A multi-level porous structure polymer-based solid amine decarbonizer and a preparation method thereof

Abstract

The application discloses a kind of multilevel pore structure polymer base solid amine decarbonizer and preparation method thereof, it is related to organic chemistry, polymer material and carbon capture technical field, comprising: S1, preparation even dispersed pouring liquid;S2, preparation copolymer / water-soluble polymer opal whole polymer pouring;S3, preparation multilevel pore structure polymer matrix;S4, preparation multilevel pore structure polymer base solid amine material.The material has interconnected open pore inverse opal structure, it has certain mesoporous structure on pore wall, and the multilevel pore structure material based on inverse opal structure is combined with mesoporous structure existing in inverse opal wall, and the specific surface area of overall material is as high as 600m 2 / g.Because material is crosslinked copolymer porous structure, thermal stability is strong, material active amine site is fixed on multilevel pore structure matrix material by chemical reaction, guarantee that active functional site can be adjusted according to demand proportion on the basis that material has porous structure.

Description

Technical Field

[0001] This invention relates to the fields of organic chemistry, polymer materials and carbon capture technology, and in particular to a multi-layered porous polymer-based solid amine decarbonizing agent and its preparation method. Background Technology

[0002] With the continuous development of society and economy, the consumption of fossil fuels is constantly increasing, and carbon dioxide (CO2), as the main product of fossil fuels, is being emitted in increasing quantities. As a greenhouse gas, CO2 accounts for 80% of global greenhouse gas emissions and is considered one of the most important factors in global climate change. (Ali AA, Roslee MO, Jinsoo K. A review on application of activated carbons for carbon dioxide capture: present performance, preparation, and surface modification for further improvement. [J]. Environmental science and pollution research international, 2021, 28(32).) The development of CO2 capture technology has attracted urgent attention. In order to meet the challenge of global warming, methods for absorbing carbon dioxide, such as liquid solvents, membranes, biological processes, and solid materials, have been extensively studied (Wu Y, Xu J, Mumford K, et al. Recent advances in carbon dioxide capture and utilization with amines and ionic liquids [J]. Green Chemical Engineering, 2020, 1(01): 16-32.). Currently, composite amine solutions are used commercially to capture CO2, with fast absorption rate and selectivity. However, this technology has some drawbacks, including high regeneration heat, low absorption capacity, severe equipment corrosion, and low resistance to acid gases (Wang M, Joel SA, Ramshaw C, et al. Process intensification for post-combustion CO2 capture with chemical absorption: A critical review [J]. Applied Energy, 2015, 158.). Solid amine adsorbents combine the advantages of solid amine solutions and solid adsorbent materials, possessing high efficiency, rapid selectivity, and low energy consumption, and can serve as a substitute for composite amine liquid latent products. Due to the high reactivity between loaded amines and CO2, solid amine adsorbents can efficiently and rapidly selectively adsorb CO2, while significantly reducing CO2 regeneration energy compared to amine solutions.(Li K, Jiang J, Yan F, et al. The influence of polyethyleneimine type and molecular weight on the CO2 capture performance of PEI-nano silica adsorbents[J]. Applied Energy, 2014, 136.) Common types of solid adsorbents include: silica, zeolite, activated carbon, resin materials, etc. (Nie L, Mu Y, Jin J, et al. Recent developments and consideration issues in solid adsorbents for CO2 capture from flue gas[J]. Chinese Journal of Chemical Engineering, 2018, 26(11): 2303-2317.) Their preparation methods are divided into three categories: impregnation, grafting and direct synthesis (Ge K, Yu Q, Chen S, et al. Modeling CO2 adsorption dynamics within solid amine sorbent based on the fundamental diffusion-reaction processes[J]. Chemical Engineering Journal, 2019, 364.). (1) Impregnation method: Amines are loaded into the scaffold through van der Waals forces to form amino solid adsorbents, but the weak link between the amine and the support leads to poor thermal stability; (2) Grafting: Amines and the support are combined through the condensation reaction between aminosilane and the active groups of the support material to form amino solid adsorbents, but their absorption capacity is affected by the number of active sites and their CO2 loading is low; (3) Direct synthesis: Amine functional groups are introduced into the pore surface of the support through molecular reaction and polymerization synthesis to directly form amino solid adsorbents. However, the synthesis method is immature and it is difficult to form a stable porous structure.

[0003] Although the aforementioned existing technologies can obtain solid amine materials through different methods, it is difficult to comprehensively achieve the desired thermal stability, number of active amine groups, and stable pore structure using these methods. Therefore, developing solid amine materials with porous structures and highly active sites is of great significance. Summary of the Invention

[0004] The present invention aims to provide a multi-layered porous polymer-based solid amine decarbonizing agent and its preparation method. This method can prepare a stable multi-porous solid amine material. The high specific surface area porous material formed by this method can increase the utilization rate of active groups, which is beneficial to improving the material's CO2 capture efficiency. To achieve the above objective, the present invention provides the following technical solution:

[0005] This invention provides a method for preparing a multi-layered porous polymer-based solid amine decarbonizing agent, the method comprising the following steps:

[0006] After mixing the monomers, initiators and organic matter, the mixture is dispersed in a mixer at a speed of 1000-8000 r / min for 5-20 min at -10 to 35°C to obtain a uniformly dispersed casting liquid.

[0007] The uniformly dispersed casting liquid is injected into and submerged in the water-soluble polymer opal in the reactor. Then the reactor is placed in a constant temperature chamber and prepolymerized at 30-60℃ for 1-12 hours, and then polymerized at 70-90℃ for 12-45 hours to obtain the integral polymer casting of copolymer / water-soluble polymer opal.

[0008] The copolymer on the surface of the monolithic polymer casting is removed, and then the monolithic polymer casting is immersed in opal removal agent for 10-44 hours, during which the opal removal agent is replaced several times; after cleaning and wetting with anhydrous ethanol, it is extracted with solvent for 4-24 hours, and finally vacuum dried at 25-70℃ for 8-12 hours to obtain a multi-layered porous polymer matrix.

[0009] The multi-layered porous polymer matrix material is immersed in a reactor containing a composite modifier solution and reacted at 40–95°C for 12–48 hours. The reacted material is washed 5–10 times with a cleaning agent and finally dried under vacuum at 25–70°C to obtain a multi-layered porous polymer-based solid amine.

[0010] Further, in step S1, the volume ratio of the polymerizable monomer to the organic compound is V. 聚合单体 V 有机物 = 1:0.05~4; the mass of the initiator is 0.1%~8% of the mass of the polymerizing monomer.

[0011] Further, in step S1, the polymerizable monomer is a blend of a mixture of single and double bond monomers and a crosslinking agent; wherein, the mixture of single and double bond monomers consists of two or three single and double bond monomers, and their mass ratio is 1:0.01~9:0~9; the mass ratio of the single and double bond monomer mixture to the crosslinking agent is 1:0.01~9.

[0012] The single and double bond monomers are mixtures of at least one of glycidyl methacrylate, vinyl acetate, 2-hydroxyethyl acrylate, or N-(3-dimethylaminopropyl)methacrylamide;

[0013] The crosslinking agent is at least one of divinylbenzene, ethylene glycol dimethacrylate, triallyl isocyanurate, and trimethylolpropane trimethacrylate.

[0014] The initiator is one of azobisisobutyronitrile, azobisisoheptanenitrile, AlCl3·6H2O, benzoyl peroxide, dodecyl peroxide, diisopropyl peroxide, or tert-butyl peroxide.

[0015] The organic compound is one or more of an organic solvent and an oligomer; wherein the organic solvent includes one or more of toluene, xylene, ethyl acetate, butyl acetate, n-hexane, cyclohexane, N,N-dimethylformamide, 2,3-dimethylbutane, n-heptane, and cycloheptane; and the oligomer is one or more of Span, polyethylene glycol, polypropylene glycol, or poly(dimethylsiloxane).

[0016] Further, in step S2, the water-soluble polymer opal is water-soluble polyacrylamide opal with a particle size range of 500–1000 nm.

[0017] Furthermore, the preparation method of the water-soluble polyacrylamide opal includes the following steps:

[0018] Anhydrous ethanol, deionized water, polyvinylpyrrolidone, and acrylamide were added sequentially at room temperature and stirred until homogeneous. The mixture was then heated to 60–90°C, and benzoyl peroxide was added. The reaction proceeded for 6–12 hours. The dispersion was then centrifuged in a centrifuge tube to remove the solvent. After washing 3–5 times with anhydrous ethanol, the mixture was centrifuged again and then vacuum dried at 25–45°C for 8–24 hours to obtain water-soluble polyacrylamide opal with an average particle size of 500–1000 nm.

[0019] Further, in step S3, the opal removal agent is a 10% methanol distilled aqueous solution;

[0020] The solvent is one of petroleum ether, anhydrous methanol, dimethylformamide, and methyl ethyl ketone.

[0021] Further, in step S4, the mass ratio of the polymer matrix material to the composite modifier is: m 聚合物基体材料 :m 复合改性剂 =1:50~150.

[0022] Further, in step S4, the composite modifier solution is one or more of an alkanolamine, alkylamine, or amino acid, mixed with the medium; wherein,

[0023] Alkylamines: monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-hydroxymethyl-1,3-propanediol, glucosamine;

[0024] Alkaneamines: piperazine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, cyclohexylamine, tert-butylamine, polyethylenepolyamine, branched polyethyleneimine;

[0025] Amino acids: asparagine, glutamic acid, gamma glutamic acid, histidine, lysine, arginine, aspartic acid, glycine, alanine, serine, threonine, tyrosine, tryptophan, cysteine;

[0026] The medium is tetrahydrofuran or dimethylformamide.

[0027] Further, in step S4, the cleaning agent is an aqueous solution of methanol or ethanol, and the mass ratio of alcohol to water is 1:0.02 to 9.

[0028] The present invention also provides a multi-level porous polymer-based solid amine decarbonizing agent, which is prepared by the above method.

[0029] The technical effects and advantages of this invention are as follows:

[0030] The multi-level porous polymer-based solid amine material prepared by the method of this invention has an interconnected open-pore inverse opal structure. The inverse opal pore walls possess a certain degree of mesoporous structure, thus forming a multi-level porous material with an inverse opal as the basic structure combined with the mesoporous structure existing on the inverse opal walls. The overall material has a specific surface area as high as 600 m². 2 / g. Because the material has a cross-linked copolymer porous structure, it has strong thermal stability. The active amine sites of the material are fixed on the multi-level porous matrix material by chemical reaction, which ensures that the active functional sites can be adjusted according to the required ratio while maintaining the porous structure of the material, thus overcoming the limitations of the other three methods mentioned above.

[0031] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention may be realized and obtained by means of the structures pointed out in the description, claims and drawings. Attached Figure Description

[0032] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0033] Figure 1 This is a flowchart of a method for preparing a multi-layered porous polymer-based solid amine decarbonizing agent according to the present invention;

[0034] Figure 2 This is a SEM image of water-soluble polyacrylamide opal with a particle size of 700 nm in Example 1 of the present invention;

[0035] Figure 3 The nitrogen adsorption-desorption curves and pore size distribution diagrams of the inverse opal structure polymer matrix material in Example 1 of this invention are shown.

[0036] Figure 4 The nitrogen adsorption-desorption curves and pore size distribution diagrams of the multi-level porous polymer matrix material in Example 1 of this invention are shown.

[0037] Figure 5 This is a SEM image of the multi-level porous polymer-based solid amine material loaded with tetraethylenepentamine and monoethanolamine in Example 2 of the present invention.

[0038] Figure 6 The nitrogen adsorption-desorption curves and pore size distribution diagrams of the multi-level porous polymer-based solid amine material loaded with tetraethylenepentamine and monoethanolamine in Example 2 of this invention are shown.

[0039] Figure 7 The nitrogen adsorption-desorption curves and pore size distribution diagrams of the multi-level porous polymer-based solid amine material supported on triethylenetetramine and meglumine in Example 3 of this invention are shown.

[0040] Figure 8 The nitrogen adsorption-desorption curves and pore size distribution diagrams of the multi-level porous polymer-based solid amine material loaded with glycine, glutamic acid and lysine in Example 4 of this invention are shown.

[0041] Figure 9 The nitrogen adsorption-desorption curves and pore size distribution diagrams of the multi-level porous polymer-based solid amine material supported on branched polyethyleneimine in Example 5 of this invention are shown. Detailed Implementation

[0042] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0043] The design concept of this invention includes: preparing a polymer-based multi-level porous matrix material using a dual-template method combining water-soluble polymer opal and organic substances; modifying the matrix material by introducing amine organic compounds to form a multi-level porous polymer-based solid amine carbon scavenger; controlling the proportion of different polymer monomers allows control of the hydroxylamine ratio in the modified material; and modifying the polymer matrix material by introducing alkanolamines, amines, and amino acid compounds of different structural types allows for the design of a polyolamine-structured solid amine CO2 scavenger. The multi-level porous polymer solid amine obtained by this invention features a hierarchical pore structure combining an inverse opal structure with mesopores. The interconnected inverse opal structure helps improve the mass transfer efficiency of carbon dioxide within the material, while the abundant microporous structure provides more CO2 capture space, thus improving capture efficiency. The overall material specific surface area is designed to range from 30 to 600 m². 2 / g, multi-layered porous solid amine materials possess structural stability, strong designability, excellent adsorption and regeneration performance, and good thermal stability, and have broad potential application value in the field of CO2 capture.

[0044] Therefore, the present invention provides a method for preparing a multi-layered porous polymer-based solid amine decarbonizing agent. Figure 1 This is a flowchart illustrating a method for preparing a multi-layered porous polymer-based solid amine decarbonizing agent according to the present invention. Figure 1 As shown, the method includes the following steps:

[0045] Step S1: After mixing the monomer, initiator and organic matter, the mixture is dispersed in a mixer at a speed of 1000-8000 r / min for 5-20 min at -10 to 35℃ to obtain a uniformly dispersed casting liquid.

[0046] In step S1 of this invention, the volume ratio of the polymeric monomer to the organic compound is V. 聚合单体 V 有机物 = 1:0.05~4; the mass of the initiator is 0.1%~8% of the mass of the polymerizing monomer;

[0047] The polymerizable monomer is a blend of a mixture of single and double bond monomers and a crosslinking agent; wherein the single and double bond monomer mixture consists of two or three single and double bond monomers in a mass ratio of 1:0.01 to 9:0 to 9; the mass ratio of the single and double bond monomer mixture to the crosslinking agent is 1:0.01 to 9.

[0048] Further, the single and double bond monomers are mixtures of at least one of glycidyl methacrylate, vinyl acetate, 2-hydroxyethyl acrylate, or N-(3-dimethylaminopropyl)methacrylamide;

[0049] The crosslinking agent is at least one of divinylbenzene, ethylene glycol dimethacrylate, triallyl isocyanurate, and trimethylolpropane trimethacrylate.

[0050] The initiator is one of azobisisobutyronitrile, azobisisoheptanenitrile, AlCl3·6H2O, benzoyl peroxide, dodecyl peroxide, diisopropyl peroxide, or tert-butyl peroxide.

[0051] The organic compound is one or more of an organic solvent and an oligomer; wherein the organic solvent includes one or more of toluene, xylene, ethyl acetate, butyl acetate, n-hexane, cyclohexane, N,N-dimethylformamide, 2,3-dimethylbutane, n-heptane, and cycloheptane; and the oligomer is one or more of Span, polyethylene glycol, polypropylene glycol, or poly(dimethylsiloxane).

[0052] Step S2: Inject the uniformly dispersed casting liquid into the water-soluble polymer opal in the reactor, then place the reactor in a constant temperature chamber, prepolymerize at 30-60℃ for 1-12 hours, and then polymerize at 70-90℃ for 12-45 hours to obtain the integral polymer casting of copolymer / water-soluble polymer opal.

[0053] In step S2 of the present invention, the water-soluble polymer opal is water-soluble polyacrylamide opal with a particle size range of 500-1000 nm.

[0054] Step S3: Remove the copolymer from the surface of the monolithic polymer casting, then immerse the monolithic polymer casting in opal removal agent for 10-44 hours, changing the opal removal agent several times during the process; after cleaning and wetting with anhydrous ethanol, extract with solvent for 4-24 hours, and finally vacuum dry at 25-70℃ for 8-12 hours to obtain a multi-layered porous polymer matrix material.

[0055] In step S3 of the present invention, the opal removal agent is a 10% methanol distilled aqueous solution;

[0056] The solvent is one of petroleum ether, anhydrous methanol, dimethylformamide, and methyl ethyl ketone;

[0057] Step S4: Immerse the multi-layered porous polymer matrix material obtained in step S3 in a reactor containing a composite modifier solution, react at 40–95°C for 12–48 h, wash the reacted material 5–10 times with a cleaning agent, and finally vacuum dry at 25–70°C to obtain a multi-layered porous polymer-based solid amine.

[0058] In step S4 of the present invention, the mass ratio of the polymer matrix material to the composite modifier is m. 聚合物基体材料 :m 复合改性剂=1:50~150;

[0059] The composite modifier solution is a mixture of one or more alkanolamines, alkylamines, and amino acids with a medium; wherein,

[0060] Alkylamines: monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-hydroxymethyl-1,3-propanediol, glucosamine;

[0061] Alkaneamines: piperazine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, cyclohexylamine, tert-butylamine, polyethylenepolyamine, branched polyethyleneimine;

[0062] Amino acids: asparagine, glutamic acid, gamma glutamic acid, histidine, lysine, arginine, aspartic acid, glycine, alanine, serine, threonine, tyrosine, tryptophan, cysteine;

[0063] The medium is tetrahydrofuran or dimethylformamide;

[0064] The cleaning agent is an aqueous solution of methanol or ethanol, with a mass ratio of alcohol to water of 1:0.02 to 9.

[0065] It should be noted that the water-soluble polyacrylamide opal used as the matrix template in this invention are all known materials, and are prepared according to the traditional dispersion polymerization method, including the following steps:

[0066] Anhydrous ethanol, deionized water, polyvinylpyrrolidone, and acrylamide were added sequentially at room temperature and stirred until homogeneous. The mixture was then heated to 60–90°C, and benzoyl peroxide was added. The reaction proceeded for 6–12 hours. The dispersion was centrifuged in centrifuge tubes to remove the solvent. After washing 3–5 times with anhydrous ethanol, the mixture was centrifuged again and then vacuum dried at 25–45°C for 8–24 hours to obtain water-soluble polyacrylamide opal with an average particle size of 500–1000 nm.

[0067] Example 1: Preparation of multi-level porous polymer matrix materials

[0068] (1) Preparation of 700nm water-soluble polyacrylamide opal

[0069] At room temperature, 145 g of anhydrous ethanol, 60 g of deionized water, 8 g of polyvinylpyrrolidone, and 24 g of acrylamide were added sequentially and stirred until homogeneous. The mixture was then heated to 75 °C, and 0.2 g of benzoyl dioxide was added, followed by reaction for 10 h. The dispersion was centrifuged in a centrifuge tube to remove the solvent. After washing 3–5 times with anhydrous ethanol, the mixture was vacuum dried at 30 °C for 20 h to obtain water-soluble opal polyacrylamide with an average particle size of 700 nm.

[0070] Figure 2This image was obtained by scanning 700nm of water-soluble polyacrylamide opal using an electron scanning electron microscope. Figure 2 It can be seen that the water-soluble polyacrylamide opal scale forms an orderly and compact pattern.

[0071] (2) Preparation of inverse opal structured polymer matrix materials

[0072] 15g of water-soluble polyacrylamide opal was placed in a polymerization container. 10g of well-dispersed triallyl isocyanurate, 1.5g of glycidyl methacrylate, 0.5g of 2-hydroxyethyl acrylate, 0.06g of azobisisobutyronitrile, 2g of butyl acetate, and 2g of cycloheptane were added to the container, and the casting solution completely submerged the opal for 20 minutes. The container was then placed in a 55℃ constant temperature oven for 6 hours, followed by an 80℃ constant temperature oven for 22 hours. After the reaction stopped, a monolithic polymer casting of copolymer / water-soluble polymer opal was obtained. This monolithic polymer casting was then removed, and the copolymer on the opal surface was removed by physical grinding. It was then immersed in a 10% methanol aqueous solution for 28 hours, with the solution changed 5 times. After removing the solvent, it was vacuum dried at 60℃ for 10 hours to obtain an inverse opal structure polymer matrix material, namely a copolymer of poly(glycidyl methacrylate) and 2-hydroxyethyl acrylate.

[0073] (3) Preparation of multi-level porous polymer matrix materials

[0074] The material from step (2) was placed in an extractor, and anhydrous methanol was added for extraction for 12 h. After removing the solvent, it was vacuum dried at 30 °C for 10 h to obtain a copolymer of poly(glycidyl methacrylate) and 2-hydroxyethyl acrylate with a multi-layered porous structure.

[0075] Figure 3 The nitrogen adsorption-desorption curves and pore size distribution diagrams of the inverse opal structure polymer matrix material in Example 1 of this invention are shown below. Figure 3 As shown, the adsorption-desorption isotherms indicate that the material has a macroporous structure, and the pore size distribution shows a macroporous distribution trend. Its specific surface area is only 51.9 m². 2 / g. Figure 4 The nitrogen adsorption-desorption curves and pore size distribution diagrams of the multi-level porous polymer matrix material in Example 1 of this invention are shown below. Figure 4 As shown, after further removing the organic solvent doped in the polymer in step (3), a multi-level porous structure with a high specific surface area is obtained, with a specific surface area of ​​only 599.7 m². 2 / g, which greatly increases the specific surface area of ​​the material compared to step (2).

[0076] Example 2: Preparation of multilayer porous polymer matrix solid amine materials supported on tetraethylenepentamine and monoethanolamine

[0077] (1) The preparation of 700nm water-soluble opal is the same as step (1) in Implementation Case 1;

[0078] (2) The preparation of the anti-opal structure polymer matrix material is the same as step (2) in Implementation Case 1;

[0079] (3) The preparation of multi-level porous polymer matrix materials is the same as step (3) in Implementation Case 1;

[0080] Take 1g of the multi-layered porous polymer matrix material obtained in step (3) and place it in a reaction flask. Add 100ml LDM, 3g tetraethylenepentamine and 1g monoethanolamine in sequence, mix and soak for 8h. Then heat to 80℃ and react for 24h. Wash the material three times with 10% methanol aqueous solution, wash with anhydrous methanol and dry under vacuum at 30℃ to obtain the multi-layered porous polymer matrix solid amine material.

[0081] Figure 5 This is a SEM image of the multi-level porous polymer-based solid amine material supported on tetraethylenepentamine and monoethanolamine, as described in Example 2 of this invention. Figure 5 It can be seen that the modified material has a distinct inverse opal structure, with a specific surface area of ​​501.6 m². 2 / g, the specific surface area is lower than that of the material obtained in step (3) of Example 1, which is due to the modified amine active groups occupying a certain space structure. Figure 6 The figures shown are the nitrogen adsorption-desorption curves and pore size distribution diagrams of the multi-level porous polymer-based solid amine material supported on tetraethylenepentamine and monoethanolamine in Example 2 of this invention. Figure 6 It can be seen that the material's pore structure still possesses a multi-level pore structure.

[0082] Example 3: Preparation of multilayer porous polymer-based solid amine materials supported on triethylenetetramine and meglumine:

[0083] (1) The preparation of 700nm water-soluble opal is the same as step (1) in Implementation Case 1;

[0084] (2) 9g triallyl isocyanurate, 2g glycidyl methacrylate, 0.5g 2-hydroxyethyl acrylate and 0.06g azobisisoheptane, 3g xylene, 1g n-hexane, and 0.5g polypropylene glycol replace 10g triallyl isocyanurate, 1.5g glycidyl methacrylate, 0.5g 2-hydroxyethyl acrylate and 0.06g azobisisoheptane, 2g butyl acetate, and 2g cycloheptane in Example 1. Other steps are the same as step (2) in Example 1.

[0085] (3) The preparation of multi-level porous polymer matrix materials is the same as step (3) in Implementation Case 1;

[0086] Take 1g of the multi-layered porous polymer matrix material obtained in step (3) and place it in a reaction flask. Add 100ml of LDM, 2g of triethylenetetramine, and 2g of meglumine in sequence, mix, and soak for 8h. Then raise the temperature to 80℃ and react for 24h. Wash the material three times with 10% methanol aqueous solution, wash with anhydrous methanol, and dry under vacuum at 30℃ to obtain the multi-layered porous polymer matrix solid amine material.

[0087] The specific surface area of ​​the multilayer porous polymer-based solid amine material loaded with triethylenetetramine and meglumine was 434.6 m², as determined by BET testing. 2 / g, Figure 7 The figures shown are the nitrogen adsorption-desorption curves and pore size distribution diagrams of the multi-level porous polymer-based solid amine material supported on triethylenetetramine and meglumine in Example 3 of this invention. Figure 7 It can be seen that the material's pore structure has a multi-level pore structure.

[0088] Example 4: Preparation of multilayer porous polymer-based solid amine materials loaded with glycine, glutamic acid, and lysine:

[0089] (1) The preparation of 700nm water-soluble opal is the same as step (1) in Implementation Case 1;

[0090] (2) 9g triallyl isocyanurate, 2g glycidyl methacrylate, 0.5g N-(3-dimethylaminopropyl)methacrylamide, 0.06g azobisisoheptane, 3g xylene, 1g n-hexane, and 0.5g polypropylene glycol replace 10g triallyl isocyanurate, 1.5g glycidyl methacrylate, 0.5g 2-hydroxyethyl acrylate, 0.06g azobisisoheptane, 2g butyl acetate, and 2g cycloheptane in Example 1. Other steps are the same as step (2) in Example 1.

[0091] (3) The preparation of the multi-layered porous polymer matrix material is the same as step (3) in Example 1, to obtain a copolymer of multi-layered porous polyglycidyl methacrylate and N-(3-dimethylaminopropyl)methacrylamide.

[0092] Take 1g of the multi-layered porous polymer matrix material obtained in step (3) and place it in a reaction flask. Add 100mL of DMF, 1g of glycine, 1g of glutamic acid, and 1g of lysine in sequence, mix, and soak for 8h. Then raise the temperature to 80℃ and react for 24h. Wash the material three times with 10% methanol aqueous solution, wash with anhydrous methanol, and dry under vacuum at 30℃ to obtain the multi-layered porous polymer matrix solid amine material.

[0093] The specific surface area of ​​the solid amine material with a multi-layered porous polymer matrix loaded with glycine, glutamic acid, and lysine was 463.4 m², as determined by BET testing.2 / g. Figure 8 The nitrogen adsorption-desorption curves and pore size distribution diagrams of the multi-level porous polymer-based solid amine material loaded with glycine, glutamic acid, and lysine in Example 4 of this invention are shown below. Figure 8 It can be seen that the material's pore structure has a multi-level pore structure.

[0094] Example 5: Preparation of multi-level porous polymer-based solid amine materials supported on branched polyethyleneimine:

[0095] (1) The preparation of 700nm water-soluble opal is the same as step (1) in Implementation Case 1;

[0096] 0.12g and 6g of ethylene glycol dimethacrylate, 3g of glycidyl methacrylate, 3g of 2-hydroxyethyl acrylate, 0.0121g of azobisisobutyronitrile, 43.632g of 2,3-dimethylbutane, and 4.858g of polypropylene glycol replace 10g of triallyl isocyanurate, 1.5g of glycidyl methacrylate, 0.5g of 2-hydroxyethyl acrylate, 0.06g of azobisisobutyronitrile, 2g of butyl acetate, and 2g of cycloheptane in Example 1. Other steps are the same as step (2) in Example 1.

[0097] (3) The preparation of the multi-layered porous polymer matrix material is the same as step (3) in Example 1, to obtain a copolymer of polyglycidyl methacrylate, vinyl acetate and 2-hydroxyethyl acrylate with a multi-layered porous structure.

[0098] Take 1g of the multi-layered porous polymer matrix material obtained in step (3) and place it in a reaction flask. Add 48ml of LDMF and 2g of branched polyethyleneimine sequentially, mix, and soak for 8h. Then raise the temperature to 80℃ and react for 24h. Wash the material three times with 10% methanol aqueous solution, wash with anhydrous methanol, and dry under vacuum at 30℃ to obtain the multi-layered porous polymer matrix solid amine material.

[0099] The specific surface area of ​​the branched polyethyleneimine multilayer porous polymer matrix solid amine material, as determined by BET testing, is 30.47 m². 2 / g. Figure 9 The figures shown are the nitrogen adsorption-desorption curves and pore size distribution diagrams of the multi-level porous polymer-based solid amine material supported on branched polyethyleneimine in Example 5 of this invention. Figure 9 It can be seen that the material's pore structure has a multi-level pore structure.

[0100] In summary, water-soluble polyacrylamide opal was selected as the matrix template. A uniformly dispersed polymer casting liquid was filled into the matrix gaps, initiating monomer polymerization within the gaps. After removing the matrix and non-polymeric materials, a multi-layered porous polymer matrix material was obtained. This multi-layered porous polymer matrix material was then reacted with different types of amine-modifying molecules to obtain a multi-layered porous polymer-based solid amine material. This invention avoids the problems existing in current impregnation, grafting, and direct synthesis methods, forming a solid amine material with controllable active sites and a stable pore structure. This method demonstrates unique advantages in the preparation of solid amine materials.

[0101] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a multi-layered porous polymer-based solid amine decarbonizing agent, characterized in that, The method includes the following steps: Step S1: After mixing the monomer, initiator and organic matter, the mixture is dispersed in a mixer at a speed of 1000-8000 r / min for 5-20 minutes at -10~35℃ to obtain a uniformly dispersed casting liquid. Step S2: Inject the uniformly dispersed casting liquid into the water-soluble polymer opal in the reactor, then place the reactor in a constant temperature chamber, prepolymerize at 30-60℃ for 1-12 hours, and then polymerize at 70-90℃ for 12-45 hours to obtain the integral polymer casting of copolymer / water-soluble polymer opal. Step S3: Remove the copolymer from the surface of the monolithic polymer casting, then immerse the monolithic polymer casting in opal removal agent for 10-44 hours, changing the opal removal agent several times during the process; after cleaning and wetting with anhydrous ethanol, extract with solvent for 4-24 hours, and finally vacuum dry at 25-70℃ for 8-12 hours to obtain a multi-layered porous polymer matrix. Step S4: Immerse the multi-layered porous polymer matrix material in a reactor containing a composite modifier solution and react at 40-95°C for 12-48 hours. Wash the reacted material 5-10 times with a cleaning agent and finally vacuum dry at 25-70°C to obtain a multi-layered porous polymer-based solid amine. The polymerizable monomer is a blend of a mixture of single and double bond monomers and a crosslinking agent. The single and double bond monomer mixture consists of two or three single and double bond monomers in a mass ratio of 1:0.01~9:0~9. The single and double bond monomers are glycidyl methacrylate, vinyl acetate, or 2-hydroxyethyl acrylate. The crosslinking agent is at least one of divinylbenzene, ethylene glycol dimethacrylate, triallyl isocyanurate, and trimethylolpropane trimethacrylate. The organic compound is one or more of an organic solvent and an oligomer; the oligomer is one or more of Span, polyethylene glycol, polypropylene glycol, or poly(dimethylsiloxane); The composite modifier solution is a mixture of one or more of the following: alkanolamines, alkylamines, and amino acids, with a medium, wherein the medium is tetrahydrofuran or dimethylformamide; The water-soluble polymer opal is water-soluble polyacrylamide opal with a particle size range of 500~1000nm. Its preparation method includes the following steps: anhydrous ethanol, deionized water, polyvinylpyrrolidone, and acrylamide are added sequentially at room temperature and stirred evenly. The temperature is raised to 60~90℃, benzoyl peroxide is added, and the reaction is carried out for 6~12h. The dispersion is placed in a centrifuge tube and centrifuged to remove the solvent. After washing with anhydrous ethanol 3~5 times, it is centrifuged and then vacuum dried at 25~45℃ for 8~24h.

2. The method for preparing a multi-layered porous polymer-based solid amine decarbonizing agent according to claim 1, characterized in that, In step S1, the volume ratio of the polymerizable monomer to the organic compound is V. 聚合单体 V 有机物 =1:0.05~4; the mass of the initiator is 0.1%~8% of the mass of the polymerized monomer.

3. The method for preparing a multi-layered porous polymer-based solid amine decarbonizing agent according to claim 1 or 2, characterized in that, In step S1, the mass ratio of the single / double bond monomer mixture to the crosslinking agent is 1:0.01-9; The initiator is one of azobisisobutyronitrile, azobisisoheptanenitrile, AlCl3·6H2O, benzoyl peroxide, dodecyl peroxide, diisopropyl peroxide, or tert-butyl peroxide. The organic solvent includes one or more of toluene, xylene, ethyl acetate, butyl acetate, n-hexane, cyclohexane, N,N-dimethylformamide, 2,3-dimethylbutane, n-heptane, and cycloheptane.

4. The method for preparing a multi-layered porous polymer-based solid amine decarbonizing agent according to claim 1, characterized in that, In step S3, the opal removal agent is a 10% methanol distilled aqueous solution; The solvent is one of petroleum ether, anhydrous methanol, dimethylformamide, and methyl ethyl ketone.

5. The method for preparing a multi-layered porous polymer-based solid amine decarbonizing agent according to claim 1, characterized in that, In step S4, the mass ratio of the polymer matrix material to the composite modifier is: m 聚合物基体材料 :m 复合改性剂 =1:50~150.

6. The method for preparing a multi-layered porous polymer-based solid amine decarbonizing agent according to claim 1, 4, or 5, characterized in that, In step S4, the composite modifier solution, Alkylamines include monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, or 2-amino-2-hydroxymethyl-1,3-propanediol; Alkylamines include piperazine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, cyclohexylamine, tert-butylamine, polyethylenepolyamine, or branched polyethyleneimine; The amino acids are asparagine, glutamic acid, gamma glutamic acid, histidine, lysine, arginine, aspartic acid, glycine, alanine, serine, threonine, tyrosine, tryptophan, or cysteine.

7. The method for preparing a multi-layered porous polymer-based solid amine decarbonizing agent according to claim 1, characterized in that, In step S4, the cleaning agent is an aqueous solution of methanol or ethanol, with a mass ratio of alcohol to water of 1:0.02~9.

8. A multi-layered porous polymer-based solid amine decarbonizing agent, characterized in that, It is prepared by the method described in any one of claims 1-7.

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