CN-121975140-A - For capturing CO2Is prepared from the adsorptive material of (A) and its preparing process

Abstract

The invention discloses an aluminum-based porous adsorption material for trapping CO 2 and a preparation method thereof. The material is prepared by taking an industrial aluminum source and formic acid radical as core components and acid radical auxiliary agents as auxiliary agents through stepwise coordination assembly of aluminum source-formic acid radical premixing and auxiliary agent adding, and other metal elements are not introduced. The invention suppresses the generation of large grains through coordination competition of acid radical auxiliary agents, constructs a hydrogen limiting domain cavity (3.8A), has the dynamic adsorption capacity of engineering CO 2 up to 48.8 cm <3 >/g, the dynamic selectivity of CO 2 /N 2 up to 12.8, has low single-tower carbon capture energy consumption, has material performance superior to that of commercial silica gel and similar commercial MOF materials, and effectively breaks through the bottlenecks of poor mass transfer, high cost and slow speed of the traditional materials. The adsorbent is suitable for a CO 2 /N 2 、CO 2 /low-carbon hydrocarbon mixed system, can be applied to industrial scenes such as flue gas decarburization, natural gas upgrading and the like, and has the advantages of low raw material cost, simple process and obvious application potential.

Inventors

• CHEN HONGWEI
• ZHANG JUNLAI
• YAO ZHONGHUA
• LIU MIN
• HUANG CHEN
• CHEN YUJIA
• LI XU
• LI YALING
• LIANG LIYOU
• YUAN YING
• JIAN SHANSHAN
• Xue tianwei

Assignees

• 西南化工研究设计院有限公司

Dates

Publication Date

20260505

Application Date

20260316

Claims (10)

1. 1. An aluminum-based porous adsorption material for trapping CO 2 is characterized in that the aluminum-based porous adsorption material is formed by taking an aluminum source and formic acid radical as core components and then assisting acid radical auxiliary agents through step-by-step coordination assembly, and the preparation method is characterized in that the aluminum source and the raw materials containing the acid radical are premixed for a period of time, and then the raw materials containing the acid radical auxiliary agents are added.
2. 2. The porous alumina-based adsorbent material for capturing CO 2 according to claim 1, wherein oxalate, maleate, malonate, fumarate, citrate and malate are used as target acid groups, the raw material containing the acid group auxiliary agent is selected from one or more corresponding compounds in the group consisting of organic acid containing target acid groups, salts containing target acid groups, and solutions formed by mixing the organic acid containing target acid groups with at least one acidic substance other than the organic acid containing target acid groups.
3. 3. The porous alumina-based adsorbent material for capturing CO 2 according to claim 1, wherein the formate-containing raw material compound is one or more of formic acid, formate and formic acid mixed solution, and the raw material compound containing aluminum source is one or more of aluminum hydroxide, aluminate, basic aluminum carbonate and solution formed by mixing aluminum chloride with an organic solvent.
4. 4. The porous adsorption material of claim 3, wherein said formate is a salt of formic acid and a base, and said basic aluminum carbonate is an aluminum-containing compound of an aluminum source and a base or carbonate.
5. 5. The porous adsorption material for capturing CO 2 , wherein the formate is selected from the group consisting of sodium formate, potassium formate and ammonium formate, the formic acid mixed solution is selected from the group consisting of formic acid-hydrochloric acid mixed solution and formic acid-acetic acid buffer solution, the basic aluminum carbonate is selected from the group consisting of sodium metaaluminate and basic aluminum magnesium carbonate, and the aluminum chloride mixed solution is selected from the group consisting of AlCl 3 -DMF solution and AlCl 3 -NMP mixed solution.
6. 6. A method for producing an aluminum-based porous adsorbent material for capturing CO 2 according to any one of claims 1 to 5, characterized by comprising the steps of: step 1, uniformly mixing a formate-containing raw material 1 and an aluminum source-containing raw material 2, and carrying out co-heating stirring, condensation and reflux under the condition of oil bath; step 2, adding a raw material 3 containing acid radical auxiliary agent into the substance obtained in the step 1, and continuously co-heating, stirring, condensing and refluxing under the condition of oil bath; and 3, cooling the substance obtained in the step 2, filtering to separate white solid, washing the separated white solid until the clear liquid is neutral, and finally drying, forming and grinding to obtain the aluminum-based porous adsorption material.
7. 7. The method according to claim 6, wherein the molar ratio of the aluminum source-containing raw material 2 to the formate-containing raw material 1 is 1 to 300 in terms of Al.
8. 8. The method of claim 6, wherein the molar ratio of the aluminum source-containing raw material 2 to the acid-group-containing auxiliary material 3 is 1 to 50 in terms of Al.
9. 9. The preparation method of the heat treatment agent, which is characterized in that the total heat stirring time in the step 1 is 30-90 min, the temperature of the oil bath in the step 1 and the step 2 is 25-120 ℃, the stirring rotating speed is not lower than 400 r/min, and the total reaction time in the step 1 and the step 2 is 2-48 hours.
10. 10. The process according to claim 6, wherein the drying temperature in step 3 is not less than 120 ℃.

Description

Adsorption material for trapping CO 2 and preparation method thereof Technical Field The invention belongs to the field of gas adsorption separation, and particularly relates to an adsorption material for capturing CO 2 and a preparation method thereof. Background The current industrial carbon trapping technology is mainly divided into three routes of pre-combustion trapping, oxygen-enriched combustion and post-combustion trapping. The method is characterized in that after combustion, the process of capturing does not need to be modified, the method can be directly adapted to the existing equipment such as power plants and kilns, the applicability is the most extensive, and the method is an important development direction of the current industrial scene. In the technology system of trapping after combustion (physical adsorption separation, chemical absorption, membrane separation and the like), the physical adsorption separation technology is regarded as one of the technologies with the most scale industrial application potential because of low comprehensive energy consumption, small equipment investment, simple process flow and no secondary pollution. The core performance of the technology depends on the adsorbent material, namely physical adsorption separation can be further subdivided into Pressure Swing Adsorption (PSA), temperature Swing Adsorption (TSA) and pressure swing coupling adsorption (PTSA), wherein the pressure swing adsorption has become the main technical direction of industrial carbon capture due to low operation cost, high separation efficiency and great working condition elasticity (being adaptable to flue gas with different CO 2 concentrations), and the performance breakthrough of the PSA technology is essentially dependent on the development of high-performance adsorbents. The Metal Organic Framework (MOF) material is used as a novel porous crystalline material, is formed by coordination self-assembly of metal ions/clusters and organic ligands, and shows remarkable advantages in separation of CO 2/N2、CO2/low-carbon hydrocarbon and other mixed systems by virtue of the characteristics of high specific surface area, adjustable pore channel structure, easy functional modification of the surface, excellent regeneration stability and the like, and is far superior to the traditional porous materials such as activated carbon, silica gel, zeolite molecular sieve and the like. Its core advantage is derived from the highly customizable pore environment that the hydrogen-limited pore (e.g., C-H bond of formic acid ligand is directed into the pore) in the MOF framework can form adsorption sites matching the electrostatic potential distribution of CO 2 molecule-while CO 2 molecule is overall nonpolar, its strong polarity of C=O bond results in partial charge separation in the molecule (O atom is partially negatively charged and C atom is partially positively charged) and the symmetrically distributed polar bond imparts higher polarizability to it, MOF can pass through H in the poreO hydrogen bond, CThe O electrostatic effect is specifically combined with CO 2, so that high-efficiency selective adsorption is realized. However, the existing MOF and porous materials still have a core bottleneck that is difficult to break through in industrial carbon capture scenarios, and are specifically expressed as follows: (1) Taking 2021 year Svante company and Pasteur cooperation amplified CALF-20 as an example, the zinc-based MOF is formed by coordination of Zn 2+, 1,2, 4-triazole and oxalate, and although the industrial demonstration of capturing 1 ton of CO 2 daily (the first industrial grade MOF application worldwide) is realized in Lafare Holcim cement plant in Canada due to high CO 2 capturing capacity and water stability, the key ligand 1,2, 4-triazole is high in price, so that the material cost is high, and the economic feasibility of a large-scale decarburization device is difficult to support; (2) The mass transfer kinetic performance is poor, the suitability is insufficient, although the Zn-MOR molecular sieve (CN 116022819A) reported by Tai principle works can prepare a carbon-trapped zeolite material at low cost and realize the removal of CO 2 in a multi-component, the adsorption kinetic performance is insufficient, the rapid adsorption requirement of high-flux industrial air flow is difficult to meet, in addition, the ultra-microporous material Al (HCOO) 3 reported by Anthony K.Cheethane subject group has the equilibrium adsorption capacity of 3.85 mmol/g (about 86.2 mL/g) to CO 2 at normal temperature and pressure, but the pore structure is formed by pore windows limited by two hydrogen atoms (small pore size and large pore size and LC) -the pore diameter of SC and LC is extremely close to the dynamic diameter (3.3A) of CO 2, the molecular sieve can be realized, the gas diffusion rate is obviously limited, meanwhile, large grains are easy to form in the synthesis process of aluminum formate, the po