Dual-functionalized resin solid amine material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of gas trapping methods, and particularly relates to a dual-functionalized resin solid amine material as well as a preparation method and application thereof. The solid amine carbon trapping material takes commercially available macroporous weak-base anion exchange resin particles as a matrix, the surfaces of carrier resin particles secondarily modify polyamine chains under the action of hydrogen bonds, and compared with a similar material prepared from a non-polar macroporous resin matrix, the solid amine carbon trapping material has more excellent carbon dioxide adsorption capacity and cyclic adsorption-desorption stability.

Description

Technical Field

[0001] This invention belongs to the field of gas trapping materials technology, and specifically relates to a bifunctional resin solid amine material, its preparation method and application. Background Technology

[0002] In the context of "dual carbon," large-scale carbon capture, utilization, and storage (CCUS) of carbon dioxide produced by the combustion of fossil fuels at point sources is an important way to reduce carbon dioxide emissions. Currently, the liquid amine absorption method for cyclic capture of carbon dioxide is a relatively mature technology, while solid amine adsorption capture technology has become a more promising development direction due to its lower desorption energy consumption.

[0003] Traditional methods for preparing solid amine materials include impregnation and grafting. The former drives the organic amine to diffuse into the pores in solution, and then loads the amine functional component into the pores by removing the solvent. The resulting solid amine material has a high amine loading, but poor stability. The latter links the reactive support to the amine functional component by chemical bonds. The resulting solid amine material has good stability, but suffers from low amine loading.

[0004] Resins are excellent supports for preparing solid amine adsorbents due to their controllable specific surface area, pore volume, and pore size, low cost, easy surface modification, ease of reaction molding, and controllable particle size. For example, CN114832796A discloses a solid amine material of polyethyleneimine supported on a D1400 macroporous adsorption resin. The material has an adsorption capacity of 163±5 mg / g for CO2, and the adsorption capacity does not change significantly after 5 desorption-cycle cycles. However, the interaction between the nonpolar support and the amine functional component is weak, and the long-term cycling stability of the material needs to be investigated. US20110088550A1 discloses a process and equipment for carbon dioxide capture using polystyrene-type weakly basic anion exchange resin grafted with primary amine functional groups. However, due to the limited amine content, the carbon dioxide adsorption capacity of most existing anion exchange resins needs further improvement. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a solid amine carbon capture material with high adsorption capacity and cycling stability, prepared using a bifunctionalization method.

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

[0007] A bifunctional solid amine material, the structure of which is shown in Formula I:

[0008]

[0009] In Formula I, "*" represents resin; m is an integer from 0 to 6; and n is an integer from 1 to 232.

[0010] Furthermore, n is 1-116, preferably 1-58, and more preferably 1-13.

[0011] Furthermore, the resin includes polystyrene or polyacrylic acid.

[0012] A method for preparing the above-mentioned bifunctionalized solid amine carbon capture material, the preparation method comprising the following steps:

[0013] The resin with amine functional groups on its surface is pretreated and then modified with amine functional groups again to obtain the bifunctionalized solid amine material.

[0014] Furthermore, the resin with amine functional groups modified on its surface is a macroporous weak base anion exchange resin, which includes polystyrene or polyacrylic acid; the specific method for washing pretreatment is to wash with alcohol or water.

[0015] Furthermore, the secondary modification of the amine functional group involves impregnating a resin with amine functional groups on its surface in a polyethyleneimine solution.

[0016] Furthermore, the mass ratio of solute to solvent in the polyethyleneimine solution is 5-38:100.

[0017] Furthermore, the mass ratio of the polyethyleneimine to the resin with amine functional groups modified on the surface is 10-75:100.

[0018] The present invention also protects a solid amine material obtained by the above-described method for preparing bifunctional solid amine carbon trapping materials.

[0019] This invention also protects the application of the above-mentioned bifunctional solid amine material in CO2 adsorption.

[0020] Furthermore, in Formula I, "*" represents organic polymer resin particles, including polystyrene particles or polyacrylic acid particles, with a D50 particle size of 0.2-1 mm;

[0021] The present invention also provides a method for preparing such a bifunctional solid amine material, which involves (1) washing and pretreating a commercially available macroporous weak base anion exchange resin, (2) interacting with a solution of polyethyleneimine for a period of time, and (3) removing the solvent by rotary evaporation to obtain the bifunctional solid amine carbon capture material.

[0022] Specifically, the macroporous weak base anion exchange resin carrier is pretreated by washing with ethanol or water; polyethyleneimine is dissolved in a solvent and added to the pretreated resin in a certain proportion, and the reaction is carried out at 25-60℃ for 2-5 hours. The mass ratio of polyethyleneimine to resin carrier particles is 10-75:100, and the solvent is any one of methanol, ethanol, acetonitrile, or toluene.

[0023] Beneficial effects:

[0024] (1) The dual-functional resin solid amine material is grafted with one layer of amine functional component and then impregnated with another layer of amine functional component, thus having a higher amine loading and CO2 adsorption capacity.

[0025] (2) The first layer functional component is covalently grafted to the resin particles, and the second layer functional component interacts with the first layer functional component through hydrogen bonds. Therefore, the material has better cycle stability. Attached Figure Description

[0026] Figure 1 Infrared spectra (KBr pellets) of bifunctionalized solid amine material ESA-7 and comparative material ESA-14;

[0027] Figure 2 CO2 adsorption process curves for ESA-7, a bifunctional solid amine material;

[0028] Figure 3 The CO2 adsorption-desorption cycle adsorption capacity of the bifunctional solid amine material ESA-7 is shown. Detailed Implementation

[0029] The present invention will be further described in detail below with reference to the embodiments.

[0030] Example 1

[0031] A bifunctional solid amine material, ESA-1, comprises aminomethylated polystyrene particles, wherein the surface of the aminomethylated polystyrene particles is secondary functionalized with 10 wt% tetraethylenepentamine, and the structure is shown below:

[0032]

[0033] Where "*" represents polystyrene, n is 4, and m is 0;

[0034] The preparation method of the bifunctional solid amine material ESA-1 provided in this embodiment is as follows: 10g of aminomethylated polystyrene particles (VPOC1065, particle size 0.3-1.25mm, purchased from Lanxess Chemicals (China) Co., Ltd.) were washed with water to neutrality in a chromatography column and then dried to constant weight. 0.05g of tetraethylenepentamine was dissolved in 1g of ethanol, and 0.5g of pretreated aminomethylated polystyrene particles were added. The mixture was stirred at 25℃ for 2h, and then dried under reduced pressure by rotary evaporation to constant weight to obtain the bifunctionalized ESA-1.

[0035] Example 2

[0036] A bifunctional solid amine material, ESA-2, comprises aminomethylated polystyrene particles, wherein the surface of the aminomethylated polystyrene particles is secondary functionalized with a 25 wt% tetraethylenepentamine component, and the structure is shown below:

[0037]

[0038] Where "*" represents polystyrene, n is 4, and m is 0;

[0039] The preparation method of the bifunctional solid amine material ESA-2 provided in this embodiment is as follows: 0.13g of tetraethylenepentamine is dissolved in 1g of methanol, 0.5g of the pretreated aminomethylated polystyrene particles in Example 1 are added, the mixture is stirred at 50°C for 3h, and then dried under reduced pressure by rotary evaporation to constant weight to obtain bifunctional ESA-2.

[0040] Example 3

[0041] A bifunctional solid amine material, ESA-3, comprises aminomethylated polystyrene particles, wherein the surface of the aminomethylated polystyrene particles is secondary functionalized with 50 wt% tetraethylenepentamine, and the structure is shown below:

[0042]

[0043] Where "*" represents polystyrene, n is 4, and m is 0;

[0044] The preparation method of the bifunctional solid amine material ESA-3 provided in this embodiment is as follows: 0.25g of tetraethylenepentamine is dissolved in 1g of acetonitrile, 0.5g of the pretreated aminomethylated polystyrene particles in Example 1 is added, the mixture is stirred at 25°C for 5h, and then dried under reduced pressure by rotary evaporation to constant weight to obtain bifunctional ESA-3.

[0045] Example 4

[0046] A bifunctional solid amine material, ESA-4, comprises aminomethylated polystyrene particles, wherein the surface of the aminomethylated polystyrene particles is secondary functionalized with a 75 wt% tetraethylenepentamine component, and the structure is shown below:

[0047]

[0048] Where "*" represents polyacrylic acid, n is 4, and m is 0;

[0049] The preparation method of the bifunctional solid amine material ESA-4 provided in this embodiment is as follows: 0.38g of tetraethylenepentamine is dissolved in 1g of toluene, 0.5g of aminomethylated polystyrene particles pretreated in Example 1 are added, the mixture is stirred at 25°C for 2h, and then dried under reduced pressure by rotary evaporation to constant weight to obtain bifunctional ESA-4.

[0050] Example 5

[0051] A bifunctional solid amine material, ESA-5, comprises aminomethylated polystyrene particles, wherein the surface of the aminomethylated polystyrene particles is secondary functionalized with 50% PEI-600 component, and the structure is shown below:

[0052]

[0053] Where “*” represents polystyrene, n = 13, and m = 0;

[0054] The preparation method of the bifunctional solid amine material ESA-5 provided in this embodiment is as follows: 0.25g of PEI-600 is dissolved in 1g of ethanol, 0.5g of aminomethylated polystyrene particles pretreated in Example 1 are added, the mixture is stirred at 25°C for 2h, and then dried under reduced pressure by rotary evaporation to constant weight to obtain bifunctional ESA-5.

[0055] Example 6

[0056] A bifunctional solid amine material, ESA-6, comprises aminomethylated polystyrene particles, wherein the surface of the aminomethylated polystyrene particles is secondary functionalized with 50% PEI-600 component, and the structure is shown below:

[0057]

[0058] Where “*” represents polystyrene, n=13, m=0;

[0059] The preparation method of the bifunctional solid amine material ESA-6 provided in this embodiment is as follows: Take 10g of aminomethylated polystyrene particles (A110, particle size 0.3-1.25mm, purchased from Purolite), wash with ethanol and water until neutral in a chromatography column, and then dry to constant weight. Dissolve 0.25g of PEI-600 in 1g of ethanol, add 0.5g of pretreated aminomethylated polystyrene particles, stir at 25℃ for 2h, and dry under reduced pressure by rotary evaporation to constant weight to obtain bifunctionalized ESA-6.

[0060] Example 7

[0061] A bifunctional solid amine material, ESA-7, comprises diethylenetriamine-methylated polystyrene particles, wherein the surface of the diethylenetriamine-methylated polystyrene particles is secondary functionalized with 50% PEI-600 component, and the structure is shown below:

[0062]

[0063] Where "*" represents polystyrene, m=2, n=13;

[0064] The preparation method of the bifunctional solid amine material ESA-7 provided in this embodiment is as follows: Take 10g of polyethyleneimine methylated polystyrene particles (SQD-96, particle size 0.32-1.25mm, purchased from Jiangsu Suqing Water Treatment Engineering Co., Ltd.), wash them sequentially with ethanol, 1M HCl, 1M NaOH, and water in a chromatography column until neutral, and dry to constant weight. Dissolve 0.25g of PEI-600 in 1g of ethanol, add 0.5g of pretreated polyethyleneimine methylated polystyrene particles, stir at 25℃ for 2h, and dry under reduced pressure by rotary evaporation to constant weight to obtain bifunctional ESA-7.

[0065] Example 8

[0066] A bifunctional solid amine material, ESA-8, comprises polymethyl methacrylate particles derived from diethylenetriamine aminolysis, wherein the surface of the diethylenetriamine aminolysis polymethyl methacrylate particles is secondary functionalized with 50% PEI-600 component, and the structure is shown below:

[0067]

[0068] Where “*” represents polystyrene, m=2, n=13;

[0069] The preparation method of the bifunctional solid amine material ESA-8 provided in this embodiment is as follows: 10g of polymethyl acrylate particles (D318, particle size 0.32-1.25mm, purchased from Jiangsu Suqing Water Treatment Engineering Co., Ltd.) obtained by aminolysis of ethylene polyamine were washed sequentially with ethanol, 1M HCl, 1M NaOH, and water in a chromatography column until neutral and dried to constant weight. 0.25g of PEI-600 was dissolved in 1g of ethanol, and 0.5g of pretreated polymethyl acrylate particles obtained by aminolysis of polyethyleneimine were added. The mixture was stirred at 25℃ for 2h, and then dried under reduced pressure by rotary evaporation to constant weight to obtain the bifunctional ESA-8.

[0070] Example 9

[0071] A bifunctional solid amine material, ESA-9, comprises diethylenetriamine-methylated polystyrene particles, wherein the surface of the diethylenetriamine-methylated polystyrene particles is secondary functionalized with 50% PEI-10000 component, and the structure is shown below:

[0072]

[0073] Where “*” represents polystyrene, m=2, n=232;

[0074] The preparation method of the bifunctional solid amine material ESA-9 provided in this embodiment is as follows:

[0075] 0.25g of PEI-10000 was dissolved in 1g of ethanol, and 0.5g of the ethylene polyamine methylated polystyrene particles pretreated in Example 7 were added. The mixture was stirred at 25°C for 2 hours and then dried under reduced pressure to constant weight to obtain bifunctionalized ESA-9.

[0076] Example 10

[0077] A bifunctional solid amine material, ESA-9, comprises poly(ethylenetriamine) methylated polystyrene particles, wherein the surface of the poly(ethylenetriamine) methylated polystyrene particles is secondary functionalized with 50% PEI-5000 component, and the structure is shown below:

[0078]

[0079] Where "*" represents polystyrene, m=2, n=116;

[0080] The preparation method of the bifunctional solid amine material ESA-9 provided in this embodiment is as follows: 0.25g of PEI-5000 is dissolved in 1g of ethanol, 0.5g of ethylene polyamine methylated polystyrene particles pretreated in Example 7 are added, the mixture is stirred at 25°C for 2h, and then dried under reduced pressure to constant weight to obtain bifunctional ESA-10.

[0081] Example 11

[0082] A bifunctional solid amine material, ESA-9, comprises diethylenetriamine-methylated polystyrene particles, wherein the surface of the diethylenetriamine-methylated polystyrene particles is secondary functionalized with 50% PEI-2500 component, and the structure is shown below:

[0083]

[0084] Where "*" represents polystyrene, m=2, n=58;

[0085] The preparation method of the bifunctional solid amine material ESA-9 provided in this embodiment is as follows: 0.25g of PEI-2500 is dissolved in 1g of ethanol, 0.5g of ethylene polyamine methylated polystyrene particles pretreated in Example 7 are added, the mixture is stirred at 25°C for 2h, and then dried under reduced pressure by rotary evaporation to constant weight to obtain bifunctional ESA-11.

[0086] Comparative Example 1

[0087] 10g of nonpolar polystyrene particles (DA201, particle size 0.32-1.25mm, purchased from Jiangsu Suqing Water Treatment Engineering Co., Ltd.) were washed sequentially with ethanol and water in a chromatography column and dried to constant weight. 0.25g of PEI-600 was dissolved in 1g of ethanol, and 0.5g of the pretreated nonpolar polystyrene particles were added. The mixture was stirred at 25℃ for 2h, and then dried under reduced pressure by rotary evaporation to constant weight to obtain ESA-12.

[0088] Comparative Example 2

[0089] 10g of nonpolar polystyrene particles (DIaIonHP20, particle size 0.32-1.25mm, purchased from Chongqing Kaiyin Chemical Co., Ltd.) were washed successively with ethanol and water in a chromatography column and dried to constant weight. 0.25g of PEI-600 was dissolved in 1g of ethanol, and 0.5g of the pretreated nonpolar polystyrene particles were added. The mixture was stirred at 25℃ for 2h, and then dried under reduced pressure by rotary evaporation to constant weight to obtain ESA-13.

[0090] Comparative Example 3

[0091] Take 10g of diethylenetriamine methylated polystyrene particles (SQD-96, particle size 0.32-1.25mm, purchased from Jiangsu Suqing Water Treatment Engineering Co., Ltd.), wash them sequentially with ethanol, 1M HCl, 1M NaOH and water in a chromatography column until neutral and dry to constant weight to obtain ESA-14.

[0092] Comparative Example 4

[0093] Take 10g of aminomethylated polystyrene particles (A110, particle size 0.3-1.25mm, purchased from Purolite), wash with ethanol and water in a chromatography column until neutral, and then dry to constant weight to obtain ESA-15.

[0094] Comparative Example 5

[0095] Take 10g of aminomethylated polystyrene particles (VPOC1065, particle size 0.3-1.25mm, purchased from Lanxess Chemicals (China) Co., Ltd.), wash with water to neutral in a chromatography column and dry to constant weight to obtain ESA-16.

[0096] Comparative Example 6

[0097] Take 10g of diethylenetriamine-hydrolyzed polymethyl acrylate particles (D318, particle size 0.32-1.25mm, purchased from Jiangsu Suqing Water Treatment Engineering Co., Ltd.), wash them sequentially with ethanol, 1M HCl, 1M NaOH and water in a chromatography column until neutral and dry to constant weight to obtain ESA-17.

[0098] Depend on Figure 1 It can be seen that, after bifunctional modification, the resulting solid amine material ESA-7 exhibits good performance at 3500 cm⁻¹. -1 The NH stretching vibration peak at the location is significantly enhanced, proving that PEI600 is effectively loaded.

[0099] Adsorption performance test:

[0100] CO2 adsorption performance: Approximately 30 mg of solid amine material was weighed into the adsorption apparatus, and CO2 gas at 1 atm (400 sccm) was introduced at 25°C. The weight gain was recorded, and the adsorption capacity was calculated. The CO2 adsorption process curve of the bifunctional solid amine material ESA-7 provided in Example 7 is shown in the figure below. Figure 1 As shown;

[0101] from Figure 1 It can be seen that the bifunctional solid amine material ESA-7 provided in Example 7 can adsorb CO2 in a CO2 atmosphere, and the adsorption capacity at 600 min is as high as 4.56 mmol / g.

[0102] CO2 cyclic adsorption performance: 30 mg of solid amine material was weighed into the adsorbent, and 1 atm CO2 gas (400 sccm) was introduced at 25°C. The weight gain was recorded, and the adsorption capacity was calculated. The inlet gas was then switched to N2, and the temperature was raised to 100°C for CO2 desorption for 45 minutes. The temperature was then lowered to 25°C, and the inlet gas was switched back to CO2 for adsorption. This process was repeated 20 times to obtain the cyclic adsorption capacity. The CO2 cyclic adsorption bar chart of the bifunctional solid amine material ESA-7 provided in Example 7 is shown below. Figure 2 As shown;

[0103] from Figure 2 It can be seen that the bifunctional solid amine material ESA-7 provided in Example 7 has excellent cycling stability. After 20 adsorption / desorption cycles, the CO2 adsorption capacity of the material decreases by less than 0.01%.

[0104] The tests were conducted using the methods described above, and the results are shown in Table 1.

[0105] Table 1

[0106]

[0107]

[0108] As can be seen from the data in Table 1, the bifunctional solid amine material ESA-1-ESA-11 provided in Examples 1-11 has a significantly higher CO2 adsorption capacity compared with the impregnation-prepared solid amine materials ESA-12 and ESA-13 provided in Comparative Examples 1-2, or the grafted solid amine material ESA-14-ESA-17 provided in Comparative Examples 3-6. At the same time, the bifunctional solid amine material ESA-7-ESA-9 provided in Examples 1-11 has better cycling stability. After 20 adsorption-desorption cycles, the CO2 adsorption capacity of the bifunctional solid amine material ESA-7 provided in Example 7 decreased by only 0.06% of that of the solid amine material provided in Comparative Example 1.

Claims

1. A bifunctional solid amine material, characterized in that, The structure of the solid amine material is shown in Formula I: In Formula I, "*" represents resin, m is an integer from 0 to 6, and n is an integer from 1 to 232.

2. The bifunctionalized solid amine material according to claim 1, characterized in that, The n is an integer from 1 to 13.

3. The bifunctionalized solid amine material according to claim 1, characterized in that, The resin includes polystyrene or polyacrylic acid.

4. A method for preparing the bifunctionalized solid amine carbon material according to any one of claims 1-3, the preparation method comprising the following steps: The resin with amine functional groups on its surface is pretreated and then modified with amine functional groups again to obtain the bifunctionalized solid amine material.

5. The preparation method according to claim 4, characterized in that: The resin with amine functional groups modified on its surface is a macroporous weak base anion exchange resin, which includes polystyrene or polyacrylic acid; the specific method for washing pretreatment is to wash with alcohol or water.

6. The preparation method according to claim 4, characterized in that: The secondary modification of amine functional groups involves impregnating a resin with amine functional groups on its surface in a polyethyleneimine solution.

7. The preparation method according to claim 6, characterized in that: The mass ratio of solute to solvent in the polyethyleneimine solution is 5-38:

100.

8. The preparation method according to claim 7, characterized in that: The mass ratio of the polyethyleneimine to the resin with amine functional groups on its surface is 10-75:

100.

9. A solid amine material obtained by the method for preparing bifunctionalized solid amine carbon materials according to any one of claims 4-8.

10. The application of the bifunctionalized solid amine material according to any one of claims 1-3 and 9 in CO2 adsorption.

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