Use of a furanyl organic amine in carbon dioxide capture

Abstract

The application provides application of furan-based organic amine in carbon dioxide capture and relates to the technical field of carbon dioxide capture. The furan-based organic amine provided by the application has one or more oxygen-containing side chains in the structure, and the synergistic effect of the furan ring, the oxygen-containing side chain and the amine group can improve the desorption efficiency and reduce the working viscosity of the system. The furan-based organic amine provided by the application can be used alone or can be used to form a furan-based organic amine solution with water, and has the advantages of high desorption efficiency and low working viscosity.

Description

Technical Field

[0001] This invention relates to the field of carbon dioxide capture technology, and more particularly to the application of a furanyl organic amine in carbon dioxide capture. Background Technology

[0002] As industrialization deepens, human emissions of carbon dioxide into the atmosphere continue to increase, making carbon dioxide the largest and most urgent greenhouse gas to control. 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 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 low efficiency, restricting the further industrial application of amine-based chemical absorption. On one hand, the chemical absorption of carbon dioxide by conventional alkanolamine absorbents requires the addition of large amounts of solvent water to mitigate the sudden increase in viscosity during absorption, resulting in correspondingly high energy consumption during regeneration. On the other hand, alkanolamines primarily absorb carbon dioxide in the form of ammonium carbamate, which is one of the main reasons for the low desorption efficiency of the alkanolamine system. Since the energy consumption and desorption efficiency problems of conventional alkanolamine absorbents cannot be fundamentally solved, how to construct a novel absorption system with high energy efficiency and high regenerability has become one of the urgent challenges to be addressed in the practical application of carbon dioxide capture technology. Summary of the Invention

[0004] The purpose of this invention is to provide an application of furanyl organic amines in carbon dioxide capture. The furanyl organic amines provided by this invention, as carbon dioxide absorbents, have the advantages of high desorption efficiency and low working viscosity, and exhibit 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 a furanyl organic amine in carbon dioxide capture, wherein the furanyl organic amine has the structure shown in Formula I: Formula I; In the aforementioned formula I: R 1 R 2It is independently H, C1~C3 alkyl, CH3OCH2CH2, CH3OCH2CH2OCH2CH2 or CH3OCH2CH2OCH2CH2OCH2CH2.

[0006] Preferably, the furanyl organic amine has the structure shown in any one of formulas I-1 to I-15: 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.

[0007] Preferably, the furanyl organic amine can be used alone or selectively mixed with water to form an absorbent solution in carbon dioxide capture; the content of each component by mass percentage is: furanyl organic amine 1%~100%, water 0%~99%.

[0008] Further preferred options are those with a furanyl organic amine content of 1%, 5%, 10%, 20%, 40%, 60%, 80%, 90%, 95%, or 100% by mass, which will not be listed exhaustively here.

[0009] Further preferred options, based on mass percentage, are: 0%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95%, and these will not be listed exhaustively here.

[0010] Preferably, a method for preparing a furanyl organic amine includes the following steps: Compound 1, Compound 2, sodium borohydride, and methanol were mixed and subjected to a reducing amination reaction under a nitrogen atmosphere to obtain the furanyl organic amine. ; In compound 1: R 1 H, C1~C3 alkyl, CH3OCH2CH2, CH3OCH2CH2OCH2CH2 or CH3OCH2CH2OCH2CH2OCH2CH2; In compound 2: R 2It can be H, C1~C3 alkyl, CH3OCH2CH2, CH3OCH2CH2OCH2CH2 or CH3OCH2CH2OCH2CH2OCH2CH2.

[0011] The temperature of the heating reduction amination reaction is 0. o C~70 o C, the heat preservation time is 1h~48h.

[0012] The molar ratio of compound 1 to compound 2 is 1:0.1~10.

[0013] The amount of sodium borohydride added is 50 to 400% of 1 mole of the compound.

[0014] 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.

[0015] Beneficial effects of the present invention This invention provides a furanyl organic amine. The furanyl organic amine provided by this invention has one or more oxygen-containing side chains in its structure: 1) By leveraging the synergistic effect of the furan ring, oxygen-containing side chains, and amine group, the reaction pathway and interaction strength between the amine group and carbon dioxide are controlled, thereby reversibly converting carbon dioxide into carbamic acid to improve desorption efficiency; 2) Utilizing the high free volume characteristics of the furan ring combined with the flexible oxygen-containing side chains, the viscosity increment during the carbon dioxide absorption process is effectively reduced, thereby enhancing the fluidity of the system.

[0016] This invention provides an application of furanyl organic amine in carbon dioxide capture. Compared with the traditional alcohol amine absorption method, furanyl organic amine has a targeted design of the absorbent structure at the molecular level, and has the following superior properties: (1) Introducing oxygen-containing side chains with specific structures at one or more specific positions in the furanyl absorbent molecule to regulate the reaction path and interaction strength between the amine group and carbon dioxide, thereby improving the desorption efficiency by reversibly converting carbon dioxide into carbamic acid. As shown in the test results of the application example, the desorption efficiency of the furanyl organic amine provided by this invention is 100% when used alone, and the desorption efficiency after mixing with water to form an absorbent solution is not less than 88%, which is much higher than the comparative example under the same conditions; (2) Utilizing the high free volume characteristics of the furan ring combined with the flexible oxygen-containing side chain, the viscosity increment during the carbon dioxide absorption process is effectively reduced, thereby enhancing the fluidity of the system. As shown in the test results of the application example, the working viscosity of the furanyl organic amine provided by this invention is 12~810 cP when used alone, and the working viscosity after mixing with water to form an absorbent solution is 2~5 cP, which is much lower than the comparative example under the same conditions. It is noted that the furanyl organic amine provided by the present invention has the advantages of high desorption efficiency and strong flowability. Detailed Implementation

[0017] 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.

[0018] Example 1: Preparation of furanyl organic amine I-3: Compound 1 (R 1 =CH3, 100mmol, 14.0g), compound 2 (R 2 =CH3, 100mmol, 25 wt% alcohol solution, 12.4g), sodium borohydride (100mmol, 3.8g), and methanol (100mL) were added sequentially to a 250mL round-bottom flask under nitrogen protection. The mixture was heated to 60°C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction was completed, the mixture was cooled to room temperature, and then the reaction solution was filtered. The filter cake was washed with methanol (30 mL × 2). The washings and filtrates were combined and distilled under reduced pressure to obtain furanyl organic amine I-3. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=2.87(s,3H),3.22(s,3H),3.56(s,2H),4.53(s,2H),6.06-6.18(m,2H).

[0019] Example 2: Preparation of furanyl organic amine I-4: Compound 1 (R 1 =CH2CH3, 100mmol, 15.4g), compound 2 (R 2 =CH3, 100mmol, 25 wt% alcohol solution, 12.4g), sodium borohydride (100mmol, 3.8g), and methanol (100mL) were added sequentially to a 250mL round-bottom flask under nitrogen protection. The mixture was heated to 60°C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction was completed, the mixture was cooled to room temperature, and then the reaction solution was filtered. The filter cake was washed with methanol (30 mL × 2). The washings and filtrates were combined and distilled under reduced pressure to obtain furanyl organic amine I-4. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=1.14(t,3H),2.87(s,3H),3.31(q,2H),3.51(s,2H),4.52(s,2H),6.07-6.15(m,2H).

[0020] Example 3: Preparation of furanyl organic amine I-5: Compound 1 (R 1 =CH2CH3, 100mmol, 15.4g), compound 2 (R 2=CH2CH3, 100mmol, 25 wt% alcohol solution, 18.0g), sodium borohydride (100mmol, 3.8g), and methanol (100mL) were added sequentially to a 250mL round-bottom flask under nitrogen protection. The mixture was then incubated at 60°C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction was completed, the mixture was cooled to room temperature, and then the reaction solution was filtered. The filter cake was washed with methanol (30 mL × 2). The washings and filtrates were combined and distilled under reduced pressure to obtain furanyl organic amine I-5. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=1.12-1.16(m,6H),2.55(q,2H),3.34(q,2H),3.48(s,2H),4.56(s,2H),6.06-6.16(m,2H).

[0021] Example 4: Preparation of furanyl organic amine I-6: Compound 1 (R 1 =CH2CH2OCH3, 100mmol, 18.4g), compound 2 (R 2 =CH3, 100mmol, 25 wt% alcohol solution, 12.4g), sodium borohydride (100mmol, 3.8g), and methanol (100mL) were added sequentially to a 250mL round-bottom flask under nitrogen protection. The mixture was heated to 60°C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction was completed, the mixture was cooled to room temperature, and then the reaction solution was filtered. The filter cake was washed with methanol (30 mL × 2). The washings and filtrates were combined and distilled under reduced pressure to obtain furanyl organic amine I-6. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=2.63(s,3H),3.34-3.71(m,9H),4.48(s,2H),6.03-6.17(m,2H).

[0022] Example 5: Preparation of furanyl organic amine I-7: Compound 1 (R 1 =CH2CH2OCH2CH2OCH3, 100mmol, 22.8g), compound 2 (R 2 =CH3, 100mmol, 25 wt% alcohol solution, 12.4g), sodium borohydride (100mmol, 3.8g), and methanol (100mL) were added sequentially to a 250mL round-bottom flask under nitrogen protection. The mixture was heated to 60°C. oThe reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction was completed, the mixture was cooled to room temperature, and then the reaction solution was filtered. The filter cake was washed with methanol (30 mL × 2). The washings and filtrates were combined and distilled under reduced pressure to obtain furanyl organic amine I-7. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=2.66(s,3H),3.31-3.78(m,13H),4.55(s,2H),6.07-6.22(m,2H).

[0023] Example 6: Preparation of furanyl organic amine I-8: Compound 1 (R 1 =CH2CH2OCH2CH2OCH3, 100mmol, 22.8g), compound 2 (R 2 =CH2CH3, 100mmol, 25 wt% alcohol solution, 18.0g), sodium borohydride (100mmol, 3.8g), and methanol (100mL) were added sequentially to a 250mL round-bottom flask under nitrogen protection. The mixture was then incubated at 60°C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was then filtered. The filter cake was washed with methanol (30 mL × 2). The washings and filtrate were combined and distilled under reduced pressure to obtain furanyl organic amine I-8. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=1.16(t,3H),2.52(q,2H),3.32-3.73(m,13H),4.52(s,2H),6.06-6.20(m,2H).

[0024] Example 7: Preparation of furanyl organic amine I-9: Compound 1 (R 1 =CH2CH2OCH2CH2OCH2CH2OCH3, 100mmol, 27.2g), compound 2 (R 2 =CH3, 100mmol, 25 wt% alcohol solution, 12.4g), sodium borohydride (100mmol, 3.8g), and methanol (100mL) were added sequentially to a 250mL round-bottom flask under nitrogen protection. The mixture was heated to 60°C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction was completed, the mixture was cooled to room temperature, and then the reaction solution was filtered. The filter cake was washed with methanol (30 mL × 2). The washings and filtrates were combined and distilled under reduced pressure to obtain furanyl organic amine I-9. NMR characterization data: 1H NMR (400MHz, CDCl3): δ=2.62(s,3H),3.26-3.81(m,17H),4.52(s,2H),6.10-6.21(m,2H).

[0025] Example 8: Preparation of furanyl organic amine I-10: Compound 1 (R 1 =CH3, 100mmol, 14.0g), compound 2 (R 2 =CH2CH2OCH3 (100 mmol, 7.5 g), sodium borohydride (100 mmol, 3.8 g), and methanol (100 mL) were added sequentially to a 250 mL round-bottom flask under nitrogen protection. The mixture was heated to 60 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction was completed, the mixture was cooled to room temperature, and then the reaction solution was filtered. The filter cake was washed with methanol (30 mL × 2). The washings and filtrates were combined and distilled under reduced pressure to obtain furanyl organic amine I-10. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=2.57(t,2H),3.34-3.77(m,10H),4.47(s,2H),6.08-6.19(m,2H).

[0026] Example 9: Preparation of furanyl organic amine I-11: Compound 1 (R 1 =CH3, 100mmol, 14.0g), compound 2 (R 2 =CH2CH2OCH2CH2OCH3, 100mmol, 11.9g), sodium borohydride (100mmol, 3.8g), and methanol (100mL) were added sequentially to a 250mL round-bottom flask under nitrogen protection. The mixture was heated to 60°C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction was completed, the mixture was cooled to room temperature, and then the reaction solution was filtered. The filter cake was washed with methanol (30 mL × 2). The washings and filtrates were combined and distilled under reduced pressure to obtain furanyl organic amine I-11. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=2.61(t,2H),3.31-3.82(m,14H),4.49(s,2H),6.06-6.15(m,2H).

[0027] Example 10: Preparation of furanyl organic amine I-12: Compound 1 (R 1 =CH3, 100mmol, 14.0g), compound 2 (R 2=CH2CH2OCH2CH2OCH2CH2OCH3, 100 mmol, 16.3 g), sodium borohydride (100 mmol, 3.8 g), and methanol (100 mL) were added sequentially to a 250 mL round-bottom flask under nitrogen protection. The mixture was heated to 60 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction was completed, the mixture was cooled to room temperature, and then the reaction solution was filtered. The filter cake was washed with methanol (30 mL × 2). The washings and filtrates were combined and distilled under reduced pressure to obtain furanyl organic amine I-12. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=2.60(t,2H),3.29-3.76(m,18H),4.55(s,2H),6.08-6.17(m,2H).

[0028] Example 11: Preparation of furanyl organic amine I-13: Compound 1 (R 1 =CH2CH2OCH3, 100mmol, 18.4g), compound 2 (R 2 =CH2CH2OCH3 (100 mmol, 7.5 g), sodium borohydride (100 mmol, 3.8 g), and methanol (100 mL) were added sequentially to a 250 mL round-bottom flask under nitrogen protection. The mixture was heated to 60 °C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction was completed, the mixture was cooled to room temperature, and then the reaction solution was filtered. The filter cake was washed with methanol (30 mL × 2). The washings and filtrates were combined and distilled under reduced pressure to obtain furanyl organic amine I-13. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=2.65(t,2H),3.26-3.74(m,14H),4.52(s,2H),6.04-6.18(m,2H).

[0029] Example 12: Preparation of furanyl organic amine I-14: Compound 1 (R 1 =CH2CH2OCH2CH2OCH3, 100mmol, 22.8g), compound 2 (R 2 =CH2CH2OCH3 (100 mmol, 7.5 g), sodium borohydride (100 mmol, 3.8 g), and methanol (100 mL) were added sequentially to a 250 mL round-bottom flask under nitrogen protection. The mixture was heated to 60 °C. oThe reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was then filtered. The filter cake was washed with methanol (30 mL × 2). The washings and filtrates were combined and distilled under reduced pressure to obtain furanyl organic amine I-14. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=2.62(t,2H),3.27-3.81(m,18H),4.54(s,2H),6.05-6.16(m,2H).

[0030] Example 13: Preparation of furanyl organic amine I-15: Compound 1 (R 1 =CH2CH2OCH3, 100mmol, 18.4g), compound 2 (R 2 =CH2CH2OCH2CH2OCH3, 100mmol, 11.9g), sodium borohydride (100mmol, 3.8g), and methanol (100mL) were added sequentially to a 250mL round-bottom flask under nitrogen protection. The mixture was heated to 60°C. o The reaction was carried out at C for 24 h with magnetic stirring at 600 r / min. After the reaction was completed, the mixture was cooled to room temperature, and then the reaction solution was filtered. The filter cake was washed with methanol (30 mL × 2). The washings and filtrates were combined and distilled under reduced pressure to obtain furanyl organic amine I-15. NMR characterization data: 1 H NMR (400MHz, CDCl3): δ=2.67(t,2H),3.33-3.84(m,18H),4.50(s,2H),6.06-6.21(m,2H).

[0031] Application Example 1-15: Add 100g of furanyl organic amine as shown in Table 1 to a 250mL round-bottom flask, stir well, and then slowly introduce carbon dioxide at a flow rate of 300mL / min, a pressure of 0.1MPa, and an oil bath temperature of 25°C. o C. Record the inlet and outlet gas flow rates in real time using a gas flow meter. Stop the gas supply after absorption is complete, and raise the oil bath temperature to 80°C after the working viscosity test is completed. o C. The outlet gas flow rate was recorded in real time using a gas flow meter. The test results of the absorption-desorption performance of furanyl organic amines for carbon dioxide are shown in Table 1: Table 1: Carbon dioxide absorption-desorption performance of furanyl organic amines

[0032] Application Example 16-30: Add 30g of furanyl organic amine and 70g of water (as shown in Table 2) 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 25°C. o C. Record the inlet and outlet gas flow rates in real time using a gas flow meter. Stop the gas supply after absorption is complete, and raise the oil bath temperature to 120°C after the working viscosity test is finished. o C. The outflow rate was recorded in real time using a gas flow meter. The results of the absorption-desorption performance test of the furanyl organic amine solution for carbon dioxide are shown in Table 2. Table 2: Carbon dioxide absorption-desorption performance of furanyl organic amine solutions

[0033] Compare and contrast with example 1-2: Add 100g of ethanolamine or 100g of 30 wt% ethanolamine solution as a contrast absorbent to a 250mL round-bottom flask, stir well, and then slowly introduce carbon dioxide at a flow rate of 300mL / min, a pressure of 0.1MPa, and an oil bath temperature of 25°C. o C. Record the inlet and outlet gas flow rates in real time using a gas flow meter. Stop the gas supply after absorption is complete, and raise the oil bath temperature to 80°C after the working viscosity test is completed. o C (ethanolamine) or 120 o C (30 wt% ethanolamine solution), with the outflow rate recorded in real time using a gas flow meter. The absorption-desorption performance test results of the comparative absorbent are shown in Table 3. Table 3: Carbon dioxide absorption-desorption performance of comparative absorbents

[0034] As shown in Tables 1, 2 and 3, the furanyl organic amine provided by the present invention has significant advantages over the comparative application examples in terms of desorption efficiency and working viscosity.

[0035] 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 a furanyl organic amine in carbon dioxide capture, characterized in that, The furanyl organic amine has the structure shown in Formula I: Equation I; In Equation I: R 1 R 2 It is independently H, C1~C3 alkyl, CH3OCH2CH2, CH3OCH2CH2OCH2CH2 or CH3OCH2CH2OCH2CH2OCH2CH2.

2. The application of a furanyl organic amine according to claim 1 in carbon dioxide capture, characterized in that, The furanyl organic amine has the structure shown in any one of formulas I-1 to I-15: Equation I-1, Equation I-2, Equation I-3, Formula I-4, Formula I-5, Formula I-6, Equation 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.

3. The application of a furanyl organic amine according to claim 1 or 2 in carbon dioxide capture, characterized in that, The furanyl organic amine is used alone in carbon dioxide capture, or mixed with water to form an absorbent solution; the content of each component by mass percentage is: furanyl organic amine 1%~100%, water 0%~99%.

4. The application of a furanyl organic amine 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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