithium manganese oxide LMO, mixing a polyvinyl alcohol PVA solution, sodium dodecyl sulfate SDS, acrylamide AM, methylene bisacrylamide MBA and LMO, obtaining a solution A after bubbles disappear, adding an ammonium persulfate APS solution into the solution A, reacting for 6-8 hours at 60 ℃ to obtain LMO@PPSH, finally soaking the prepared LMO@PPSH into a 0.5M HCl solution, and washing with deionized water to obtain the HMO@PPSH composite material. The method specifically comprises the following steps: (1) Li 1.33Mn1.67O4 is prepared by mixing MnCO 3 and Li 2CO3 according to the mole ratio of Li/Mn of 1.33:1.67, and performing heat treatment on the mixture in 500 ℃ air for 4 hours to obtain a precursor lithium manganese oxide LMO; (2) Preparation of lmo@ppsh composite a 5% polyvinyl alcohol (PVA) solution was first prepared (PVA dissolved in deionized water, swollen for 1h at 60 ℃ and then dissolved for 1h at 90 ℃). Taking 1.2-3.5 g wt% PVA solution, adding 0.0577-0.1154g SDS and 0.25-0.5mL water, stirring in a 50 ℃ water bath until no bubble exists, adding 0.5g AM, 0.015-0.030g MBA and 0.5-1mL deionized water at room temperature, stirring at room temperature for 1h, adding LMO obtained in the step (1) according to the mass ratio of LMO/LMO composite hydrogel of 10%,20%,30%,40% and 50%, stirring at room temperature for 1h until the bubble disappears, and obtaining solution A; 30-150mg of APS is dissolved in 0.5-2.5mL of deionized water to form solution B, the solution B is added into the solution A while stirring, the solution A is stirred for 1-2min at room temperature to be fully dissolved in the solution A, and the solution is reacted for 6-8h at 60 ℃ to obtain the LMO@PPSH composite material; (3) And (3) preparing the HMO@PPSH composite material, namely soaking the LMO@PPSH obtained in t