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CN-121988306-A - Impregnation method amine modified solid amine adsorbent and preparation method thereof

CN121988306ACN 121988306 ACN121988306 ACN 121988306ACN-121988306-A

Abstract

The invention belongs to the technical field of solid amine adsorbent preparation, and particularly relates to an impregnation method amine modified solid amine adsorbent and a preparation method thereof. The preparation method comprises the steps of taking fly ash as a raw material, calcining and acid etching to obtain an acid activated SiO 2 precursor, then dissolving the precursor in a chelate resin exchange alkali solution, adding a macroporous guiding agent to obtain a hierarchical pore SiO 2 , preparing a spherical precursor by combining polyvinyl alcohol, nucleating the spherical precursor with terephthalaldehyde, 1,3, 5-triaminobenzene and the like at low temperature, carrying out heat preservation treatment in an inert atmosphere to obtain a composite spherical carrier, finally immersing the composite spherical carrier in an impregnating solution, and carrying out ultrasonic impregnation and sectional heating solidification to obtain the solid amine adsorbent.

Inventors

  • LIU GUANLI
  • LI XIAOLIN
  • GE CHENGMIN
  • CHEN HAO
  • WANG LIANG

Assignees

  • 山东东源新材料科技有限公司

Dates

Publication Date
20260508
Application Date
20260410

Claims (8)

  1. 1. The preparation method of the solid amine adsorbent modified by the dipping method is characterized by comprising the following steps of: S100, adopting a raw material comprising fly ash, calcining, acid etching, washing and drying to obtain an acid activated SiO 2 precursor, then carrying out chelating resin exchange, washing and drying, adding a macroporous guiding agent after alkali solution is dissolved, reacting, filtering and washing to be neutral, and drying to obtain a graded hole SiO 2 , wherein the dosage of the macroporous guiding agent is 5-10% of the mass of the fly ash; S200, adopting raw materials comprising graded holes SiO 2 , polyvinyl alcohol and water to prepare a SiO 2 spherical precursor, adopting raw materials comprising SiO 2 spherical precursor, terephthalaldehyde, 1,3, 5-triaminobenzene, boric acid, a crystallization accelerator and a catalyst, carrying out constant temperature reaction for 8-10 hours at 50-60 ℃, then raising the temperature to 70-90 ℃ to continue the reaction for 16-18 hours, carrying out heat preservation treatment under inert atmosphere, and carrying out vacuum drying to obtain a composite spherical carrier, wherein the mass ratio of the graded holes SiO 2 , the polyvinyl alcohol and the water is 100:15-22:65-85, the mass ratio of the SiO 2 spherical precursor, terephthalaldehyde, 1,3, 5-triaminobenzene, boric acid, the crystallization accelerator and the catalyst is 100:18-25:12-20:6-10:3-5:2-4; S300, preparing an impregnating solution by adopting raw materials of cetyl trimethyl ammonium bromide, diethylenetriamine pentaacetic acid, tetraethylenepentamine, ethylene glycol diglycidyl ether and ethylene glycol aqueous solution, wherein the mass ratio of the cetyl trimethyl ammonium bromide to the diethylenetriamine pentaacetic acid to the tetraethylenepentamine to the ethylene glycol diglycidyl ether to the ethylene glycol aqueous solution is 2-5:3-6:12-18:6.5-10:80-100; S400, immersing the composite spherical carrier in impregnating solution, and carrying out ultrasonic impregnation, sectional heating, curing, washing and drying to obtain the solid amine adsorbent, wherein the solid-to-liquid ratio (g: mL) of the composite spherical carrier to the impregnating solution is 1:8-12.
  2. 2. The method for preparing an impregnation-process amine-modified solid amine adsorbent according to claim 1, wherein step S100 specifically comprises: S110, crushing the fly ash, calcining for 2-3 hours at 500-600 ℃, adding a nitric acid solution, stirring for 4-5 hours at room temperature, filtering, washing to be neutral, and drying to obtain an acid activated SiO 2 precursor; S120, adding an acid-activated SiO 2 precursor into a chelate resin column, introducing deionized water for ion exchange, eluting the resin with hydrochloric acid after the ion exchange is completed, and then washing and drying to obtain a clean SiO 2 precursor; S130, mixing a clean SiO 2 precursor with a sodium hydroxide solution, stirring for 3-5 hours at 60-80 ℃, adding a macroporous guiding agent, filtering and washing to be neutral after the reaction is finished, and drying to obtain the hierarchical pore SiO 2 .
  3. 3. The method for preparing the solid amine adsorbent modified by the dipping method according to claim 2, wherein the pulverized fuel ash is pulverized to a particle size of less than or equal to 100 μm.
  4. 4. The method for preparing an impregnation-process amine-modified solid amine adsorbent according to claim 1, wherein step S200 specifically comprises: S210, mixing hierarchical pore SiO 2 , polyvinyl alcohol and water into paste, extruding and rounding to prepare spherical particles, and drying to obtain a SiO 2 spherical precursor; S220, dispersing SiO 2 spherical precursor, terephthalaldehyde and 1,3, 5-triaminobenzene in an ethanol solvent, carrying out ultrasonic treatment until the mixture is uniformly dispersed, adding a catalyst, boric acid and a crystallization accelerator, carrying out constant-temperature reaction for 8-10h at 50-60 ℃, and then raising the temperature to 70-90 ℃ for continuous reaction for 16-18h to obtain a composite spherical carrier precursor; And S230, under the inert atmosphere, carrying out vacuum drying on the precursor of the composite spherical carrier at the temperature of 250-350 ℃ for 2-3 hours to obtain the composite spherical carrier.
  5. 5. The method for preparing the dipping method amine modified solid amine adsorbent according to claim 1, wherein the step S300 is that cetyl trimethyl ammonium bromide and diethylenetriamine pentaacetic acid are added into glycol aqueous solution, stirred until the mixture is completely dissolved, tetraethylenepentamine is added, ultrasonic dispersion is carried out until the mixture is uniform, and then glycol diglycidyl ether is added, and ultrasonic dispersion is continued to obtain the dipping liquid.
  6. 6. The method for preparing the solid amine adsorbent modified by the dipping method according to claim 5, wherein the glycol aqueous solution is prepared by mixing glycol and water according to a volume ratio of 2-6:1.
  7. 7. The method for preparing the solid amine adsorbent modified by the impregnation method according to claim 1, wherein the step S400 specifically comprises the steps of immersing the composite spherical carrier in an immersion liquid, carrying out ultrasonic immersion at 40-45 ℃ for 2-3 hours, then drying at 50-60 ℃ for 8-10 hours, heating to 130-140 ℃ and preserving heat for 3-4 hours, and washing and drying to obtain the solid amine adsorbent.
  8. 8. An amine-modified solid amine adsorbent by an impregnation method is characterized in that, the solid amine adsorbent modified by the dipping method according to any one of claims 1 to 7.

Description

Impregnation method amine modified solid amine adsorbent and preparation method thereof Technical Field The invention belongs to the technical field of solid amine adsorbent preparation, and particularly relates to an impregnation method amine modified solid amine adsorbent and a preparation method thereof. Background As the concentration of carbon dioxide in the global atmosphere continues to rise, environmental problems such as global warming and extreme weather frequency caused by the continuous rise of the concentration of carbon dioxide in the global atmosphere have become a great challenge for sustainable development of human society. Wherein carbon capture has become a key technology to achieve the goal of carbon neutralization as a core component of a carbon dioxide removal technology system. The carbon trapping technology can be divided into a chemical adsorption method, a physical adsorption method, a membrane separation method, a low-temperature distillation method and the like according to a separation principle, wherein the chemical absorption/adsorption technology based on amine materials is one of the most mature technical paths in the current industrial application due to the advantages of high carbon dioxide selectivity, large adsorption capacity and the like. The traditional liquid amine absorption method has the problems of easy oxidative degradation of amine and the like, and limits the popularization and application of the method in wider scenes. In contrast, the solid amine adsorption technology has the advantages of high selectivity of a chemical absorption method and low regeneration energy consumption of a physical adsorption method by loading amino functional groups on the surface and in pore channels of a porous carrier material, and becomes a carbon trapping technology with great development potential. The solid amine adsorbent is mainly divided into an impregnation type solid amine adsorbent, a grafting type solid amine adsorbent and an in-situ polymerization type solid amine adsorbent. The impregnated solid amine adsorbent is prepared by loading amine compounds on pore channels and surfaces of a porous carrier through a physical impregnation method, penetrating and adsorbing amine liquid into the carrier through capillary action, surface tension and hydrogen bonding, and drying to remove solvents to form a stable solid adsorption material. According to different impregnation processes, the method can be further divided into a solution impregnation method, a vapor deposition method and a plasma enhanced impregnation method, wherein the solution impregnation method is a preparation method with wider application due to simple process, flexible operation and low cost. The Chinese patent publication No. CN112403441B discloses a preparation method of a CO 2 solid adsorbent loaded with organic amine by chemical bonds, mesoporous silica MPS is used as a carrier, and the CO 2 solid adsorbent is prepared by the steps of carboxyl activation, carrier surface modification, chemical bond reaction immobilization, solid adsorbent preparation and the like, so that the problems of low stability and high-temperature easy decomposition of the organic amine loaded CO 2 adsorbent are effectively solved, and the cycle stability and the adsorption rate of the CO 2 adsorbent are increased. The Chinese patent publication No. CN113877539B discloses a CO 2 solid adsorbent and preparation and application thereof, wherein organic amine is dissolved in water to obtain solution A, then metal salt is added to obtain solution B, a porous carrier is immersed in the solution B, the impregnating is completed, the aqueous solution is evaporated to obtain the CO 2 solid adsorbent, and the interaction force between organic amine molecules is reduced by preparing organic amine solution with lower viscosity, so that the organic amine has high dispersibility in carrier pore channels, the diffusion of CO 2 molecules in the adsorption process is facilitated, the transfer is enhanced, and the kinetic adsorption rate is improved. Although the impregnated solid amine adsorbent has the advantage of simple and convenient preparation process, the impregnated solid amine adsorbent has defects in the aspects of circulation stability, complex working condition adaptability and the like, so that the development of the impregnated solid amine adsorbent capable of solving the technical bottleneck has important application value. Disclosure of Invention In order to solve at least one of the problems, the invention provides a preparation method of an impregnating-method amine-modified solid amine adsorbent, which comprises the following steps: s100, adopting a raw material comprising fly ash, calcining, acid etching, washing and drying to obtain an acid activated SiO 2 precursor, then carrying out chelating resin exchange, washing and drying, adding a macroporous guiding agent after alkali solution is dissolved, reacting, filtering and