Application of a piperidine polyamine in carbon dioxide capture

Abstract

This invention provides an application of piperidinyl polyamine in carbon dioxide capture, relating to the field of carbon dioxide capture technology. The piperidinyl polyamine provided by this invention has additional amino or hydroxyl groups bonded to the ring rather than within the ring. This allows for the construction of a synergistic effect with multiple active sites while simultaneously enhancing anti-volatility by promoting intermolecular hydrogen bonding, thereby achieving the dual effects of increased reactivity and reduced volatilization loss. The piperidinyl polyamine and water described in this invention form a piperidinyl polyamine combined absorbent, which has the advantages of large absorption capacity and low volatilization loss.

Description

Technical Field

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

[0002] Global energy, metallurgy, and chemical industries contribute enormous amounts of industrial carbon emissions to the atmosphere each year, making carbon dioxide the most pressing greenhouse gas to control. Carbon capture, utilization, and storage (CCUS) technology is the most effective means of achieving carbon emission reduction, with carbon capture being the most energy-intensive and costly component, forming the foundation and fundamental premise of this technology.

[0003]

[0004] The carbon dioxide chemical absorption method using traditional 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 built and put into operation both domestically and internationally. However, due to the inherent structural limitations of conventional alkanolamine absorbent molecules, problems such as high energy consumption and significant losses occur during the carbon capture process, restricting the further industrial application of the amine liquid chemical absorbent method. During high-throughput capture and high-temperature desorption of conventional alkanolamines, due to their high vapor pressure, a large number of absorbent molecules escape into the purified gas and carbon dioxide desorption gas through mist entrainment and thermal volatilization, causing environmental pollution and a decrease in product purity. Furthermore, the high volatility of alkanolamine absorbents necessitates the addition of extra gas-liquid separation devices to industrial carbon capture equipment, increasing investment costs and generating unnecessary cooling energy consumption. Since it is impossible to avoid the volatilization loss of conventional alcohol amine absorbents at the source, how to construct a highly efficient absorption system with high activity and low volatility 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

[0005] The purpose of this invention is to provide an application of piperidinyl polyamine in carbon dioxide capture. The piperidinyl polyamine provided by this invention, as the main agent of a carbon dioxide absorbent, has the advantages of large absorption capacity and low volatilization loss, and exhibits excellent performance in the absorption-desorption cycle of carbon dioxide.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] An application of piperidinyl polyamine in carbon dioxide capture, wherein the piperidinyl polyamine has the structure shown in Formula I:

[0008] Formula I;

[0009] In Equation I: R 1 and R2 It is H, NH2 or OH, and R 1 and R 2 There is one and only one H; R 3 Only when R 1 When it is OH, it is H or CH3; otherwise, it is R. 3 Both are H; R 4 R 5 and R 6 It is independently H or C1~C3 alkyl.

[0010] Preferred, R 4 R 5 and R 6 The C1-C3 alkyl group is methyl, ethyl, n-propyl or isopropyl.

[0011] Preferably, the piperidinyl polyamine has the structure shown in any one of formulas I-1 to I-26:

[0012] 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.

[0013] Preferably, the method for preparing the piperidinyl polyamine includes the following steps:

[0014] Compound 1, Compound 2, an acidic promoter, a transition metal catalyst, and a polar solvent were mixed and alkylated under a nitrogen atmosphere to obtain the piperidinyl polyamine.

[0015] ;

[0016] In compound 1: R 1 and R 2 It is H, NH2 or OH, and R 1 and R 2 There is one and only one H; R 3 Only when R 1 When it is OH, it is H or CH3; otherwise, it is R. 3 All are H.

[0017] In compound 2: R 4 R 5 and R 6 It is independently H or C1~C3 alkyl.

[0018] The alkylation reaction was carried out at a temperature of 80°C. o C~200 o C, more preferably 120 o C~180 o C, more preferably 135 o C~165 o C.

[0019] The alkylation reaction takes 10 h to 72 h, more preferably 12 h to 56 h, and even more preferably 15 h to 36 h.

[0020] The molar ratio of compound 1 to compound 2 is 1:0.1~10. When the R... 3 When the form is CH3, the molar ratio of compound 1 to compound 2 is more preferably 1:1 to 4.

[0021] The acid accelerator is hydrogen chloride, hydrogen bromide, sulfuric acid, sodium bisulfate, potassium bisulfate, phosphoric acid, sodium dihydrogen phosphate, potassium dihydrogen phosphate, methanesulfonic acid, or p-toluenesulfonic acid, and the molar ratio of the acid accelerator to compound 1 is 1:0.2~20. More preferably, it is 1:0.5~15, and even more preferably, it is 1:2~10.

[0022] The transition metal catalyst is copper trifluoromethanesulfonate, zinc trifluoromethanesulfonate, ferric trifluoromethanesulfonate, aluminum trifluoromethanesulfonate, copper chloride, zinc chloride, ferric chloride, aluminum chloride, or zinc sulfate. The mass of the transition metal catalyst added is 1% to 20% of the total mass of compound 1 and compound 2, more preferably 2% to 12%, and even more preferably 3% to 10%.

[0023] The polar solvent is water, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), or N-methylpyrrolidone (NMP). There are no special requirements on the amount of the polar solvent used, as long as it is sufficient to dissolve the raw material.

[0024] The alkylation reaction is preferably carried out under stirring conditions, and the present invention does not have special requirements on the stirring rate. In the present invention, the alkylation reaction is preferably carried out in a high-pressure reactor.

[0025] After the alkylation reaction is completed, the present invention preferably further includes post-treatment of the obtained reaction solution. The post-treatment preferably includes: cooling the reaction solution and adding potassium carbonate solution, extracting the reaction solution with methyl tert-butyl ether, combining the methyl tert-butyl ether extractants, removing the solvent methyl tert-butyl ether using a rotary evaporator, and obtaining piperidinyl polyamine by vacuum distillation.

[0026] Preferably, piperidine polyamine is selectively added to water during carbon dioxide capture to form a combined absorbent, wherein the content of each component, by mass percentage, is: piperidine polyamine 1%~50%, water 50%~99%. More preferably, the content of piperidine polyamine can be 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, etc., and will not be listed exhaustively here.

[0027] 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.

[0028] The beneficial effects of this invention are:

[0029] This invention provides an application of piperidinyl polyamines in carbon dioxide capture. The piperidinyl polyamines provided by this invention have additional amino or hydroxyl groups bonded to the ring rather than within the ring. This allows for the construction of a synergistic effect with multiple active sites while simultaneously enhancing anti-volatility by promoting intermolecular hydrogen bonding, thereby achieving the dual benefits of increased reactivity and reduced volatilization loss.

[0030] This invention provides a method for preparing the piperidinyl polyamine described in the above technical solution. The preparation method provided by this invention is simple to operate and suitable for industrial production.

[0031] This invention provides a combined absorbent comprising a mixture of piperidinyl polyamine and water as described in the above technical solution. Compared with the traditional alkanolamine absorption method, this invention specifically designs the main agent structure of the combined absorbent at the molecular level, resulting in the following superior properties: (1) It introduces a six-membered heterocycle with structural toughness as the molecular skeleton of the absorbent, and at the same time introduces additional amino or hydroxyl groups on the ring rather than inside the ring, thereby constructing a synergistic effect of multiple active sites to further improve the carbon dioxide absorption capacity. As shown in the test results of the application example, at 40 oC. Under 0.1 MPa conditions, the carbon dioxide absorption capacity of the piperidinyl polyamine combined absorbent provided by the present invention can reach up to 19.1 wt%; (2) By bonding to the amino or hydroxyl groups on the ring, the intermolecular hydrogen bonding between piperidinyl polyamine and between piperidinyl polyamine and water is promoted, thereby enhancing the anti-volatility of the absorbent, thereby reducing the volatilization loss of the capture system and the cooling energy consumption of gas-liquid separation. As shown in the test results of the application example, at 55 o Under conditions of prolonged and continuous purging with nitrogen gas, the content of piperidinyl polyamine provided by this invention in the circulating nitrogen gas is no higher than 15 ppm. This indicates that the piperidinyl polyamine absorbent provided by this invention has a large absorption capacity, low volatilization loss, and excellent performance in the absorption-desorption cycle of carbon dioxide. Detailed Implementation

[0032] The following detailed description, with examples, illustrates the piperidinyl polyamines provided by this invention, their preparation methods, and applications. However, these descriptions should not be construed as limiting the scope of protection of this invention.

[0033] Example 1:

[0034] Synthesis of piperidinyl polyamine I-1:

[0035] The corresponding compound 1 (R) 1 =NH2,R 2 =H,R 3 =H, 100mmol, 10.0g), and the corresponding compound 2 (R 4 =H,R 5 =H,R 6 =H (100 mmol, 8.7 g), concentrated sulfuric acid (10 mmol, 1.0 g), copper trifluoromethanesulfonate (0.5 g), and DMSO (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air. The high-pressure reactor was then heated to 100 mL. 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 transferred to a pre-cooled 250 mL beaker, and 30 mL (30 wt%) of potassium carbonate solution was added. The mixture was stirred for 30 min. The mixture was then transferred to a 500 mL separatory funnel and extracted with methyl tert-butyl ether (100 mL × 2). The methyl tert-butyl ether extracts were combined, and the solvent methyl tert-butyl ether was removed using a rotary evaporator. The extract was then distilled under reduced pressure to obtain piperidinyl polyamine I-1. NMR characterization data: 1 H NMR (400MHz, CDCl3) δ=1.61-1.84(m,4H),2.31-2.89(m,9H).

[0036] Example 2:

[0037] Synthesis of piperidinyl polyamine I-2:

[0038] The corresponding compound 1 (R) 1 =NH2,R 2 =H,R 3 =H, 100mmol, 10.0g), and the corresponding compound 2 (R 4 =CH3,R 5 =H,R 6 =H, 100 mmol, 10.1 g), concentrated sulfuric acid (20 mmol, 2.0 g), copper trifluoromethanesulfonate (0.6 g), and DMSO (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air. The high-pressure reactor was heated to 130 °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 transferred to a pre-cooled 250 mL beaker, and 30 mL (30 wt%) of potassium carbonate solution was added. The mixture was stirred for 30 min. The mixture was then transferred to a 500 mL separatory funnel and extracted with methyl tert-butyl ether (100 mL × 2). The methyl tert-butyl ether extracts were combined, and the solvent methyl tert-butyl ether was removed using a rotary evaporator. The extract was then distilled under reduced pressure to obtain piperidinyl polyamine I-2. NMR characterization data: 1 H NMR (400MHz, CDCl3) δ=1.14(d,3H),1.42-1.85(m,4H),2.22-2.84(m,8H).

[0039] Example 3:

[0040] Synthesis of piperidinyl polyamine I-6:

[0041] The corresponding compound 1 (R) 1 =NH2,R 2 =H,R 3 =H, 100mmol, 10.0g), and the corresponding compound 2 (R 4 =H,R 5 =H,R 6 =CH(CH3)2 (100 mmol, 12.9 g), concentrated sulfuric acid (20 mmol, 2.0 g), copper trifluoromethanesulfonate (0.8 g), and DMSO (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air. The high-pressure reactor was then heated to 150 °C. oThe reaction was carried out at C for 28 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 transferred to a pre-cooled 250 mL beaker, and 30 mL (30 wt%) of potassium carbonate solution was added. The mixture was stirred for 30 min. The mixture was then transferred to a 500 mL separatory funnel and extracted with methyl tert-butyl ether (100 mL × 2). The methyl tert-butyl ether extracts were combined, and the solvent methyl tert-butyl ether was removed by rotary evaporation. The extract was then distilled under reduced pressure to obtain piperidinyl polyamine I-6. NMR characterization data: 1 H NMR (400MHz, CDCl3) δ=1.05(d,3H),1.08(d,3H),1.44-1.84(m,4H),2.28-2.95(m,10H).

[0042] Example 4:

[0043] Synthesis of piperidinyl polyamine I-7:

[0044] The corresponding compound 1 (R) 1 =OH,R 2 =H,R 3 =H, 100mmol, 10.1g), and the corresponding compound 2 (R 4 =H,R 5 =H,R 6 =H, 100 mmol, 8.7 g), methanesulfonic acid (20 mmol, 1.9 g), zinc trifluoromethanesulfonate (0.4 g), and NMP (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air. The high-pressure reactor was heated to 110 °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 transferred to a pre-cooled 250 mL beaker, and 30 mL (30 wt%) of potassium carbonate solution was added. The mixture was stirred for 30 min. The mixture was then transferred to a 500 mL separatory funnel and extracted with methyl tert-butyl ether (100 mL × 2). The methyl tert-butyl ether extracts were combined, and the solvent methyl tert-butyl ether was removed by rotary evaporation. The extract was then distilled under reduced pressure to obtain piperidinyl polyamine I-7. NMR characterization data: 1 H NMR (400MHz, CDCl3) δ=1.50-1.91(m,4H),2.41-2.82(m,8H),3.79-3.86(m,1H).

[0045] Example 5:

[0046] Synthesis of piperidinyl polyamine I-8:

[0047] The corresponding compound 1 (R) 1=OH,R 2 =H,R 3 =H, 100mmol, 10.1g), and the corresponding compound 2 (R 4 =CH3,R 5 =H,R 6 =H, 100 mmol, 10.1 g), methanesulfonic acid (20 mmol, 1.9 g), zinc trifluoromethanesulfonate (0.7 g), and NMP (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air. The high-pressure reactor was then heated to 130 °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 transferred to a pre-cooled 250 mL beaker, and 30 mL (30 wt%) of potassium carbonate solution was added. The mixture was stirred for 30 min. The mixture was then transferred to a 500 mL separatory funnel and extracted with methyl tert-butyl ether (100 mL × 2). The methyl tert-butyl ether extracts were combined, and the solvent methyl tert-butyl ether was removed by rotary evaporation. The extract was then distilled under reduced pressure to obtain piperidinyl polyamine I-8. NMR characterization data: 1 H NMR (400MHz, CDCl3) δ=1.21(d,3H),1.58-1.81(m,4H),2.41-2.87(m,7H),3.81-3.88(m,1H).

[0048] Example 6:

[0049] Synthesis of piperidinyl polyamine I-10:

[0050] The corresponding compound 1 (R) 1 =OH,R 2 =H,R 3 =H, 100mmol, 10.1g), and the corresponding compound 2 (R 4 =CH3,R 5 =CH3,R 6 =H, 100 mmol, 11.5 g), methanesulfonic acid (20 mmol, 1.9 g), zinc trifluoromethanesulfonate (1.5 g), and NMP (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air. The high-pressure reactor was then heated to 160 °C. oThe 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 transferred to a pre-cooled 250 mL beaker, and 30 mL (30 wt%) of potassium carbonate solution was added. The mixture was stirred for 30 min. The mixture was then transferred to a 500 mL separatory funnel and extracted with methyl tert-butyl ether (100 mL × 2). The methyl tert-butyl ether extracts were combined, and the solvent methyl tert-butyl ether was removed by rotary evaporation. The extract was then distilled under reduced pressure to obtain piperidinyl polyamine I-10. NMR characterization data: 1 H NMR (400MHz, CDCl3) δ=1.21(s,3H),1.23(s,3H),1.53-1.80(m,4H),2.44-2.81(m,6H),3.85-3.91(m,1H).

[0051] Example 7:

[0052] Synthesis of piperidine polyamine I-17:

[0053] The corresponding compound 1 (R) 1 =OH,R 2 =H,R 3 =CH3, 100mmol, 15.7g), and the corresponding compound 2 (R 4 =H,R 5 =H,R 6 =CH3 (100 mmol, 10.1 g), p-toluenesulfonic acid (15 mmol, 2.6 g), ferric trifluoromethanesulfonate (1.5 g), and DMSO (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air. The high-pressure reactor was then heated to 180 °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 transferred to a pre-cooled 250 mL beaker, and 30 mL (30 wt%) of potassium carbonate solution was added. The mixture was stirred for 30 min. The mixture was then transferred to a 500 mL separatory funnel and extracted with methyl tert-butyl ether (100 mL × 2). The methyl tert-butyl ether extracts were combined, and the solvent methyl tert-butyl ether was removed using a rotary evaporator. The extract was then distilled under reduced pressure to obtain piperidinyl polyamine I-17. NMR characterization data: 1 H NMR (400MHz, CDCl3) δ=1.19(s,6H),1.22(s,6H),1.42-1.75(m,4H),2.40-2.84(m,7H),3.96-4.01(m,1H).

[0054] Example 8:

[0055] Synthesis of piperidinyl polyamine I-18:

[0056] The corresponding compound 1 (R) 1 =H,R 2 =NH2,R 3 =H, 100mmol, 10.0g), and the corresponding compound 2 (R 4 =H,R 5 =H,R 6 =H (100 mmol, 8.7 g), phosphoric acid (30 mmol, 3.5 g), zinc sulfate (1.2 g), and NMP (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air. The high-pressure reactor was then heated to 120 °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 transferred to a pre-cooled 250 mL beaker, and 30 mL (30 wt%) of potassium carbonate solution was added. The mixture was stirred for 30 min. The mixture was then transferred to a 500 mL separatory funnel and extracted with methyl tert-butyl ether (100 mL × 2). The methyl tert-butyl ether extracts were combined, and the solvent methyl tert-butyl ether was removed using a rotary evaporator. The extract was then distilled under reduced pressure to obtain piperidinyl polyamine I-18. NMR characterization data: 1 H NMR (400MHz, CDCl3) δ=1.36-1.82(m,4H),2.32-2.88(m,9H).

[0057] Example 9:

[0058] Synthesis of piperidine polyamine I-19:

[0059] The corresponding compound 1 (R) 1 =H,R 2 =NH2,R 3 =H, 100mmol, 10.0g), and the corresponding compound 2 (R 4 =CH3,R 5 =H,R 6 =H (100 mmol, 10.1 g), phosphoric acid (30 mmol, 3.5 g), zinc sulfate (1.8 g), and NMP (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air. The high-pressure reactor was then heated to 130 °C. oThe 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 transferred to a pre-cooled 250 mL beaker, and 30 mL (30 wt%) of potassium carbonate solution was added. The mixture was stirred for 30 min. The mixture was then transferred to a 500 mL separatory funnel and extracted with methyl tert-butyl ether (100 mL × 2). The methyl tert-butyl ether extracts were combined, and the solvent methyl tert-butyl ether was removed by rotary evaporation. The extract was then distilled under reduced pressure to obtain piperidinyl polyamine I-19. NMR characterization data: 1 H NMR (400MHz, CDCl3) δ = 1.15 (d, 3H), 1.40-1.79 (m, 4H), 2.42-2.88 (m, 8H).

[0060] Example 10:

[0061] Synthesis of piperidinyl polyamine I-20:

[0062] The corresponding compound 1 (R) 1 =H,R 2 =NH2,R 3 =H, 100mmol, 10.0g), and the corresponding compound 2 (R 4 =CH3,R 5 =CH3,R 6 =H (100 mmol, 11.5 g), phosphoric acid (30 mmol, 3.5 g), zinc sulfate (2.5 g), and NMP (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air. The high-pressure reactor was then heated to 170 °C. o The reaction was carried out at C for 48 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 transferred to a pre-cooled 250 mL beaker, and 30 mL (30 wt%) of potassium carbonate solution was added. The mixture was stirred for 30 min. The mixture was then transferred to a 500 mL separatory funnel and extracted with methyl tert-butyl ether (100 mL × 2). The methyl tert-butyl ether extracts were combined, and the solvent methyl tert-butyl ether was removed by rotary evaporation. The extract was then distilled under reduced pressure to obtain piperidinyl polyamine I-20. NMR characterization data: 1 H NMR (400MHz, CDCl3) δ=1.24(s,3H),1.27(s,3H),1.40-1.69(m,4H),2.52-2.78(m,7H).

[0063] Example 11:

[0064] Synthesis of piperidine polyamine I-22:

[0065] The corresponding compound 1 (R) 1=H,R 2 =OH,R 3 =H, 100mmol, 10.1g), and the corresponding compound 2 (R 4 =H,R 5 =H,R 6 =H, 100 mmol, 8.7 g), sodium bisulfate (25 mmol, 3.0 g), aluminum trifluoromethanesulfonate (0.5 g), and DMF (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air. The high-pressure reactor was heated to 110 °C. o The reaction was carried out at C for 18 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 transferred to a pre-cooled 250 mL beaker, and 30 mL (30 wt%) of potassium carbonate solution was added. The mixture was stirred for 30 min. The mixture was then transferred to a 500 mL separatory funnel and extracted with methyl tert-butyl ether (100 mL × 2). The methyl tert-butyl ether extracts were combined, and the solvent methyl tert-butyl ether was removed by rotary evaporation. The extract was then distilled under reduced pressure to obtain piperidinyl polyamine I-22. NMR characterization data: 1 H NMR (400MHz, CDCl3) δ=1.35-1.77(m,4H),2.34-2.89(m,8H),4.06-4.10(m,1H).

[0066] Example 12:

[0067] Synthesis of piperidinyl polyamine I-24:

[0068] The corresponding compound 1 (R) 1 =H,R 2 =OH,R 3 =H, 100mmol, 10.1g), and the corresponding compound 2 (R 4 =CH2CH3,R 5 =H,R 6 =H (100 mmol, 11.5 g), sodium bisulfate (25 mmol, 3.0 g), aluminum trifluoromethanesulfonate (0.8 g), and DMF (100 mL) were sequentially added to a 250 mL high-pressure reactor. After sealing, nitrogen gas was introduced to replace the air. The high-pressure reactor was then heated to 140 °C. oThe reaction was carried out at C for 28 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 transferred to a pre-cooled 250 mL beaker, and 30 mL (30 wt%) of potassium carbonate solution was added. The mixture was stirred for 30 min. The mixture was then transferred to a 500 mL separatory funnel and extracted with methyl tert-butyl ether (100 mL × 2). The methyl tert-butyl ether extracts were combined, and the solvent methyl tert-butyl ether was removed by rotary evaporation. The extract was then distilled under reduced pressure to obtain piperidinyl polyamine I-24. NMR characterization data: 1 H NMR (400MHz, CDCl3) δ = 0.85 (t, 3H), 1.41-1.88 (m, 6H), 2.44-2.97 (m, 7H), 4.08-4.13 (m, 1H).

[0069] Application Example 1-12:

[0070] Add 30g of piperidinyl polyamine and 70g of deionized water (as shown in Table 1) to a 250mL round-bottom flask. After stirring thoroughly, introduce a carbon dioxide-nitrogen mixture with a carbon dioxide volume content of 15% at a flow rate of 400mL / 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 flow of the mixed gas and raise the oil bath temperature to 120°C. o C. The outflow rate was recorded in real time using a gas flow meter. The absorption-desorption performance of the composition formed primarily by piperidine polyamine for carbon dioxide is shown in Table 1.

[0071]

[0072] As shown in Table 1, the piperidine polyamine combination absorbent provided by the present invention has excellent absorption-desorption effect on carbon dioxide.

[0073] Application Example 13-24:

[0074] Add 30g of piperidinyl polyamine and 70g of deionized water (as shown in Table 2) to a 250mL closed reactor with a gas inlet and outlet. After stirring evenly, introduce preheated nitrogen gas (55g) through the gas inlet. o C), nitrogen flow rate is 800 mL / min, pressure is 0.1 MPa, and oil bath jacket temperature is set to 42°C. o C. The content of organic amines in the circulating nitrogen gas was recorded in real time at the outlet using a high-temperature gas infrared analyzer for 300 hours. The test results of the anti-volatilization performance of piperidine polyamines are shown in Table 2.

[0075]

[0076] Application Comparative Examples 1-4:

[0077] Add 30g of the comparative absorbent and 70g of deionized water (as shown in Table 3) to a 250mL closed reactor with a gas inlet and outlet. After stirring evenly, introduce preheated nitrogen gas (55g) through the inlet. o C), nitrogen flow rate is 800 mL / min, pressure is 0.1 MPa, and oil bath jacket temperature is set to 42°C. o C. The content of organic amines in the circulating nitrogen was recorded in real time at the outlet using a high-temperature gas infrared analyzer for 300 hours. The results of the anti-volatilization performance test of the comparative absorbent are shown in Table 3.

[0078] Table 3: Anti-volatilization performance of comparative absorbents

[0079]

[0080] As can be seen from Tables 2 and 3, the anti-volatilization performance of the piperidinyl polyamine provided by the present invention is much better than that of comparative application examples 1-4 under high-flux gas flow.

[0081] 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. Use of a piperidinyl polyamine in carbon dioxide capture, characterized in that, The The piperidinyl polyamine has a structure shown in any one of formula I-1 to formula I-26: 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.

2. Use of a piperidyl polyamine according to claim 1 in carbon dioxide capture, characterized in that, The piperidinyl polyamine is used in carbon dioxide capture, and a combined absorbent is formed by adding water to the piperidinyl polyamine, and the content of each component is 1% to 50% by mass of the piperidinyl polyamine and 50% to 99% by mass of water.

3. Use of a piperidyl polyamine according to claim 1 in carbon dioxide capture, characterized in that, The application includes removing carbon dioxide from flue gas, waste gas, tail gas, product gas, raw material gas, decomposition gas, water gas, natural gas and / or biogas.

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