High-adsorption-capacity solid polyamine carbon capture material and preparation method thereof

Abstract

The invention relates to the technical field of CO2 capture, in particular to a high-adsorption-capacity solid polyamine carbon capture material and a preparation method thereof. The amine loading amount and CO2 adsorption capacity of a conventional grafted solid polyamine adsorption material are relatively low, the amine loading amount is difficult to reach 9mmol / g or above, and the CO2 adsorption capacity is difficult to reach 4.5 mmol / g or above. In order to solve the technical problems, the invention provides the high-adsorption-capacity solid polyamine carbon capture material which is prepared by grafting polyamine compounds (such as L-arginine and guanidinopropionic acid) on the surface of polystyrene primary amine resin through amidation reaction, so that the active amino density on the surface of a polystyrene primary amine resin adsorption material is remarkably improved, and the adsorption capacity of the solid polyamine carbon capture material is improved. The prepared amino resin has the advantages that the amino loading capacity can reach 9mmol / g or more and is far higher than that of the traditional amino resin (generally less than or equal to 6mmol / g), the CO2 adsorption capacity breaks through 4.5 mmol / g and is at a leading level in a solid adsorption material, and the unit CO2 capture cost can be greatly reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of CO2 capture, and in particular to a solid polyamine carbon capture material with high adsorption capacity and a preparation method thereof. Background Art

[0002] Against the backdrop of the intensifying global climate crisis, carbon capture, utilization, and storage (CCUS) technology has garnered widespread international attention. The International Energy Agency (IEA) predicts that global CO2 capture will need to reach 800 million tons by 2030, and CCUS technology is expected to contribute 15% of global CO2 emissions reductions by 2050. While liquid amine absorption has achieved industrial application, its inherent drawbacks significantly hinder its large-scale adoption: equipment corrosion leads to high maintenance costs, the energy consumption of the absorption-desorption process accounts for over 60% of the total carbon capture system cost, and the volatilization of amines can easily cause secondary environmental pollution. Therefore, the development of a new generation of high-efficiency, low-energy CO2 adsorption materials has become a key focus for CCUS technological breakthroughs.

[0003] In recent years, solid-state amine adsorbents have emerged as a promising field due to their unique advantages. Compared to liquid amine systems, solid-state amine adsorbents based on silica, carbon materials, and organic polymers exhibit significant advantages, such as low operating costs, low amine volatility (volatile losses reduced by over 90%), and low regeneration temperatures (<120°C). There are two main preparation technology routes in this field: Physical impregnation: Polyamine molecules are loaded onto the surface of a porous support via van der Waals forces. This method is simple to operate and can achieve amino group loadings of 30-50 wt%. However, the physical bonding method results in poor material stability, with polyamine leaching exceeding 40% after 3-5 cycles, severely limiting its industrial application.

[0004] Chemical grafting: Polyamine molecules are chemically bonded to the support surface using covalent bonds. Typical techniques, such as the Mannich reaction and amine exchange reaction, reduce polyamine leaching rates to below 5% under high-temperature regeneration (100-150°C). However, limitations such as the density of reactive sites on the support surface (typically <2.0 mmol / g) and the steric hindrance of polyamine molecules (a single molecule can occupy 3-5 active sites) prevent amine loadings exceeding 15 wt%, and adsorption capacities generally fall below 3.0 mmol / g. For example, the PEI-MF resin (based on melamine formaldehyde resin) and PEI-MF / PAM composite resin developed by Chen Shuijia's team have saturated carbon dioxide adsorption capacities of only 1.32 mmol / g and 2.80 mmol / g, respectively, significantly lower than the theoretical adsorption capacity of a liquid amine system (approximately 4.5 mmol / g).

[0005] The current technical bottleneck can be summarized as follows: Traditional grafted solid-state amine materials struggle to achieve a synergistic increase in amine loading and adsorption capacity while maintaining high stability. Existing grafting methods fail to effectively address the conflict between polyamine molecular occupancy and active site utilization. Therefore, developing novel grafted solid-state polyamine adsorbent materials that combine high stability, high amine loading (>20wt%), and high adsorption capacity (>4.0mmol / g) has become a key technical challenge in promoting the commercialization of CCUS technology. Summary of the Invention

[0006] Problems with existing technologies include low amine loading and low CO2 adsorption capacity of conventional grafted solid polyamine adsorption materials. It is difficult to achieve an amine loading exceeding 9 mmol / g, and a CO2 adsorption capacity exceeding 4.5 mmol / g. To address these technical issues, the present invention provides a high-adsorption capacity solid polyamine carbon capture material comprising a polyamine compound grafted onto the surface of a polystyrene primary amine resin via an amidation reaction.

[0007] Preferably, the polystyrene primary amine resin includes one of Purolite A110 primary amine resin, Suqing D309 primary amine resin, and Lewatit VP OC 1065 primary amine resin.

[0008] Preferably, the polyamine compound includes one or more amino acids and / or amino acid derivatives.

[0009] Preferably, the amino acid comprises L-arginine.

[0010] Preferably, the amino acid derivative comprises guanidinopropionic acid and / or guanidinoacetic acid.

[0011] Preferably, the preparation method of the high adsorption capacity solid polyamine carbon capture material comprises the following steps: (1) Adding polystyrene primary amine resin to solvent molecules, utilizing the solvation effect between the hydrophilic groups in the polystyrene primary amine resin and the solvent molecules to fully swell (the solvent molecules penetrate into the interior of the polystyrene primary amine resin through capillary action, and the hydrophilic groups in the polystyrene primary amine resin interact with the solvent molecules to form a solvation layer. The osmotic pressure generated by the solvation effect and the elastic contraction force of the resin skeleton reach a dynamic balance, thereby obtaining a fully swollen polystyrene primary amine resin); (2) The polyamine compound is added to the swelling system of step (1), and concentrated sulfuric acid is added as a catalyst. The primary amine groups on the surface of the swollen polystyrene primary amine resin undergo amidation reaction with the polyamine compound. After the reaction is completed, the reaction product is sequentially filtered, washed with anhydrous ethanol, washed with deionized water, acid washed (pH of the filtrate = 1), washed with deionized water, washed with alkali (pH of the filtrate = 14), and washed with deionized water until the filtrate is neutral. The obtained solid product is dried to obtain a high adsorption capacity solid polyamine carbon capture material.

[0012] Preferably, the solvent molecules include one or more of anhydrous ethanol, deionized water, N,N-dimethylformamide, and dimethyl sulfoxide.

[0013] Preferably, the temperature of the amidation reaction is 80-120°C.

[0014] The present invention has the following beneficial effects: (1) Through the amidation reaction, polyamine compounds (such as L-arginine, guanidine propionic acid, etc.) are precisely grafted on the surface of polystyrene primary amine resin, which significantly increases the density of active amine groups. The amine loading can reach more than 9 mmol / g, which is much higher than that of traditional amino resins (usually ≤6 mmol / g). The adsorption capacity has exceeded 4.5 mmol / g, which is at the leading level among solid adsorption materials and can significantly reduce the unit C capture costs; (2) The polyamine compound is firmly grafted to the polystyrene primary amine resin skeleton through a chemical bond (amide bond), avoiding the dissolution loss of the amine component in the traditional physical impregnation method; the acid / alkaline washing process (pH=1 acid washing → pH=14 alkaline washing) completely removes unreacted impurities, ensuring that the material maintains structural integrity at high temperatures (80-120℃) and multiple adsorption-desorption cycles; (3) Swelling pretreatment (solvation balances osmotic pressure and skeleton elasticity) allows solvent molecules (such as DMF, DMSO) to fully penetrate the resin, greatly improving the reaction efficiency of polyamine compounds and primary amine groups. Concentrated sulfuric acid is not a commonly used catalyst for the amidation reaction between polystyrene primary amine resin and amino acids or amino acid derivatives. Concentrated sulfuric acid catalyzes the amidation reaction under mild conditions (80–120°C), is easy to operate, and is suitable for large-scale production. Concentrated sulfuric acid can increase the sensitivity of carboxyl carbon atoms to nucleophilic attack by amines, thereby accelerating the heterogeneous amidation reaction. Concentrated sulfuric acid also has extremely strong water absorption and dehydration properties. It can effectively absorb water molecules produced in the reaction and drive the heterogeneous amidation reaction toward the product direction; (4) Solid materials can be directly filled into fixed bed reactors, and are suitable for low-concentration C In capture scenarios, the high amine density and chemical stability give it long-term applicability in temperature swing adsorption (TSA) or pressure swing adsorption (PSA) processes. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 : It is the CO2 adsorption process curve of MZJ-1 obtained in Example 1 of the present invention and DMZJ-1 obtained in Comparative Example 1. DETAILED DESCRIPTION

[0016] The present invention will be described in detail below with reference to the following examples. However, it should be understood that the following examples are merely illustrative of the embodiments of the present invention and are not intended to limit the scope of the present invention.

[0017] Example 1

[0018] A high-adsorption capacity solid polyamine carbon capture material, MZJ-1, is prepared by grafting guanidine acetic acid onto the surface of Purolite A110 primary amine resin via an amide bond. The specific preparation method is as follows: (1) Swelling: Place 1.0 g of Purolite A110 primary amine resin in a 25 mL Shrek tube, add 10 mL of anhydrous ethanol, and swell for 12 h. (2) Grafting reaction: 8.1 g of guanidine acetic acid (10 mmol) was added to the reaction system after swelling, and 0.5 g of concentrated sulfuric acid was added. The mixture was stirred in an oil bath at 80 °C for 12 h. After the reaction was completed, anhydrous ethanol and guanidine acetic acid were removed by filtration. The obtained solid reaction product was then placed in a chromatography column and washed with anhydrous ethanol, deionized water, 1 mol / L hydrochloric acid (washed until the pH of the filtrate was 1), deionized water, 1 mol / L sodium hydroxide aqueous solution (washed until the pH of the filtrate was 12), and deionized water (washed until the pH of the filtrate was 7). The obtained solid product was then placed in an oven (temperature of 65 °C) and dried at normal pressure for 6 h. It was then placed in a vacuum drying oven (vacuum degree of -0.1 MPa, temperature of 65 °C) and dried for 6 h to obtain a high adsorption capacity solid polyamine carbon capture material MZJ-1.

[0019] Example 2

[0020] A high adsorption capacity solid polyamine carbon capture material MZJ-2 is prepared by grafting guanidine propionic acid onto the surface of Suqing D309 primary amine resin via an amide bond. The specific preparation method is as follows: (1) Swelling: Place 1.0 g of Suqing D309 primary amine resin in a 25 mL Shrek tube, add 5 mL of deionized water, and swell for 24 h. (2) Grafting reaction: 4.5 g of guanidine propionic acid (5 mmol) was added to the reaction system after swelling, and 1 g of concentrated sulfuric acid was added. The reaction was stirred in an oil bath at 120 °C for 48 h. After the reaction was completed, the deionized water and guanidine propionic acid were removed by filtration. The obtained solid reaction product was then placed in a chromatography column and washed with anhydrous ethanol, deionized water, 1 mol / L hydrochloric acid (washed to the pH of the filtrate = 1), deionized water, 1 mol / L sodium hydroxide aqueous solution (washed to the pH of the filtrate = 12), and deionized water (washed to the pH of the filtrate = 7). The obtained solid product was then placed in an oven (temperature of 65 °C) and dried at normal pressure for 6 h. It was then placed in a vacuum drying oven (vacuum degree of -0.1 MPa, temperature of 65 °C) and dried for 6 h to obtain a high adsorption capacity solid polyamine carbon capture material MZJ-2.

[0021] Example 3

[0022] A high-adsorption capacity solid polyamine carbon capture material, MZJ-3, is prepared by grafting L-arginine onto the surface of Lewatit VP OC 1065 primary amine resin via an amide bond. The specific preparation method is as follows: (1) Swelling: Place 1.0 g of Lewatit VP OC 1065 primary amine resin in a 25 mL Shrek tube, add 7 mL of N,N-dimethylformamide, and swell for 18 h. (2) Grafting reaction: 1.2 g of L-arginine (1 mmol) was added to the swelling reaction system, and 0.8 g of concentrated sulfuric acid was added. The reaction was stirred in an oil bath at 90 °C for 48 h. After the reaction was completed, N,N-dimethylformamide and L-arginine were removed by filtration. The obtained solid reaction product was then placed in a chromatography column and washed with anhydrous ethanol, deionized water, 1 mol / L hydrochloric acid (washed to the pH of the filtrate = 1), deionized water, 1 mol / L sodium hydroxide aqueous solution (washed to the pH of the filtrate = 12), and deionized water (washed to the pH of the filtrate = 7). The obtained solid product was then placed in an oven (temperature of 65 °C) and dried at normal pressure for 6 h. It was then placed in a vacuum drying oven (vacuum degree of -0.1 MPa, temperature of 65 °C) and dried for 6 h to obtain a high adsorption capacity solid polyamine carbon capture material MZJ-3.

[0023] Example 4

[0024] A high-adsorption capacity solid polyamine carbon capture material, MZJ-4, is prepared by grafting guanidine acetic acid onto the surface of Lewatit VP OC 1065 primary amine resin via an amide bond. The specific preparation method is as follows: (1) Swelling: Place 1.0 g of Lewatit VP OC 1065 primary amine resin in a 25 mL Shrek tube, add 5 mL of dimethyl sulfoxide, and allow to swell for 15 h. (2) Grafting reaction: 2.4 g of guanidine acetic acid (3 mmol) was added to the swelling reaction system, and 0.5 g of concentrated sulfuric acid was added. The reaction was stirred in an oil bath at 100 °C for 36 h. After the reaction was completed, dimethyl sulfoxide and guanidine acetic acid were removed by filtration. The obtained solid reaction product was then placed in a chromatography column and washed with anhydrous ethanol, deionized water, 1 mol / L hydrochloric acid (washed to the pH of the filtrate = 1), deionized water, 1 mol / L sodium hydroxide aqueous solution (washed to the pH of the filtrate = 12), and deionized water (washed to the pH of the filtrate = 7). The obtained solid product was then placed in an oven (temperature of 65 °C) and dried at normal pressure for 6 h. It was then placed in a vacuum drying oven (vacuum degree of -0.1 MPa, temperature of 65 °C) and dried for 6 h to obtain a high adsorption capacity solid polyamine carbon capture material MZJ-4.

[0025] Example 5

[0026] A high-adsorption capacity solid polyamine carbon capture material, MZJ-5, is prepared by grafting guanidine propionic acid onto the surface of Purolite A110 primary amine resin via an amide bond. The specific preparation method is as follows: (1) Swelling: Place 1.0 g of Lewatit VP OC 1065 primary amine resin in a 25 mL Shrek tube, add 8 mL of anhydrous ethanol, and swell for 24 h. (2) Grafting reaction: 5.4 g of guanidine propionic acid (6 mmol) was added to the reaction system after swelling, and 0.6 g of concentrated sulfuric acid was added. The reaction was stirred in an oil bath at 80 °C for 36 h. After the reaction was completed, the anhydrous ethanol and guanidine propionic acid were removed by filtration. The obtained solid reaction product was then placed in a chromatography column and washed with anhydrous ethanol, deionized water, 1 mol / L hydrochloric acid (washed to the pH of the filtrate = 1), deionized water, 1 mol / L sodium hydroxide aqueous solution (washed to the pH of the filtrate = 12), and deionized water (washed to the pH of the filtrate = 7). The obtained solid product was then placed in an oven (temperature of 65 °C) and dried at normal pressure for 6 h. It was then placed in a vacuum drying oven (vacuum degree of -0.1 MPa, temperature of 65 °C) and dried for 6 h to obtain a high adsorption capacity solid polyamine carbon capture material MZJ-5.

[0027] Example 6

[0028] A high adsorption capacity solid polyamine carbon capture material MZJ-6 is prepared by grafting L-arginine onto the surface of Suqing D309 primary amine resin via an amide bond. The specific preparation method is as follows: (1) Swelling: Place 1.0 g of Suqing D309 primary amine resin in a 25 mL Shrek tube, add 10 mL of deionized water, and swell for 12 h. (2) Grafting reaction: 3.6 g L-arginine (3 mmol) was added to the swelling reaction system, and 0.9 g concentrated sulfuric acid was added. The reaction was stirred in an oil bath at 100 °C for 24 h. After the reaction was completed, the deionized water and L-arginine were removed by filtration. The solid reaction product was then placed in a chromatography column and washed with anhydrous ethanol, deionized water, 1 mol / L hydrochloric acid (washed to the pH of the filtrate = 1), deionized water, 1 mol / L sodium hydroxide aqueous solution (washed to the pH of the filtrate = 12), and deionized water (washed to the pH of the filtrate = 7). The solid product was then placed in an oven (temperature of 65 °C) and dried at normal pressure for 6 h. It was then placed in a vacuum drying oven (vacuum degree of -0.1 MPa, temperature of 65 °C) and dried for 6 h to obtain a high adsorption capacity solid polyamine carbon capture material MZJ-6.

[0029] Example 7

[0030] A high-adsorption capacity solid polyamine carbon capture material, MZJ-7, is prepared by grafting L-arginine onto the surface of Purolite A110 primary amine resin via an amide bond. The specific preparation method is as follows: (1) Swelling: Place 1.0 g of Purolite A110 primary amine resin in a 25 mL Shrek tube, add 8 mL of N,N-dimethylformamide, and swell for 20 h. (2) Grafting reaction: 2.4 g L-arginine (2 mmol) was added to the swelling reaction system, and 0.8 g concentrated sulfuric acid was added. The reaction was stirred in an oil bath at 110 °C for 24 h. After the reaction was completed, N,N-dimethylformamide and L-arginine were removed by filtration. The solid reaction product was then placed in a chromatography column and washed with anhydrous ethanol, deionized water, 1 mol / L hydrochloric acid (washed to the pH of the filtrate = 1), deionized water, 1 mol / L sodium hydroxide aqueous solution (washed to the pH of the filtrate = 12), and deionized water (washed to the pH of the filtrate = 7). The solid product was then placed in an oven (temperature of 65 °C) and dried at normal pressure for 6 h. It was then placed in a vacuum drying oven (vacuum degree of -0.1 MPa, temperature of 65 °C) and dried for 6 h to obtain a high adsorption capacity solid polyamine carbon capture material MZJ-7.

[0031] Example 8

[0032] A high adsorption capacity solid polyamine carbon capture material MZJ-8 is prepared by grafting guanidine propionic acid onto the surface of Suqing D309 primary amine resin via an amide bond. The specific preparation method is as follows: (1) Swelling: Place 1.0 g of Suqing D309 primary amine resin in a 25 mL Shrek tube, add 5 mL of dimethyl sulfoxide, and swell for 15 h. (2) Grafting reaction: 4.5 g of guanidine propionic acid (5 mmol) was added to the reaction system after swelling, and 1.0 g of concentrated sulfuric acid was added. The reaction was stirred in an oil bath at 100 °C for 24 h. After the reaction was completed, dimethyl sulfoxide and guanidine propionic acid were removed by filtration. The obtained solid reaction product was then placed in a chromatography column and washed with anhydrous ethanol, deionized water, 1 mol / L hydrochloric acid (washed to the pH of the filtrate = 1), deionized water, 1 mol / L sodium hydroxide aqueous solution (washed to the pH of the filtrate = 12), and deionized water (washed to the pH of the filtrate = 7). The obtained solid product was then placed in an oven (temperature of 65 °C) and dried at normal pressure for 6 h. It was then placed in a vacuum drying oven (vacuum degree of -0.1 MPa, temperature of 65 °C) and dried for 6 h to obtain a high adsorption capacity solid polyamine carbon capture material MZJ-8.

[0033] Example 9

[0034] A high adsorption capacity solid polyamine carbon capture material MZJ-9 is prepared by grafting guanidine propionic acid onto the surface of Suqing D309 primary amine resin via an amide bond. The specific preparation method is as follows: (1) Swelling: Place 1.0 g of Lewatit VP OC 1065 primary amine resin in a 25 mL Shrek tube, add 7 mL of deionized water, and swell for 20 h. (2) Grafting reaction: 9.0 g of guanidine propionic acid (10 mmol) was added to the reaction system after swelling, and 1.0 g of concentrated sulfuric acid was added. The reaction was stirred in an oil bath at 110 °C for 40 h. After the reaction was completed, dimethyl sulfoxide and guanidine propionic acid were removed by filtration. The obtained solid reaction product was then placed in a chromatography column and washed with anhydrous ethanol, deionized water, 1 mol / L hydrochloric acid (washed to the pH of the filtrate = 1), deionized water, 1 mol / L sodium hydroxide aqueous solution (washed to the pH of the filtrate = 12), and deionized water (washed to the pH of the filtrate = 7). The obtained solid product was then placed in an oven (temperature of 65 °C) and dried at normal pressure for 6 h. It was then placed in a vacuum drying oven (vacuum degree of -0.1 MPa, temperature of 65 °C) and dried for 6 h to obtain a high adsorption capacity solid polyamine carbon capture material MZJ-9.

[0035] Comparative Example 1 is Purolite A110 primary amine resin.

[0036] Comparative Example 2 is Suqing D309 primary amine resin.

[0037] Comparative Example 3 is Lewatit VP OC 1065 primary amine resin.

[0038] Comparative Example 4 is the same as Example 1, except that 0.5 g of concentrated sulfuric acid is not added to the reaction system in step (2) of Comparative Example 4.

[0039] Comparative Example 5 is the same as Example 1, except that 0.5 g of concentrated sulfuric acid in Example 1 is replaced by 0.5 g of phenylboric acid in Comparative Example 5.

[0040] Comparative Example 6 is the same as Example 1, except that 0.5 g of concentrated sulfuric acid in Example 1 is replaced by 0.5 g of propyl phosphoric anhydride.

[0041] Comparative Example 7 is the same as Example 1, except that 0.5 g of concentrated sulfuric acid in Example 1 is replaced by 0.5 g of N,N'-diisopropylcarbodiimide.

[0042] Comparative Example 8 is the same as Example 1, except that the amount of guanidinoacetic acid used in the grafting reaction of Comparative Example 8 is 15 mmol, and the ratio of Purolite A110 primary amine resin to guanidinoacetic acid is less than 1 g:10 mmol.

[0043] Comparative Example 9 is the same as Example 3, except that the amount of L-arginine used in the grafting reaction of Comparative Example 9 is 0.5 mmol, and the ratio of Lewatit VP OC 1065 primary amine resin to L-arginine is > 1 g: 1 mmol.

[0044] Comparative Example 10 is the same as Example 1, except that the amount of guanidinoacetic acid used in the grafting reaction of Comparative Example 10 is 0.8 mmol, and the ratio of Purolite A110 primary amine resin to guanidinoacetic acid is >1 g:10 mmol.

[0045] Performance Testing

[0046] (1) Amine loading (E): Weigh m (0.1 g) of high adsorption capacity solid polyamine carbon capture material into a 100 mL conical flask, then transfer 50 mL of HCl solution with a concentration of C2 (0.10 mol / L) into the flask and stir at 25 After shaking in a water bath at 400 °C for 12 h, 10 mL of the supernatant was removed and titrated with NaOH solution of concentration C1 (0.05 mol / L) using phenolphthalein as an indicator until the color turned slightly red and remained unchanged for 15 s, which was the titration endpoint. The volume of NaOH consumed was V (mL). The titration was repeated three times in parallel according to the titration method. Calculate and obtain the amine loading in mmol / g.

[0047] (2) Adsorption capacity (Q): refers to the saturated adsorption capacity of amine functionalized adsorption capture material for carbon dioxide, in units of mmol / g. The determination is carried out using the DVS atmospheric pressure dynamic weight method, specifically: weigh about 30 mg of material sample and put it into a crucible, purge it with high-purity nitrogen at a flow rate of 400 SCCM, and at the same time raise the temperature to 105°C at a rate of 10°C / min, maintain the temperature and high-purity nitrogen flow rate for more than 60 minutes until the sample weighs a constant weight, cool it to 25°C, and measure the sample weight as G0. Switch the high-purity nitrogen to carbon dioxide (molar mass is M A ), continue to purge the sample at a flow rate of 400 SCCM until the sample reaches a constant weight again, which is considered adsorption saturation. The sample weight is measured as G1. The saturated adsorption capacity is calculated according to the formula: Q = [(G1-G0) / M A ] / G0 was used to calculate the saturated adsorption capacity, in units of mmol / g.

[0048] (3) Cyclic stability: It is expressed as the adsorption capacity of the solid polyamine carbon capture material after 20 adsorption / desorption cycles. The CO2 adsorption process curves of MZJ-1 obtained in Example 1 of the present invention and DMZJ-1 obtained in Comparative Example 1 are shown in the attached manual. Figure 1 shown.

[0049] The test was carried out according to the above test method. The test results are shown in Table 1: Table 1 .

[0050] The experimental data in Table 1 demonstrate that the functionalization of macroporous polystyrene primary amine resin with amine-rich amino acids and their derivatives can significantly increase the adsorbent's amine loading (≥9.8 mmol / g) and CO2 saturation adsorption capacity (≥4.5 mmol / g). Cyclic stability experiments on novel polyamine-functionalized polystyrene resin adsorbents provided in Examples 1-9 demonstrate that the amide bond between the macroporous polystyrene primary amine resin and the functionalizing agent enhances the adsorbent's cyclic stability. The experimental results in Comparative Examples 4-7 demonstrate that the presence of concentrated sulfuric acid as a catalyst is crucial for the functionalization of the macroporous polystyrene primary amine resin.

[0051] With the above-described preferred embodiments of the present invention as a guide, and with reference to the above description, relevant personnel are fully capable of making various changes and modifications without departing from the technical scope of this invention. The technical scope of this invention is not limited to the contents of the specification and must be determined according to the scope of the claims.

Claims

1. A high adsorption capacity solid polyamine carbon capture material, characterized in that: The method is to graft polyamine compounds onto the surface of polystyrene primary amine resin through amidation reaction.

2. A high adsorption capacity solid polyamine carbon capture material according to claim 1, characterized in that: The polystyrene primary amine resin includes one of Purolite A110 primary amine resin, Suqing D309 primary amine resin, and Lewatit VP OC 1065 primary amine resin.

3. The high adsorption capacity solid polyamine carbon capture material according to claim 1, characterized in that: The polyamine compound includes one or more of amino acids and / or amino acid derivatives.

4. A high adsorption capacity solid polyamine carbon capture material according to claim 3, characterized in that: The amino acids include L-arginine.

5. The high adsorption capacity solid polyamine carbon capture material according to claim 3, characterized in that: The amino acid derivatives include guanidinopropionic acid and / or guanidinoacetic acid.

6. The high adsorption capacity solid polyamine carbon capture material according to claim 1, characterized in that: The preparation method comprises the following steps: (1) Adding polystyrene primary amine resin to solvent molecules, utilizing the solvation effect between the hydrophilic groups in the polystyrene primary amine resin and the solvent molecules to fully swell (the solvent molecules penetrate into the interior of the polystyrene primary amine resin through capillary action, and the hydrophilic groups in the polystyrene primary amine resin interact with the solvent molecules to form a solvation layer. The osmotic pressure generated by the solvation effect and the elastic contraction force of the resin skeleton reach a dynamic balance, thereby obtaining a fully swollen polystyrene primary amine resin); (2) The polyamine compound is added to the swelling system of step (1), and concentrated sulfuric acid is added as a catalyst. The primary amine groups on the surface of the swollen polystyrene primary amine resin undergo amidation reaction with the polyamine compound. After the reaction is completed, the reaction product is sequentially filtered, washed with anhydrous ethanol, washed with deionized water, acid washed (pH of the filtrate = 1), washed with deionized water, washed with alkali (pH of the filtrate = 14), and washed with deionized water until the filtrate is neutral. The obtained solid product is dried to obtain a high adsorption capacity solid polyamine carbon capture material.

7. A high adsorption capacity solid polyamine carbon capture material according to claim 6, characterized in that: The solvent molecules include one or more of anhydrous ethanol, deionized water, N,N-dimethylformamide, and dimethyl sulfoxide.

8. The high adsorption capacity solid polyamine carbon capture material according to claim 6, characterized in that: The temperature of the amidation reaction is 80-120°C.

9. A CO2 capture method, characterized in that: The high adsorption capacity solid polyamine carbon capture material obtained according to any one of claims 1 to 8 is used as a CO2 adsorption material.

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