Application of alkyl hydroxyethyl ethylenediamine in carbon dioxide capture

Abstract

The invention provides application of alkyl hydroxyethyl ethylenediamine in carbon dioxide capture, and relates to the technical field of carbon dioxide capture. The alkyl hydroxyethyl ethylenediamine structure provided by the invention has one or more alkyl side chains, and the reaction path and action strength of amino and carbon dioxide can be regulated and controlled by changing the alkyl structure and number, so that the purpose of enhancing the degradation resistance is achieved while the desorption energy consumption is reduced and the desorption efficiency is improved. The alkyl hydroxyethyl ethylenediamine combined absorbent composed of alkyl hydroxyethyl ethylenediamine, water and an activator has the advantages of low reaction heat, high desorption efficiency and strong degradation resistance.

Description

Technical Field

[0001] This invention relates to the field of carbon dioxide capture technology, and more particularly to the application of an alkyl hydroxyethyl ethylenediamine in carbon dioxide capture. Background Technology

[0002] Since the Industrial Revolution, human emissions of carbon dioxide into the atmosphere have been increasing daily, making carbon dioxide the most pressing greenhouse gas that needs to be controlled. Carbon capture, utilization, and storage (CCUS) technology is the most effective means of reducing carbon emissions, with carbon capture processes having the highest energy consumption and cost, forming the foundation and fundamental premise of this technology.

[0003] The chemical absorption of carbon dioxide using conventional alkanolamine solutions (reaction formula 1) is currently the most mature and feasible carbon capture strategy, boasting advantages such as fast reaction rate, good selectivity, wide applicability, and low material cost. Multiple demonstration plants have been established and put into operation both domestically and internationally. However, due to the inherent structural limitations of conventional alkanolamine absorbents, the carbon capture process suffers from high energy consumption and significant losses, restricting the further industrial application of amine liquid chemical absorption. On one hand, the chemical absorption of carbon dioxide by conventional alkanolamine absorbents generally involves substantial heat of reaction, resulting in correspondingly high energy consumption during regeneration. On the other hand, the recycling process of conventional alkanolamine absorbents involves two processes: long-term contact with high-volume oxygen-containing flue gas (absorption tower) and high-temperature desorption (desorption tower). This inevitably leads to oxidative and thermal degradation, which not only impairs the operational stability of the carbon capture system but also causes environmental pollution and a decrease in product purity. Since the energy consumption and loss problems of conventional amine absorbents cannot be solved at the source, how to construct a new high-efficiency absorption system with high energy efficiency and resistance to degradation has become one of the urgent problems to be solved in the field of practical application of carbon dioxide capture technology. Summary of the Invention

[0004] The purpose of this invention is to provide an application of alkylhydroxyethyl ethylenediamine in carbon dioxide capture. The alkylhydroxyethyl ethylenediamine provided by this invention, as a carbon dioxide absorbent, has the advantages of low heat of reaction, good desorption effect, and strong resistance to degradation, and exhibits excellent performance in the absorption-desorption cycle of carbon dioxide.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: An application of alkylhydroxyethyl ethylenediamine in carbon dioxide capture, wherein the alkylhydroxyethyl ethylenediamine has the structure shown in Formula I: Formula I; In Equation I: R 1 R 2 R3 R 4 and R 5 Independently H or C1~C3 alkyl, and R 1 R 2 R 4 and R 5 They are not both H.

[0006] Preferably, the alkylhydroxyethylethylenediamine has the structure shown in any one of formulas I-1 to I-36: Formula I-1, Formula I-2, Formula I-3, Formula I-4, Formula I-5, Formula I-6, Formula I-7, Formula I-8, Formula I-9, Formula I-10, Formula I-11, Formula I-12, Formula I-13, Formula I-14, Formula I-15, Formula I-16, Formula I-17, Formula I-18, Formula I-19, Formula I-20, Formula I-21, Formula I-22, Formula I-23, Formula I-24, Formula I-25, Formula I-26, Formula I-27, Formula I-28, Formula I-29, Formula I-30, Formula I-31, Formula I-32, Formula I-33, Formula I-34, Formula I-35, Formula I-36.

[0007] Preferably, the alkyl hydroxyethyl ethylenediamine is selectively mixed with water and an activator during carbon dioxide capture to form a combined absorbent for use; the content of each component in the combined absorbent is as follows, by mass percentage: alkyl hydroxyethyl ethylenediamine 0.1%~60%, water 0.1%~99%, activator 0%~50%.

[0008] Further preferred options are those with the following content by mass percentage: 1%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, or 60%, which will not be listed exhaustively here.

[0009] Further preferred options, based on mass percentage, are: 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95%, and these will not be listed exhaustively here.

[0010] Further preferred options are: 1%, 5%, 10%, 20%, 30%, 40%, or 50% by mass percentage, and these will not be listed exhaustively here.

[0011] More preferably, the activator is one or a mixture of two or more of piperazine, 1-methylpiperazine, 2-methylpiperazine, 4-methylpiperazine, 3-hydroxypiperidine, 4-hydroxypiperidine, 2,6-dimethylpiperazine, 1-(β-aminoethyl)piperazine, 1-(β-aminopropyl)piperazine, 1-(β-methyl-β-aminopropyl)piperazine, 1,4-bis(β-aminoethyl)piperazine, 1,4-bis(β-aminopropyl)piperazine and 1,4-bis(β-methyl-β-aminopropyl)piperazine.

[0012] Preferably, a method for preparing alkylhydroxyethyl ethylenediamine includes the following steps: Compound 1, Compound 2, Raney nickel, and diethylene glycol dimethyl ether were mixed and subjected to a heating alkylation reaction under a hydrogen atmosphere to obtain the alkyl hydroxyethyl ethylenediamine. ; In compound 1: R 1 and R 2 Independently H or C1~C3 alkyl; in compound 2: R 3 R 4 and R 5 Independently H or C1~C3 alkyl; in compounds 1 and 2: R 1 R 2 R 4 and R 5 They are not both H.

[0013] The temperature of the heating alkylation reaction is 120°C. o C~240o C, the heat preservation time is 12h~48h, and the hydrogen pressure is 0.1MPa~5MPa.

[0014] The molar ratio of compound 1 to compound 2 is 1:0.1~10.

[0015] The Raney nickel is added at a mass of 1% to 30% of the total mass of compound 1 and compound 2.

[0016] Preferably, the application includes the removal of carbon dioxide from flue gas, waste gas, tail gas, product gas, raw material gas, decomposed gas, water gas, natural gas and / or biogas.

[0017] The beneficial effects of this invention are: This invention provides an alkylhydroxyethyl ethylenediamine. The alkylhydroxyethyl ethylenediamine provided by this invention has one or more alkyl side chains: 1) By controlling the reaction form, reaction pathway, and reaction strength between the alkyl group and carbon dioxide through the alkyl structure, number of alkyl groups, and substitution position, the desorption energy consumption is reduced and the desorption efficiency is improved by optimizing the reaction heat; 2) By utilizing the active sites in the chemically inert alkyl shielding absorbent molecule structure that are prone to side reactions, the purpose of enhancing anti-degradation performance is achieved.

[0018] This invention provides an application of alkyl hydroxyethyl ethylenediamine in carbon dioxide capture. Compared with the traditional amine absorption method, alkyl hydroxyethyl ethylenediamine has a targeted design of the main agent structure of the absorbent at the molecular level, and has the following superior properties: (1) By introducing alkyl groups with specific structures at one or more specific positions in the absorbent molecule, the reaction form, reaction path and intensity of the amine group with carbon dioxide are controlled, thereby reducing desorption energy consumption and improving desorption efficiency by optimizing the reaction heat. As shown in the test results of the application example, the alkyl hydroxyethyl ethylenediamine combined absorbent provided by this invention has a minimum reaction heat of 55 kJ / mol and a maximum desorption efficiency of 100%; (2) By shielding the active sites in the absorbent molecule structure that are prone to side reactions through the chemically inert alkyl group, the anti-degradation performance is enhanced. As shown in the test results of the application example, the alkyl hydroxyethyl ethylenediamine combined absorbent provided by this invention has a high resistance to degradation at high temperatures and in air atmosphere (140°C). o C. After being sealed for 144 hours under conditions of initial air pressure of 0.1 MPa, its carbon dioxide absorption capacity under standard conditions did not decrease significantly. This indicates that the alkylhydroxyethyl ethylenediamine provided by this invention has the advantages of low heat of reaction, high desorption efficiency, and strong resistance to degradation. Detailed Implementation

[0019] The present invention will be described in detail below with reference to examples, but these examples should not be construed as limiting the scope of protection of the present invention.

[0020] Example 1: Preparation of alkylhydroxyethyl ethylenediamine I-1: Compound 1 (R 1 =CH3,R 2 =H, 100mmol, 7.5g), compound 2 (R 3 =H,R 4 =H,R 5 =H, 100 mmol, 6.1 g), Raney nickel (1.5 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 140 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-1. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=1.09(d,3H),2.66-2.97(m,5H),3.75(t,2H).

[0021] Example 2: Preparation of alkylhydroxyethyl ethylenediamine I-2: Compound 1 (R 1 =H,R 2 =H, 100mmol, 6.1g), compound 2 (R 3 =H,R 4 =CH3,R 5 =H, 100 mmol, 7.5 g), Raney nickel (1.5 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 150 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-2. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=1.11(d,3H),2.71-2.88(m,5H),3.18-3.35(m,2H).

[0022] Example 3: Preparation of alkylhydroxyethyl ethylenediamine I-3: Compound 1 (R 1 =CH3,R 2 =H, 100mmol, 7.5g), compound 2 (R3 =CH3,R 4 =H,R 5 =H, 100 mmol, 7.5 g), Raney nickel (1.8 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 150 °C. o The reaction was carried out at C for 20 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-3. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=1.10(d,3H),2.48-2.91(m,8H),3.62(t,2H).

[0023] Example 4: Preparation of alkylhydroxyethyl ethylenediamine I-5: Compound 1 (R 1 =CH3,R 2 =H, 100mmol, 7.5g), compound 2 (R 3 =CH2CH3, R 4 =H,R 5 =H, 100 mmol, 8.9 g), Raney nickel (2.0 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 150 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-5. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=1.11(d,3H),1.14(t,3H),2.44-3.01(m,7H),3.58(t,2H).

[0024] Example 5: Preparation of alkylhydroxyethyl ethylenediamine I-9: Compound 1 (R 1 =CH3,R 2 =H, 100mmol, 7.5g), compound 2 (R 3 =CH(CH3)2,R 4 =H,R 5=H, 100 mmol, 10.3 g), Raney nickel (2.0 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 160 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-9. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=1.01-1.05(m,6H),1.10(d,3H),2.49-3.05(m,6H),3.24-3.51(m,2H).

[0025] Example 6: Preparation of alkylhydroxyethyl ethylenediamine I-11: Compound 1 (R 1 =CH3,R 2 =H, 100mmol, 7.5g), compound 2 (R 3 =H,R 4 =CH3,R 5 =H, 100 mmol, 7.5 g), Raney nickel (1.6 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 140 °C. o The reaction was carried out at C for 30 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-11. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=1.06-1.12(m,6H), 2.59-3.07(m,4H), 3.20-3.46(m,2H).

[0026] Example 7: Preparation of alkylhydroxyethyl ethylenediamine I-12: Compound 1 (R 1 =CH3,R 2 =CH3, 100mmol, 8.9g), compound 2 (R 3 =H,R 4 =H,R 5=H, 100 mmol, 6.1 g), Raney nickel (1.5 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (3 MPa) was introduced. The high-pressure reactor was heated to 140 °C. o The reaction was carried out at C for 40 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-12. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=1.18(s,3H),1.20(s,3H),2.64-2.97(m,4H),3.50(t,2H).

[0027] Example 8: Preparation of alkylhydroxyethyl ethylenediamine I-13: Compound 1 (R 1 =H,R 2 =H, 100mmol, 6.1g), compound 2 (R 3 =H,R 4 =CH3,R 5 =CH3 (100 mmol, 8.9 g), Raney nickel (2.5 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (4 MPa) was introduced. The high-pressure reactor was heated to 170 °C. o The reaction was carried out at C for 25 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-13. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=1.19(s,3H),1.22(s,3H),2.62-2.87(m,4H),3.31(s,2H).

[0028] Example 9: Preparation of alkylhydroxyethyl ethylenediamine I-14: Compound 1 (R 1 =CH3,R 2 =CH3, 100mmol, 8.9g), compound 2 (R 3 =H,R 4 =CH3,R 5=H, 100 mmol, 7.5 g), Raney nickel (2.2 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (3 MPa) was introduced. The high-pressure reactor was heated to 160 °C. o The reaction was carried out at C for 20 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-14. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=1.07(d,3H),1.21(s,3H),1.23(s,3H),2.54-2.81(m,3H),3.19-3.44(m,2H).

[0029] Example 10: Preparation of alkylhydroxyethyl ethylenediamine I-15: Compound 1 (R 1 =CH3,R 2 =H, 100mmol, 7.5g), compound 2 (R 3 =H,R 4 =CH3,R 5 =CH3 (100 mmol, 8.9 g), Raney nickel (2.8 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (4 MPa) was introduced. The high-pressure reactor was heated to 170 °C. o The reaction was carried out at C for 40 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-15. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=1.09(d,3H),1.20(s,3H),1.23(s,3H),2.71-3.12(m,3H),3.28(s,2H).

[0030] Example 11: Preparation of alkylhydroxyethyl ethylenediamine I-16: Compound 1 (R 1 =CH3,R 2 =CH3, 100mmol, 8.9g), compound 2 (R 3 =H,R 4 =CH3,R 5=CH3 (100 mmol, 8.9 g), Raney nickel (3.2 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (4 MPa) was introduced. The high-pressure reactor was heated to 180 °C. o The reaction was carried out at C for 30 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-16. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=1.21-1.27(m,12H),2.73(s,2H),3.36(s,2H).

[0031] Example 12: Preparation of alkylhydroxyethyl ethylenediamine I-19: Compound 1 (R 1 =CH2CH3, R 2 =H, 100mmol, 8.9g), compound 2 (R 3 =H,R 4 =H,R 5 =H, 100 mmol, 6.1 g), Raney nickel (1.5 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 140 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-19. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=0.89(t,3H),1.49-1.61(m,2H),2.62-2.96(m,5H),3.55(t,2H).

[0032] Example 13: Preparation of alkylhydroxyethyl ethylenediamine I-20: Compound 1 (R 1 =H,R 2 =H, 100mmol, 6.1g), compound 2 (R 3 =H,R 4 =CH2CH3, R 5=H, 100 mmol, 8.9 g), Raney nickel (1.5 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 160 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-20. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=0.88(t,3H),1.41-1.54(m,2H),2.53-2.81(m,5H),3.12-3.33(m,2H).

[0033] Example 14: Preparation of alkylhydroxyethyl ethylenediamine I-21: Compound 1 (R 1 =CH2CH3, R 2 =H, 100mmol, 8.9g), compound 2 (R 3 =CH3,R 4 =H,R 5 =H, 100 mmol, 7.5 g), Raney nickel (1.5 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 140 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-21. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=0.90(t,3H),1.51-1.60(m,2H),2.32-2.88(m,8H),3.51(t,2H).

[0034] Example 15: Preparation of alkylhydroxyethyl ethylenediamine I-23: Compound 1 (R 1 =CH2CH3, R 2 =H, 100mmol, 8.9g), compound 2 (R 3 =H,R 4 =CH3,R 5=H, 100 mmol, 7.5 g), Raney nickel (1.8 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 150 °C. o The reaction was carried out at C for 30 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-23. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=0.87(t,3H),1.08(d,3H),1.48-1.63(m,2H),2.64-2.98(m,4H),3.17-3.31(m,2H).

[0035] Example 16: Preparation of alkylhydroxyethyl ethylenediamine I-24: Compound 1 (R 1 =CH3,R 2 =H, 100mmol, 7.5g), compound 2 (R 3 =H,R 4 =CH2CH3, R 5 =H, 100 mmol, 8.9 g), Raney nickel (2.0 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 160 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-24. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=0.91(t,3H),1.11(d,3H),1.43-1.55(m,2H),2.71-3.08(m,4H),3.19-3.36(m,2H).

[0036] Example 17: Preparation of alkylhydroxyethyl ethylenediamine I-25: Compound 1 (R 1 =CH2CH3, R 2 =H, 100mmol, 8.9g), compound 2 (R 3 =H,R 4 =CH2CH3, R 5=H, 100 mmol, 8.9 g), Raney nickel (2.0 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 160 °C. o The reaction was carried out at C for 36 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-25. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=0.86-0.95(m,6H),1.40-1.67(m,4H),2.53-2.88(m,4H),3.15-3.37(m,2H).

[0037] Example 18: Preparation of alkylhydroxyethyl ethylenediamine I-26: Compound 1 (R 1 =CH2CH3, R 2 =H, 100mmol, 8.9g), compound 2 (R 3 =H,R 4 =CH3,R 5 =CH3 (100 mmol, 8.9 g), Raney nickel (2.5 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (3 MPa) was introduced. The high-pressure reactor was heated to 170 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-26. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=0.85(t,3H),1.23(s,3H),1.25(s,3H),1.44-1.66(m,2H),2.52-2.93(m,3H),3.41(s,2H).

[0038] Example 19: Preparation of alkylhydroxyethyl ethylenediamine I-27: Compound 1 (R 1 =CH3,R 2 =CH3, 100mmol, 8.9g), compound 2 (R 3 =H,R 4 =CH2CH3, R 5=H, 100 mmol, 8.9 g), Raney nickel (2.0 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 160 °C. o The reaction was carried out at C for 32 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-27. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=0.86(t,3H),1.20(s,3H),1.22(s,3H),1.43-1.57(m,2H),2.55-2.81(m,3H),3.11-3.30(m,2H).

[0039] Example 20: Preparation of alkylhydroxyethyl ethylenediamine I-30: Compound 1 (R 1 =CH(CH3)2,R 2 =H, 100mmol, 10.3g), compound 2 (R 3 =H,R 4 =CH3,R 5 =H, 100 mmol, 7.5 g), Raney nickel (2.0 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 140 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-30. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=0.85-0.91(m,6H),1.08(d,3H),1.51-1.56(m,1H),2.48-2.96(m,4H),3.13-3.32(m,2H).

[0040] Example 21: Preparation of alkylhydroxyethyl ethylenediamine I-31: Compound 1 (R 1 =CH3,R 2 =H, 100mmol, 7.5g), compound 2 (R 3 =H,R 4=CH(CH3)2,R 5 =H, 100 mmol, 10.3 g), Raney nickel (2.2 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (3 MPa) was introduced. The high-pressure reactor was heated to 150 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-31. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=0.87-0.92(m,6H),1.12(d,3H),1.58-1.64(m,1H),2.40-3.06(m,4H),3.15-3.34(m,2H).

[0041] Example 22: Preparation of alkylhydroxyethyl ethylenediamine I-32: Compound 1 (R 1 =CH(CH3)2,R 2 =H, 100mmol, 10.3g), compound 2 (R 3 =H,R 4 =CH2CH3, R 5 =H, 100 mmol, 8.9 g), Raney nickel (2.2 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (2 MPa) was introduced. The high-pressure reactor was heated to 150 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-32. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=0.87-0.94(m,9H),1.47-1.59(m,3H),2.42-2.88(m,4H),3.16-3.28(m,2H).

[0042] Example 23: Preparation of alkylhydroxyethyl ethylenediamine I-34: Compound 1 (R 1 =CH(CH3)2,R 2 =H, 100mmol, 10.3g), compound 2 (R 3 =H,R4 =CH3,R 5 =CH3 (100 mmol, 8.9 g), Raney nickel (2.4 g), and diethylene glycol dimethyl ether (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air, and finally hydrogen gas (3 MPa) was introduced. The high-pressure reactor was heated to 160 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction, the high-pressure reactor was immersed in an ice-water bath for 0.5 h. The reaction solution was then filtered, and the filter cake was washed with diethylene glycol dimethyl ether (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain alkylhydroxyethylethylenediamine I-34. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=0.84-0.88(m,6H),1.21(s,3H),1.24(s,3H),1.53-1.57(m,1H),2.32-2.81(m,3H),3.46(s,2H).

[0043] Application Example 1-23: Add 30g of alkylhydroxyethyl ethylenediamine, 3g of 1-(β-aminoethyl)piperazine, and 67g of deionized water as shown in Table 1 to a 250mL round-bottom flask. After stirring evenly, slowly introduce carbon dioxide at a flow rate of 300mL / min, a pressure of 0.1MPa, and an oil bath temperature of 40°C. o C. Record the inlet and outlet gas flow rates in real time using a gas flow meter. After absorption is complete, stop the gas supply and raise the oil bath temperature to 110°C. o C. The outflow rate was recorded in real time using a gas flow meter. The heat of reaction for the carbon dioxide absorption process of the corresponding alkylhydroxyethyl ethylenediamine was measured by a calorimeter. The absorption-desorption performance of the combined absorbent with alkylhydroxyethyl ethylenediamine as the main agent for carbon dioxide is shown in Table 1: Table 1: Carbon dioxide absorption-desorption performance of alkyl hydroxyethyl ethylenediamine combination absorbents

[0044] Application Example 24-32: Add 100g of alkyl hydroxyethyl ethylenediamine combined absorbent saturated with carbon dioxide to a 250mL high-pressure reactor, seal the reactor under air atmosphere, and place it at 140°C. o Heated in an oil bath for 144 hours. After immersing the high-pressure reactor in an ice-water bath for 1 hour, the absorbent solution was transferred to a 250 mL round-bottom flask. Nitrogen gas was slowly introduced for 30 minutes with magnetic stirring. The nitrogen flow rate was 100 mL / min, the pressure was 0.1 MPa, and the oil bath temperature was 110 °C. oC. After the residual carbon dioxide is purged, the oil bath temperature is reduced to 40°C. o C. Carbon dioxide was slowly introduced at a flow rate of 300 mL / min and a pressure of 0.1 MPa. The inlet and outlet flow rates were recorded in real time using a gas flow meter. The carbon dioxide absorption results of the alkyl hydroxyethyl ethylenediamine combined absorbent after the anti-degradation test are shown in Table 2. Table 2: Carbon dioxide absorption performance of the alkyl hydroxyethyl ethylenediamine combination absorbent after anti-degradation test

[0045] Application examples 33-34: Add 100g of alkylhydroxyethylethylenediamine as shown in Table 3 to a 250mL round-bottom flask, stir well, and then slowly introduce carbon dioxide at a flow rate of 300mL / min and a pressure of 0.1MPa. The oil bath temperature is 40°C. o C. Record the inlet and outlet gas flow rates in real time using a gas flow meter. After absorption is complete, stop the gas supply and raise the oil bath temperature to 110°C. o C. The outlet gas flow rate was recorded in real time using a gas flow meter. The absorption-desorption performance test results of alkyl hydroxyethyl ethylenediamine for carbon dioxide are shown in Table 3: Table 3: Carbon dioxide absorption-desorption performance of alkyl hydroxyethyl ethylenediamine

[0046] Comparative application example 1: Add 30g of the contrast absorbent hydroxyethyl ethylenediamine, 3g of 1-(β-aminoethyl)piperazine, and 67g of deionized water to a 250mL round-bottom flask. After stirring thoroughly, slowly introduce carbon dioxide at a flow rate of 300mL / min and a pressure of 0.1MPa. The oil bath temperature is 40°C. o C. Record the inlet and outlet gas flow rates in real time using a gas flow meter. After absorption is complete, stop the gas supply and raise the oil bath temperature to 110°C. o C. Record the outlet gas flow rate in real time using a gas flow meter. Add 100g of saturated comparative absorbent solution to a 250mL high-pressure reactor, seal it under air atmosphere, and place it at 140°C. o Heated in an oil bath for 144 hours. After immersing the high-pressure reactor in an ice-water bath for 1 hour, the absorbent solution was transferred to a 250 mL round-bottom flask. Nitrogen gas was slowly introduced for 30 minutes with magnetic stirring. The nitrogen flow rate was 100 mL / min, the pressure was 0.1 MPa, and the oil bath temperature was 110 °C. o C. After the residual carbon dioxide is purged, the oil bath temperature is reduced to 40°C. oC. Carbon dioxide was slowly introduced at a flow rate of 300 mL / min and a pressure of 0.1 MPa. The inlet and outlet flow rates were recorded in real time using a gas flow meter. The heat of reaction during the absorption of carbon dioxide by the comparative absorbent was measured using a calorimeter. The performance test results of the above comparative absorbent are shown in Table 3. Table 4: Overall Performance of Comparative Absorbents

[0047] As can be seen from Tables 1, 2, 3 and 4, the alkyl hydroxyethyl ethylenediamine provided by the present invention has significant advantages over Comparative Application Example 1 in terms of reaction heat, desorption efficiency and anti-degradation performance.

[0048] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An application of an alkylhydroxyethyl ethylenediamine in carbon dioxide capture, characterized in that, The alkylhydroxyethylethylenediamine has the structure shown in Formula I: Equation I; In Equation I: R 1 R 2 R 3 R 4 and R 5 Independently H or C1~C3 alkyl, and R 1 R 2 R 4 and R 5 Not both H; The alkyl hydroxyethyl ethylenediamine is selectively mixed with water and an activator during carbon dioxide capture to form a combined absorbent. The content of each component by mass percentage is: alkyl hydroxyethyl ethylenediamine 0.1%~60%, water 0.1%~99%, and activator 0%~50%.

2. The application of an alkylhydroxyethyl ethylenediamine according to claim 1 in carbon dioxide capture, characterized in that, The alkylhydroxyethylethylenediamine has the structure shown in any one of formulas I-1 to I-36: Equation I-1, Equation I-2, Equation I-3, Formula I-4, Formula I-5, Formula I-6, Equation I-7, Formula I-8, Equation I-9, Formula I-10, Formula I-11, Formula I-12, Formula I-13, Formula I-14, Formula I-15, Formula I-16, Formula I-17, Formula I-18, Formula I-19, Formula I-20, Formula I-21, Formula I-22, Formula I-23, Formula I-24, Formula I-25, Formula I-26, Formula I-27, Formula I-28, Formula I-29, Formula I-30, Formula I-31, Formula I-32, Formula I-33, Formula I-34, Formula I-35, Formula I-36.

3. The application of an alkylhydroxyethyl ethylenediamine according to claim 1 in carbon dioxide capture, characterized in that, The activator is one or a mixture of two or more of piperazine, 1-methylpiperazine, 2-methylpiperazine, 4-methylpiperazine, 3-hydroxypiperidine, 4-hydroxypiperidine, 2,6-dimethylpiperazine, 1-(β-aminoethyl)piperazine, 1-(β-aminopropyl)piperazine, 1-(β-methyl-β-aminopropyl)piperazine, 1,4-bis(β-aminoethyl)piperazine, 1,4-bis(β-aminopropyl)piperazine and 1,4-bis(β-methyl-β-aminopropyl)piperazine.

4. The application of an alkylhydroxyethyl ethylenediamine according to claim 1 or 2 in carbon dioxide capture, characterized in that, The applications include the removal of carbon dioxide from flue gas, waste gas, tail gas, product gas, raw material gas, decomposed gas, water gas, natural gas and / or biogas.

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