KR20170119829A - Carbon dioxide Adsorbent Exhibiting Improved Long-term Adsorption Performance Using Core/Cross-linked Amine Shell And Method of Preparation Thereof - Google Patents

Abstract

The present invention relates to a CO ₂ adsorbent having improved amine structure for forming an amine linkage and forming a core / shell structure in a porous support to improve long-term adsorption / desorption performance as well as fluidity of particles and a method for producing the same. The carbon dioxide adsorbent is crosslinked by a crosslinking agent and has a layer containing an amine improved in structure so that irreversible side reaction such as formation of an element does not occur and the amount of carbon dioxide adsorption is kept excellent even during repeated reuse. Also, the amine structure crosslinked between amine groups is formed inside the porous support, so that the adsorption amount is maintained over a long period of time because the amine groups do not leach out and the adsorbent does not aggregate due to the leached amine. In the case of the crosslinked amine, the impregnation of the support into the support is difficult due to its high viscosity and molecular weight. However, the method for preparing the carbon dioxide adsorbent according to the present invention is characterized in that the amine is impregnated into the support before the crosslinking takes place, It has excellent impregnation rate. In addition, the crosslinking agent reacts with the primary amine of the impregnated amine material to reduce the ratio of the primary amine, thereby suppressing the side reaction of urea formation and maintaining high carbon dioxide adsorption ability.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon dioxide adsorbent having improved long-term adsorption performance through amine crosslinking and a core / shell structure, and a method for producing the same. 2. Description of the Related Art Carbon dioxide adsorbent exhibits improved long-

The present invention relates to a carbon dioxide adsorbent and a method for producing the same, and more particularly, to a carbon dioxide adsorbent and a method for producing the same, which are capable of improving long term adsorption / desorption performance as well as enhancing fluidity of particles through formation of a core / shell structure in a porous support, ₂ adsorbent and a method for producing the same.

Carbon dioxide capture, utilization and storage technologies (CCUS), a key technology for reducing global warming and carbon dioxide emissions, should be done first and foremost.

Collecting carbon dioxide from large scale point sources such as power plants and steel mills is considered to be the most effective way to capture carbon dioxide. The technology currently being used for this purpose is a wet absorption process using an amine aqueous solution. However, the absorption process consumes a large amount of energy due to the latent heat of water, sensible heat, etc., and causes a serious problem such as corrosion of the apparatus.

As an alternative to this, the adsorption process, which replaces the water that causes the increase in energy consumption, with a porous solid support, and carries the amine compound, which is an active substance, on the adsorbent. The amine compounds used are mainly ethyleneamine repeating structures.

When a solid adsorbent carrying an amine substance is used, the adsorption amount of carbon dioxide is excellent. However, when the adsorbent is reused, it is repeatedly exposed to a high concentration of carbon dioxide and a high temperature environment. In this case, the activity is decreased due to the generation of urea due to irreversible side reaction, (Leaching) out of the pores and aggregation of the adsorbents.

DISCLOSURE Technical Problem The present invention has been made to solve the above problems and it is an object of the present invention to provide a method for producing a carbon dioxide adsorbent in which when a primary amine in the amine compound is exposed to a high temperature environment containing carbon dioxide, And to prevent the phenomenon that the amine compound is reduced in viscosity at a high temperature and leached to the outside from the inside of the support.

The present invention is to provide a new carbon dioxide adsorbent which prevents irreversible side reactions by reducing the structure of the adsorbent itself by forming an amine bridge between the amine compounds, and prevents the phenomenon of leaching from the support after the adsorption, and a method for producing the same.

In order to solve the above problems, the present invention provides a novel structure in which a core / shell structure complex amine compound having an uncrosslinked amine compound as a core and an amine compound as a shell crosslinked with a cross-linking agent is carried as a shell in pores of a porous support Of carbon dioxide adsorbent.

More specifically, the present invention provides a porous support and an amine adsorbent formed inside the pores of the porous support, wherein the amine adsorbent comprises a core layer formed along the pore inner wall surface and a shell formed on the core layer, Layer, wherein the core layer is an amine compound, and the shell layer is characterized in that the amine compound is crosslinked with a cross-linking agent.

The present invention also provides a process for producing a carbon dioxide adsorbent comprising the steps of:

(1-1) injecting a mixed solution containing an amine compound and an organic solvent into pores of a porous support,

(1-2) selectively evaporating an organic solvent in the mixed solution to form a core layer impregnated with an amine compound in the porous support along the pore wall surface,

(2-1) injecting a mixed solution containing an amine compound, a cross-linking agent and an organic solvent into the pores of the porous support on which the core layer is formed,

(2-2) Crosslinking agent and amine compound in the mixed solution injected in the pores of the porous support formed with the core layer react to form an amine cross-linking,

(2-3) forming the crosslinking agent and selectively evaporating the organic solvent to form an amine compound crosslinked with the crosslinking agent on the core layer.

The carbon dioxide adsorbent according to the present invention has a layer containing an amine improved in structure due to crosslinking by a crosslinking agent and does not cause irreversible side reaction such as formation of urea, so that the adsorption amount of carbon dioxide is kept excellent even during repeated use.

Also, the amine structure crosslinked between amine groups is formed inside the porous support, so that the adsorption amount is maintained over a long period of time because the amine groups do not leach out and the adsorbent does not aggregate due to the leached amine.

In the case of the crosslinked amine, the impregnation of the support into the support is difficult due to its high viscosity and molecular weight. However, the method for preparing the carbon dioxide adsorbent according to the present invention is characterized in that the amine is impregnated into the support before the crosslinking takes place, It has excellent impregnation rate.

In addition, the crosslinking agent reacts with the primary amine of the impregnated amine material to reduce the ratio of the primary amine, thereby suppressing the side reaction of urea formation and maintaining high carbon dioxide adsorption ability.

1 is a conceptual view showing an adsorbent of a core / shell structure according to the present invention.
2 is a structural view of a carbon dioxide adsorbent according to the present invention in which an adsorbent having a core / shell structure is formed in pores inside a porous support.
FIG. 3 is a cross-sectional view showing an enlarged part of a cross-sectional view showing an adsorbent according to the present invention, in which a core layer is impregnated in pores in a porous support, and a shell layer is impregnated on the porous layer.
4 is a view showing the structure of an amine adsorbent cross-linked with a cross-linking agent in the carbon dioxide adsorbent according to the present invention.
5 and 6 are graphs showing changes in weight with time (adsorption capacity and desorption mass characteristics) with respect to Production Example 1 and Comparative Example 2 according to the present invention.
7 is a graph showing the validity of the structure for the adsorbent of Production Example 1 and Comparative Example 2 according to the present invention.

Hereinafter, the present invention will be described in more detail.

One aspect of the present invention relates to an amine structure formed by reacting a cross-linking agent that forms a crosslink between an amine compound and an amine compound by covalent bonding with an amine group, the amine structure being physically impregnated into the pores of the porous support and structurally comprising an uncrosslinked amine compound And a shell layer composed of a core layer and a crosslinked amine compound.

In the case of the amine adsorbent formed on the support in the prior art, the amine is leached out during the repeated reuse process, and the adsorbent aggregates, and the problem that the amine is dispersed low and the low molecular weight amine compound is lost and the primary amine is side- Resulting in deterioration of adsorption performance.

The present invention relates to a carbon dioxide adsorbent having a novel structure capable of simultaneously solving the above problems, and includes a porous support and an amine adsorbent formed inside the pores of the porous support, as shown in FIGS. 1 to 4, A core layer formed along the wall surface and a shell layer formed on the core layer, wherein the core layer is an amine compound, and the shell layer is characterized in that the amine compound is crosslinked with a cross-linking agent.

The shell layer containing the amine compound crosslinked with the crosslinking agent acts like a semipermeable membrane and is capable of diffusing to allow the inflow of carbon dioxide while preventing leaching and evaporation of the amine impregnated in the core.

Also, the cross-linking agent included in the shell layer reacts with the primary amine of the impregnated amine material formed inside the pores to prevent deactivation of the amine due to urea formation.

According to various embodiments of the present invention, the shell layer may be replaced by another semi-permeable coating.

In one embodiment of the present invention, a carbon material, graphite, graphene, carbon nanotube, zeolite, MOFs, porous silica, porous polymer, clay, porous titania, etc. may be used as the porous material. May be porous silica particles.

In one embodiment of the invention, the amine compound is selected from the group consisting of tris (2-aminoethyl) amine, 1,2-ethanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, (Diethylamino) ethanol, 2-dimethylaminoethanol, N-methyldiethanolamine, 2- (methylamino) Ethanol, 1,2-bis ((2-hydroxyethyl) amino) ethane, 1,3-bis [tris (hydroxymethyl) methylamino] propane, (tetrahydroxyethyl) ethylenediamine, Diethylaminoethanol, 2-isopropylaminoethanol, 2-piperidine methanol, 2,2 '- (ethylene diimino) diethanol, 2- (2-aminoethoxy) ) Ethylamine, 1,7-diaza-12-crown-4, and mixtures thereof.

In addition, SO _X, NO _X (2-aminoethyl) aniline, 3- (aminomethyl) aniline, 2-amino-1-naphthylamine, 1-ol, 2,3-dihydro-1H-indene-2,5-diamine, 1,2,3,4-tetrahydroisoquinoline-7- And can be any one selected.

In one embodiment of the present invention, the crosslinking agent is selected from the group consisting of 1,3-butadiene diepoxide, glycerol diglycidyl ether, ethylene glycol aglycidyl ether, diepoxy octane, bisphenol adeglycidyl ether, N, N, N ', N'-tetraglycidyl-4,4'-methylenedianiline, 3,4-epoxycyclohexylmethyl 3', 4'-epoxycyclohexanecarboxylate, p-glycidyloxystyrene, It may be at least one member selected from the group consisting of primary, secondary, and tertiary amines selected from the group consisting of primary, secondary and tertiary amines, such as primary, secondary and tertiary amines, It is preferable to use an epoxy crosslinking agent which produces a hydroxyl group (OH) capable of promoting amine-CO ₂ adsorption.

According to an embodiment of the present invention, the content of the crosslinking agent in the carbon dioxide adsorbent may be 5-90% by weight of the amine compound.

In one embodiment of the present invention, the amine compound is modified with a modifying material, and the modifying material is selected from the group consisting of ethylene oxide, propylene oxide, 1,2-epoxybutene, 1,2- Epoxy heptane, 1,2-epoxycycloheptane, glycidol, styrene oxide, styrene, vinylpyridine and acrylonitrile.

In another aspect of the present invention, there is provided a method for preparing a porous support, comprising the steps of: curing an amine structure formed by reacting a crosslinking agent that forms a crosslinking between amine compounds by covalent bonding with an amine group, And a shell layer composed of a crosslinked amine compound. The present invention relates to a method for producing a carbon dioxide adsorbent, wherein an amine compound is injected into a porous support before cross-linking so that a cross-linking agent and an amine compound react within the pore .

The method for producing a carbon dioxide adsorbent according to the present invention is characterized by comprising the following steps.

(1-1) injecting a mixed solution containing an amine compound and an organic solvent into pores of a porous support,

(1-2) selectively evaporating an organic solvent in the mixed solution to form a core layer impregnated with an amine compound in the porous support along the pore wall surface,

(2-1) injecting a mixed solution containing an amine compound, a cross-linking agent and an organic solvent into the pores of the porous support on which the core layer is formed,

(2-2) Crosslinking agent and amine compound in the mixed solution injected in the pores of the porous support formed with the core layer react to form an amine cross-linking,

(2-3) forming the crosslinking agent and selectively evaporating the organic solvent to form an amine compound crosslinked with the crosslinking agent on the core layer.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.

Example

Examples of the porous support that can be used in the present invention include carbon bodies, graphite, graphene, carbon nanotubes, zeolites, MOFs, silica, porous polymers, clay and titania. Porous silica support-1 and silica support-2, which satisfy the structural characteristics of pores, were used.

division S _BET (m < 2 > / g) V _p (cm < 3 > / g) D _p (nm) Possible support range 200-2000 0.5-3.5 2-50 (average: 5-35) Silica support-1 300.75 2.4 33 Silica support-2 307.4 1.06 15

Production Example 1

(1) 24 g of a silica support-1 (PQCS2129, LPSG) sufficiently removed from moisture and impurities in a 100 ° C. vacuum oven was weighed out first and then polyethyleneimine (EVA) modified with epoxy butene 18EB-PEI1200-methanol) was prepared by mixing 45.7 mL of methanol with 12 g of methanol (18EB-PEI1200), and heat was generated during this process.

The solution of the mixed organic solution (18EB-PEI1200-methanol) was dropwise added to a pre-weighed porous silica support and stirred. During the stirring, the solution was sufficiently stirred so that the amine adsorbent could be dispersed without aggregation, For 8 hours to evaporate the methanol to form a core (LPSG / 18EB-PEI1200 core) by impregnating a polyethyleneimine amine adsorbent into the porous support.

(2) Next, 3.5 g of 3.7EB-PEI 1200 modified with epoxy butene (butylene oxide; BO, EB) and 36.7 mL of methanol were mixed (PEI1200-methanol), 0.5 g of diepoxyoctane (DEO) After 5.3 mL of DEO-methanol was added, the PEI1200-methanol solution and DEO-methanol solution were mixed.

The mixture solution was dropped by dropping to the LPSG / 18EB-PEI 1200 core, stirring was performed. In this process, the amine adsorbent was sufficiently stirred so that the amine adsorbent could be dispersed without being clumped by the solution, followed by heating at 45 ° C for 12 hours, Evaporation and 3.7EB-PEI 1200 and DEO were subjected to an amine-epoxy reaction to form 18EB-PEI 1200 impregnated in the pores of the porous support. 3.7EB-PEI 1200 (3.7EB-PEI 1200 + DEO) The structure of the LPSG / 18EB-PEI 1200 core / 3.7EB-PEI 1200+ DEO shell thus formed was prepared and reacted sufficiently by heating at 80 ° C for 8 hours or more.

The structures according to Preparation Example 1 were 60.6 wt% of porous silica support (LPSG), 31.8 wt% of 18EB-PEI 1200 core, and 7.5 wt% of 3.7EB-PEI 1200 + DEO.

Production Example 2

Production Example 2 was prepared in the same manner as in Preparation Example 1, except that PEI 1200 not modified with epoxy butene (EB, BO) was used in the shell.

Production Example 3

Production Example 3 was prepared in the same manner as in Preparation Example 1, except that PEI 1200, which was not modified with epoxy butene (EB, BO), was used in the shell and DEO content as a crosslinking agent was different.

Comparative Example 1

Comparative Example 1 was prepared by impregnating a core with a porous support without forming a shell using the method described in Production Example 1 above.

Comparative Example 2

In Comparative Example 2, the method described in Preparation Example 1 was used, except that PEI, EB (BO) and DEO were added in the same amount as the core / shell but the whole was mixed and impregnated into the pores of the porous support .

Experiment and Result Example 1

The stability, adsorption amount and amine efficiency of the carbon dioxide adsorbent having the core / shell structure according to the present invention were confirmed according to the degree of crosslinking of the cells, and the production examples 1 to 3 and the comparative examples 1 to 2 The results are shown in [Table 2] below.

division Silica (60) The core layer (30) Shell layer
(10) Amount of impregnation before washing Amount of impregnation after washing Loss rate Adsorption amount
(wt%) BO (EB) EB DEO Amine efficiency Comparative Example 1 LPSG 18EB-PEI1200 - 34.44 6.96 79.80 5.8 65.6 34.4 0.212 Production Example 1 LPSG 18EB-PEI1200 3.7EB-PEI1200 + 7.5DEO 39.37 9.45 76.00 7.3 60.6 31.8 7.5 0.233 Production Example 2 LPSG 18EB-PEI1200 0EB-PEI1200 + 15DEO 39.69 25.72 35.21 6.5 60.3 31.7 8.0 0.212 Production Example 3 LPSG 18EB-PEI1200 0EB-PEI1200 + 30DEO 39.39 36.88 10.07 5.9 60.6 29.9 9.5 0.205

Before washing = y / (x + y) * 100 (y is the total amount of amine adsorbent, x is the total amount of silica support)

Y '/ (x + y') * 100 (y 'is the total amount of amine adsorbent, x is the total amount of silica support)

Loss rate = (y-y ') / y * 100

As shown in Table 2, in the case of Production Example 1 according to the present invention, the crosslinked PEI is the same as the semi-permeable separator, and the leaching of the impregnated amine adsorbent inside the core is prevented, diffusion is possible, And the loss ratio is similar to that of Comparative Example 1, and it can be confirmed that the amine adsorption amount and efficiency are improved.

Experiment and Result Example 2

Table 3 below shows the comparison of the constituent components of the present invention with respect to Production Example 1 and Comparative Example 2 and their characteristics are shown in Table 4 and Table 5 below, Is Comparative Example 2, and Table 5 is Production Example 1 according to the present invention.

division LPSG
(g / g sorbent) PEI1200
(g / g sorbent) BO (EB)
(g / g sorbent) DEO
(g / g sorbent) Comparative Example 2 0.604 0.274 0.071 0.051 Production Example 1 0.599 0.280 0.071 0.050

cycle Adsorption amount (%) Desorption mass based on the first cycle Amine efficiency
(mmol CO 2 /
mmol N) One 4.4 100 0.152 2 5.5 100.2 0.19 3 5.4 100.4 0.186 4 5.2 100.5 0.181 5 5.1 100.5 0.178 6 5.1 100.6 0.174 7 5 100.6 0.172 8 4.9 100.6 0.17 9 4.9 100.6 0.168 10 4.8 100.6 0.166

cycle Adsorption amount (%) Desorption mass based on the first cycle Amine efficiency
(mmol CO 2 /
mmol N) One 5.9 100 0.205 2 6.2 100.4 0.216 3 6 100.7 0.208 4 5.8 100.9 0.201 5 5.6 101 0.196 6 5.5 101 0.192 7 5.5 101.1 0.19 8 5.4 101.1 0.187 9 5.3 101.2 0.184 10 5.2 101.2 0.182

As shown above, Comparative Example 2 was formed by mixing PEI, BO, and DEO in the same amount as in Production Example 1, although the core / shell structure was not formed.

It can be confirmed that Production Example 1 according to the present invention in which the core / shell structure is formed by impregnation in the pores of the porous support in succession has a relatively high adsorption amount.

As such, the crosslinking agent has a low selectivity with respect to the primary amine, which may deteriorate the amine efficiency and speed. In the case of Comparative Example 2, the crosslinking agent is distributed throughout, resulting in a decrease in adsorption amount and a decrease in speed. However, in Production Example 1 according to the present invention, since the crosslinking agent is distributed only in the shell region, the adsorption amount of the core can be preserved.

Further, as shown in FIGS. 6 to 8, it can be seen that the carbon dioxide adsorbent having the structure according to the present invention has a high adsorption amount and a low desorption mass characteristic, and the long-term effectiveness of the structure can be confirmed.

Claims (14)

A porous support and an amine adsorbent formed inside the pores of the porous support,
Wherein the amine adsorbent comprises a core layer formed along the pore inner wall surface and a shell layer formed on the core layer,
Wherein the core layer is an amine compound, and the shell layer is an amine compound crosslinked with a cross-linking agent. The method according to claim 1,
Wherein the porous substrate is any one selected from the group consisting of a carbon body, graphite, graphene, carbon nanotube, zeolite, MOFs, porous silica, porous polymer, clay and porous titania. The method according to claim 1,
The amine compound may be at least one selected from the group consisting of tris (2-aminoethyl) amine, 1,2-ethanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 3,6,9,12,15- (2-dimethylaminoethanol, N-methyldiethanolamine, 2- (methylamino) ethanol, 1,2-bis (2-hydroxyethyl) amino) ethane, 1,3-bis [tris (hydroxymethyl) methylamino] propane, (tetrahydroxyethyl) ethylenediamine, diethanolamine, Diethylaminoethanol, 2-isopropylaminoethanol, 2-piperidinemethanol, 2,2 '- (ethylenediimino) diethanol, 2- (2-aminoethoxy) ethylamine, Diaza-12-crown-4, and mixtures thereof. The method according to claim 1,
The amine compound may be selected from the group consisting of 1,3-phenylenediamine, 4-aminophenethylamine, 3- (2-aminoethyl) aniline, 3- (aminomethyl) aniline, 1-ol, 2,3-dihydro-1H-indene-2,5-diamine, 1,2,3,4-tetrahydroisoquinoline-7-amine and mixtures thereof. Carbon dioxide adsorbent. The method according to claim 1,
The crosslinking agent may be at least one selected from the group consisting of 1,3-butadiene diepoxide, glycerol diglycidyl ether, ethylene glycol aglycidyl ether, diepoxy octane, bisphenol-A diglycidyl ether, N, N, N ' Epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexanecarboxylate, p-glycidyloxystyrene, glycidyl methacrylate, triglycidyl glycerol, Wherein the carbon dioxide adsorbent is at least one selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, carbosuccinic acid, dichloromethane, dichloroethane and epichlorohydrin. The method according to claim 1,
Wherein the content of the crosslinking agent contained in the carbon dioxide adsorbent is 5-90 wt% of the amine compound. The method according to claim 1,
The amine compound is modified with a modifying material, and the modifying material is at least one selected from the group consisting of ethylene oxide, propylene oxide, 1,2-epoxybutene, 1,2-epoxypentane, 1,2-epoxyheptane, Wherein the carbon dioxide adsorbent is at least one selected from the group consisting of cycloheptane, glycidol, styrene oxide, styrene, vinylpyridine and acrylonitrile. (1-1) injecting a mixed solution containing an amine compound and an organic solvent into pores of a porous support;
(1-2) selectively evaporating an organic solvent in the mixed solution to form a core layer impregnated with an amine compound in the porous support along the pore wall surface;
(2-1) injecting a mixed solution containing an amine compound, a cross-linking agent and an organic solvent into pores of the porous support on which the core layer is formed;
(2-2) Crosslinking agent and amine compound react with each other in the mixed solution injected in the pores of the porous support on which the core layer is formed to form an amine cross-linking; And
(2-3) forming the crosslinking agent and selectively evaporating the organic solvent to form an amine compound crosslinked with the crosslinking agent on the core layer. 9. The method of claim 8,
Wherein the porous substrate is any one selected from the group consisting of a carbon body, graphite, graphene, carbon nanotube, zeolite, MOFs, porous silica, porous polymer, clay, and porous titania. 9. The method of claim 8,
The amine compound may be at least one selected from the group consisting of tris (2-aminoethyl) amine, 1,2-ethanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 3,6,9,12,15- (2-dimethylaminoethanol, N-methyldiethanolamine, 2- (methylamino) ethanol, 1,2-bis (2-hydroxyethyl) amino) ethane, 1,3-bis [tris (hydroxymethyl) methylamino] propane, (tetrahydroxyethyl) ethylenediamine, diethanolamine, Diethylaminoethanol, 2-isopropylaminoethanol, 2-piperidinemethanol, 2,2 '- (ethylenediimino) diethanol, 2- (2-aminoethoxy) ethylamine, Diaza-12-crown-4, and mixtures thereof. 9. The method of claim 8,
The amine compound may be selected from the group consisting of 1,3-phenylenediamine, 4-aminophenethylamine, 3- (2-aminoethyl) aniline, 3- (aminomethyl) aniline, 1-ol, 2,3-dihydro-1H-indene-2,5-diamine, 1,2,3,4-tetrahydroisoquinoline-7-amine and mixtures thereof. Of the carbon dioxide adsorbent. 9. The method of claim 8,
The crosslinking agent may be at least one selected from the group consisting of 1,3-butadiene diepoxide, glycerol diglycidyl ether, ethylene glycol aglycidyl ether, diepoxy octane, bisphenol-A diglycidyl ether, N, N, N ' Epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexanecarboxylate, p-glycidyloxystyrene, glycidyl methacrylate, triglycidyl glycerol, Wherein the carbon dioxide adsorbent is at least one selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, carbosuccinic acid, dichloromethane, dichloroethane and epichlorohydrin. 9. The method of claim 8,
Wherein the content of the crosslinking agent contained in the carbon dioxide adsorbent is 5-90 wt% of the amine compound. 9. The method of claim 8,
The amine compound is modified with a modifying material, and the modifying material is at least one selected from the group consisting of ethylene oxide, propylene oxide, 1,2-epoxybutene, 1,2-epoxypentane, 1,2-epoxyheptane, Wherein the carbon dioxide adsorbent is at least one selected from the group consisting of cycloheptane, glycidol, styrene oxide, styrene, vinylpyridine and acrylonitrile.

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