KR20150069268A - Mesoporous carbon dioxide adsorbent and fabricating method thereof - Google Patents

Abstract

Provided is a manufacturing method of a mesoporous carbon dioxide adsorbent, which comprises the steps of: providing a mesoporous support; treating an alkoxysilane compound having an amine terminal group to the mesoporous support, and then grafting the alkoxysilane compound to the mesoporous support; and forming a hydrophobic mesoporous organic-inorganic composite by alkylating the amine terminal group by treating the grafted alkoxysilane compound with an alkylating agent.

Description

Technical Field [0001] The present invention relates to a mesoporous carbon dioxide adsorbent and a mesoporous carbon dioxide adsorbent,

The techniques disclosed herein relate to mesoporous carbon dioxide sorbents and methods for their manufacture.

Carbon dioxide is produced by the combustion of fossil fuels and its emissions are directly linked to global warming. Therefore, carbon dioxide removal and separation is a very important problem. There are two methods for removing carbon dioxide: absorption, adsorption, and membrane separation. Among them, the absorption method is advantageous for treating a large amount of gas, and the adsorption method is a technique for separating by a difference in adsorption amount depending on a pressure difference using a solid adsorbent. The membrane separation method is a technique of separating by using a membrane. Of these, the adsorption method and the membrane separation method are advantageous for a small-capacity removal device. However, the membrane separation method is disadvantageous in that the production of the membrane is difficult and the unit cost is high. Therefore, the adsorption method is suitable for removing a small amount of carbon dioxide rather than a large amount of separation as in a factory. A dry adsorbent is used for this adsorption method, and the adsorption ability depends largely on the performance of the adsorbent. The better the adsorbent for carbon dioxide is, the better the performance of the dry adsorbent. It is also important to develop an adsorbent that does not deteriorate its adsorption ability even in the presence of water because it is difficult to construct a regeneration system by moisture separately. In particular, when CO2 and CO2 are adsorbed at the same time, additional water is required to be removed. Therefore, it is required to develop a carbon dioxide adsorbent which is more economical and has excellent adsorption performance.

According to an aspect of the present invention, there is provided a method of forming a mesoporous support comprising: providing a mesoporous support; Treating the mesoporous support with an alkoxysilane compound having an amine terminal group to graft the alkoxysilane compound to the mesoporous support; And treating the grafted alkoxysilane compound with an alkylating agent to alkylate the amine terminal group to form a hydrophobic mesoporous organic-inorganic hybrid material.

According to another aspect of the present invention, there is provided a method for preparing a mixture comprising: mixing a mesoporous silica, an alkoxysilane compound having an amine terminal group and an organic solvent to form a mixture; Heating the mixture at 50 to 170 ° C. to react the alkoxysilane compound with the mesoporous silica to obtain an organic / inorganic hybrid; Mixing the organic-inorganic hybrid material with an organic solvent containing an alkylating agent; And heating the mixture at 30 to 100 DEG C to alkylate the amine end group of the organic-inorganic hybrid substance.

According to another aspect of the present invention, there is provided a mesoporous support comprising: a mesoporous support; And comprising an amine compound of from 1 to 10% by weight of a graft in the meso-porous support, wherein the amine compound is provided as one provided with a -NR _'2 end groups in the alkylene main chain of C ₁ to C _12, wherein the mesoporous and the graft through the -Si-O- bound to a support, wherein R 'is alkyl of a carbon dioxide adsorbent is provided in the C ₁ to C _6.

According to another aspect of the present invention, there is provided a mesoporous silica; And comprising the amine compound grafted to the mesoporous silica, the amine compounds, -Si-O- bond to said meso porous support as having provided with a -NR _'2 end groups in the alkylene main chain of C1 to C12 , Wherein R 'is C ₁ to C ₆ alkyl and a pKa of from 10 to 30 is provided.

1 is a process flow diagram illustrating a method for producing a carbon dioxide adsorbent according to an embodiment of the present invention.
2 is a schematic diagram illustrating the adsorption process of a carbon dioxide adsorbent grafted with an amine compound having two or more amine functional groups.
FIG. 3 is a graph showing the adsorption capacity of carbon dioxide according to changes in the pKa value of the adsorbent according to an embodiment of the present invention.
FIG. 4 is a graph showing the results obtained by grafting 3-aminopropyltriethoxysilane onto MCM-41 (Comparative Example 2), 3-aminopropyltriethoxysilane on MCM-41 and further methylating carbon dioxide adsorbent (Example 1). ≪ tb >< TABLE >
5 is an infrared spectroscopy (IR) spectrum of a carbon dioxide adsorbent (Example 4) obtained by grafting N-3-triethoxysilylpropyl-4,5-dihydroimidazole to MCM-41 and further methylating it.
6 is a graph showing adsorption amounts of carbon dioxide in P / P ₀ ranging from 0 to 1 as a result of adsorption experiments using the carbon dioxide adsorbents of Comparative Example 1, Comparative Example 2 and Example 1. FIG.
FIG. 7 is a graph showing adsorption amounts of carbon dioxide from 0 to 1 of P / P ₀ as a result of adsorption experiments using the adsorbents of Comparative Example 1 and Examples 1, 2 and 4.
FIG. 8 shows carbon dioxide adsorption experiments using the carbon dioxide adsorbents of Comparative Examples 1 and 2 and the carbon dioxide adsorbent of Example 1 which was methylated after amine grafting. As a result, the adsorbent of Example 1 was tested for adsorption of carbon dioxide Fig.

In order to capture a small amount of carbon dioxide, it is important to develop an adsorbent having a large initial adsorption capacity. When a substance having a large pKa value is applied to the adsorbent, the efficiency of collecting carbon dioxide can be greatly increased. The existing activated carbon has low adsorption capacity and is higher than activated carbon even in the case of silica gel and zeolite alumina, but the initial adsorption rate is not high. Therefore, it is important to develop a substance having a high initial adsorption efficiency that enables carbon dioxide to be adsorbed immediately upon discharge. It is also required that the carbon dioxide capture ability of the adsorbent is not lowered by moisture.

Accordingly, the present invention proposes a technique of utilizing carbon dioxide as a carbon dioxide-trapping dry adsorbent which improves hydrophobicity by alkylating an organic-inorganic complex containing amine to improve the above problems.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process flow diagram illustrating a method for producing a carbon dioxide adsorbent according to an embodiment of the present invention. Referring to FIG. 1, a mesoporous support is provided in step S1. The mesoporous support is made of a mesoporous material and forms the framework of a carbon dioxide adsorbent. The mesoporous material may be a metal-organic composite material (MOF), a mesoporous carbon, a mesoporous silica, or the like. In view of the existence of more than 4 mmol / g of an effective hydroxyl group capable of grafting on the surface Mesoporous silica is preferred. In general, mesoporous materials are synthesized by hydrothermal reaction using organic molecules such as surfactants or amphipathic polymers as structure inducing materials. It is well known that a surfactant or amphipathic polymer is composed of a hydrophilic head and a hydrophobic tail so that it is self-assembled in an aqueous solution to form a micelle or a liquid crystal structure. MCM-41, MCM-48, MCM-50, SBA-1, SBA-3, SBA-6, SBA-15, SBA-16 and the like can be used for various types of mesoporous materials. . As the preferred mesoporous support of the present invention, for example, mesoporous silica having a specific surface area of vacuum-dried of 900 to 1000 m ² / g and a diameter of 2.1 to 2.7 nm can be used.

In step S2, the mesoporous support is treated with an alkoxysilane compound having an amine terminal group to graft the alkoxysilane compound to the mesoporous support. The graft reaction may be carried out, for example, by mixing a mesoporous silica, an alkoxysilane compound having an amine end group and an organic solvent to form a mixture, and heating the mixture at 50 to 170 ° C to separate the alkoxysilane compound and the mesoporous silica , Followed by filtration, washing and purification, followed by drying to obtain an organic-inorganic hybrid material.

The alkoxysilane compound may have the structure of H ₂ NL-Si (OR) ₃ . Wherein L is C ₁ to C ₁₂ alkylene or C ₆ to C ₂₀ arylene, or the alkylene and arylene may be optionally bonded. And a part of the main chain of L may be substituted with 0 to 4 -NH-. Preferably, a part of the main chain of L may be substituted with at least one -NH-. The R may be hydrogen or C ₁ to C ₈ alkyl. Specifically, the alkoxysilane compound is selected from the group consisting of aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and (3-trimethoxysilylpropyl) diethylenetriamine It may be at least one selected.

In one embodiment, the alkoxysilane compound may be an ionic liquid. The ionic liquid has a combination of a cation and an anion, and a lower aliphatic quaternary ammonium is used as a cation. As the anion, an imide compound such as metal chloride ion, metal fluoride ion and bis (fluorosulfonyl) imide is used .

In step S3, the alkoxysilane compound grafted is treated with an alkylating agent to alkylate the amine terminal group to form a hydrophobic mesoporous organic-inorganic hybrid material, thereby producing a carbon dioxide adsorbent. Specifically, the amine-terminated group of the organic-inorganic hybrid substance can be alkylated by mixing the organic-inorganic hybrid substance formed in Step S2 with an organic solvent containing an alkylating agent, and then heating the mixture at 30 to 100 ° C.

The alkylating agent may be a precursor compound having a C ₁ to C ₆ alkyl group, and preferably the alkylating agent may be at least one haloalkane selected from the group consisting of halomethane, haloethane, halopropane and halobutane . Specifically, the haloalkane may be iodomethane, iodoethane, iodopropane, bromomethane, bromoethane, bromopropane, chloromethane, chloroethane, chloropropane, or the like.

When the mesoporous organic / inorganic hybrid material is alkylated, the amine group has a higher basicity due to the strong electron donating effect of the alkyl group, so that the carbon dioxide capture ability at low pressure can be greatly improved. As a result of the alkylation, the alkylated compound may have a pKa of 10 to 30, preferably 15 to 30. In this range, the effect as a carbon dioxide adsorbent can be maximized. On the other hand, when the pKa is less than 10, the carbon dioxide capturing ability is not high. When the pKa is more than 30, the energy is required to be desorbed.

Alternatively, an alkylated mesoporous organic / inorganic hybrid can be obtained by firstly alkylating an organosilane and carrying it on a silica carrier, instead of grafting and alkylating an organosilane having an amine terminus to a support. However, in this case, the hydrophobicity is increased and the steric hindrance caused by the alkyl of the amine group is increased, so grafting to the mesoporous support may be difficult.

Generally, in a high-capacity adsorption apparatus, even if the performance of the adsorbent due to moisture deteriorates, it is easy to regenerate the system, but in the case of a low-capacity adsorbent, such a system is not easy to construct. However, if the hydrophobicity is increased by using an adsorbent having an alkylation process, it can be suitably used for a small capacity carbon dioxide adsorption system which can withstand relatively moisture. In this case, the cost of the process of further water removal can be reduced.

The amount of the alkoxysilane compound having an alkylated amine end group may be 1 to 20 wt%, preferably 1 to 10 wt%, based on the total carbon dioxide adsorbent. If the amount of the alkylated compound is less than the above range, the desired effect can not be obtained. If the amount is less than the above range, the diffusion of carbon dioxide is limited and the adsorption efficiency may be deteriorated. And the effective hydroxyl group that can be supported on the silica can not exceed 20% by weight.

According to one embodiment of the present invention, there is provided a carbon dioxide adsorbent having an alkylated amine compound. Wherein the carbon dioxide adsorbent comprises a mesoporous support; And an amine compound grafted to the mesoporous support. In addition, the amine compounds having an alkylene main chain of C ₁ to C _12, and as having a -NR _'2 end groups, are grafted by a -Si-O- bond to said meso porous support. Here, the R 'is an alkyl of C ₁ to C _6. In some embodiments, the amine compound may contain one or more, for example one to four, -NH- in the main chain.

Advantages of the amine compound having at least one amine functional group in addition to the terminal amine functional group are as follows. 2 is a schematic diagram illustrating the adsorption process of a carbon dioxide adsorbent grafted with an amine compound having two or more amine functional groups. Referring to FIG. 2, as the total nitrogen content increases, the number of sites capable of adsorbing carbon dioxide increases, and nitrogen in the main chain structure assists the remaining amine groups and carbon dioxide to bond well. The more amine groups available, the greater the carbon dioxide adsorption capacity.

According to the above-described carbon dioxide adsorbent and its production method, alkoxysilane-grafted mesoporous support having an amine end group is alkylated to obtain a hydrophobic substance having a high pKa value, and by using it as a carbon dioxide adsorbent, the initial adsorption property is remarkably high, Can be produced. The use of such an adsorbent can increase important initial adsorption capacity in a small carbon dioxide capture device.

Hereinafter, the present invention will be described in more detail with reference to various embodiments. However, it should be understood that the technical scope of the present invention is not limited by the following embodiments.

(Example)

Example 1: Preparation of amine group adsorbent (3-aminopropyltriethoxysilane, MCM-41)

1 g of mesoporous silica (MCM-41, specific surface area 1000 m ² / g, pore size 2.7 nm) was vacuum-treated for 12 hours or more under heat treatment. 50 ml of anhydrous toluene [Aldrich] was added to the treated silica and dispersed evenly. Then, 1.09 g of aminopropyltriethoxysilane [Aldrich] was added. And the mixture was stirred and refluxed in an argon atmosphere at 120 DEG C for one day or more. After filtration, the filtrate was separated, and the unreacted material was allowed to escape by stirring for 12 hours or more in ethanol, followed by filtration and drying at 100 ° C for 24 hours or more.

The reaction was again vacuum-treated for 12 hours or more under heat treatment. 0.08 g of potassium iodide and 1.3 g of methyl iodide were added to the silica adsorbent grafted with the amine group, and the mixture was stirred for more than 4 hours while maintaining the temperature at 70 ° C. After filtration, the filtrate was separated and stirred with ethanol for 12 hours or longer to allow the unreacted material to escape. The filtrate was filtered and dried at 100 ° C. for 24 hours or more.

Aminopropyl silane groups are coordinated under the amino group (-NH ₂₎ group and ethyl (-CH ₂ CH ₂ -) it was confirmed by infrared spectroscopy for the presence in the 2800-3000cm ^-1 and 3200-3400 cm ^-1, a methyl group Was found to be present at 2800-2900 cm ^-1 of the methyl group (-CH ₃ ) (see FIG. 4).

Amine content was also analyzed by nitrogen content analysis. The result showed that the nitrogen content of the aminopropyltriannyl functionalized MCM-41 was 1.7 wt%.

Example 2: Preparation of amine group adsorbent (3-2-aminoethylaminopropyltrimethoxysilane, MCM-41)

Was carried out in the same manner as in Example 1, except that 3-2-aminoethylaminopropyltrimethoxysilane was used as the amine precursor.

Example 3: Preparation of amine group adsorbent (N1-3 trimethoxysilylpropyldiethylenetriamine, MCM-41)

The procedure of Example 1 was repeated except that N1-3 trimethoxysilylpropyl diethylenetriamine was used as the amine precursor.

Example 4: Preparation of amine group adsorbent (N-3-triethoxysilylpropyl-4,5-dihydroimidazole, MCM-41)

N-3-triethoxysilylpropyl-4, 5-dihydroimidazole was used as the amine precursor in the same manner as in Example 1 above.

The N-3- triethoxy silyl propyl-4,5-dihydro-imidazole under the coordination was already 1562cm ^-1 peak, indicating the jolring CH confirmed through the 2932 cm ^-1 peak that is connected to the nitrogen. In addition, a peak at 1102 cm < ^-1 > which is a stretch of 3447 cm < ^-1 > ethyl group Si-O indicating a Si-OH group was confirmed (see Fig. 5).

Example 5: Preparation of an amine group adsorbent (ethyl iodide, MCM-41)

The procedure of Example 1 was repeated except that ethyl iodide was used as an alkylating agent.

Example 6: Preparation of amine group adsorbent (propyl iodide, MCM-41)

Was carried out in the same manner as in Example 1, except that propyl iodide was used as an alkyl group precursor.

Example 7: Adsorption Capacity of Different Absorbents on Change of pKa

The adsorption capacity of carbon dioxide was measured by changing the pKa value while varying the type and amount of the alkylating agent or the alkylation step such as methyl iodide, ethyl iodide and propyl iodide. FIG. 3 is a graph showing the adsorption capacity of carbon dioxide according to changes in the pKa value of the adsorbent according to an embodiment of the present invention.

When the pKa value is changed, there is no significant change in the carbon dioxide adsorption capacity at P / P ₀ = 1, but it can be seen that the pKa value of 10 to 30 is suitable for the initial carbon dioxide adsorption capacity which is important in the present invention. Since pKa value is too small, the value initial carbon dioxide absorption P / P ₀ value is lowered can not be obtained the desired effect in the present invention, when pKa value of more than 30 are carbon dioxide is very strongly bonded to the absorbent lift a lot of desorption energy efficiency Falls. Therefore, a pKa value of 10 to 30 is most suitable.

Comparative Example 1: Preparation of amine group adsorbent (aminopropyltriethoxysilane, MCM-41)

1 g of mesoporous silica (MCM-41, specific surface area 1000 m ² / g, pore size 2.7 nm) was vacuum-treated for 12 hours or more under heat treatment.

Comparative Example 2: Preparation of amine group adsorbent (3-aminopropyltriethoxysilane, MCM-41)

1 g of mesoporous silica (MCM-41, specific surface area 1000 m ² / g, pore size 2.7 nm) was vacuum-treated for 12 hours or more under heat treatment. 50 ml of anhydrous toluene [Aldrich] was added to the treated silica and dispersed evenly. Then, 1.09 g of 3-aminopropyltriethoxysilane [Aldrich] was added. And the mixture was stirred and refluxed in an argon atmosphere at 120 DEG C for one day or more. After filtration, the filtrate was separated, and the unreacted material was allowed to escape by stirring for 12 hours or more in ethanol, followed by filtration and drying at 100 ° C for 24 hours or more.

Aminopropyl silane groups are coordinated under the amino group (-NH ₂₎ and an ethyl group was confirmed by infrared spectroscopy that the presence in the 2800-3000cm ^-1 and 3200-3400 cm ^-1 (Fig. (-CH ₂ CH ₂₎ 4).

Comparative Example 3: Preparation of amine group adsorbent (3-2-aminoethylaminopropyltrimethoxysilane, MCM-41)

Was carried out in the same manner as in Example 1, except that 3-2-aminoethylaminopropyltrimethoxysilane was used as the amine precursor.

 Comparative Example 4: Preparation of amine group adsorbent (N1-3-trimethoxysilylpropyldiethylenetriamine, MCM-41)

The procedure of Example 1 was repeated except that N1-3 trimethoxysilylpropyl diethylenetriamine was used as the amine precursor.

Comparative Example 5: Preparation of amine group adsorbent (N-3-triethoxysilylpropyl-4,5-dihydroimidazole, MCM-41)

N-3-triethoxysilylpropyl-4, 5-dihydroimidazole was used as the amine precursor in the same manner as in Example 1 above.

Test Example 1:

The fixed bed reactor made of glass was filled with the adsorbent prepared in the above example to measure the carbon dioxide adsorption performance. The sample was pretreated at 150 ° C for more than 12 hours and put into a fixed bed reactor. The temperature of the sample was maintained at 30 ° C, and the amount of carbon dioxide adsorbed was measured while supplying carbon dioxide into the reactor. The results are shown in Fig. 6 and Fig. The graphs of FIGS. 6 and 7 are graphs showing the adsorption amount of carbon dioxide according to the pressure. Color filled shapes show adsorption and empty shapes show desorption.

Test Example 2:

The sample was pretreated at 150 ° C for more than 12 hours, then placed in a fixed bed reactor. While maintaining the temperature at 30 ° C, a gas having a ratio of 1 atm of water of 6.3% and carbon dioxide of 90% Were measured according to time. The results are shown in Fig.

In the case of the MCM-41 adsorbent of Comparative Example 1, the adsorption amount of carbon dioxide at P / P ₀ = 1 is 0.6 mmol / g. Grafting 3-aminopropyltriethoxysilane increases to 1.2 mmol / g (Comparative Example 2). Further, when methylation is further performed on the amine group, the value is 1.2 mmol / g, which is twice as high as that of MCM-41 (Example 1).

The adsorption amount at P / P ₀ = 0.1 is a numerical value showing the initial adsorption characteristic of carbon dioxide. As the initial rate is higher, it shows that water and competitive adsorption are more advantageous. Therefore, the higher the value, the lower the adsorption characteristic of carbon dioxide It can be said that it shows that it does not.

At P / P ₀ = 0.1, MCM-41 has a carbon dioxide adsorption of 0.1 mmol / g. Grafting of 3-aminopropyltriethoxysilane increases to 0.4 mmol / g. In addition, when methylation is further performed on the amine group, the value is 0.7 mmol / g, which indicates that the initial speed is 7 times that of MCM-41 and 2 times that of 3-aminopropyltriethoxysilane grafted have. In particular, the methylation of P / P ₀ = 1 shows a tendency to increase the amount of carbon dioxide adsorbed almost at the same rate, and there is no significant change after methylation, but at the initial adsorption rate P / P _{0 =} 0.1, the adsorption amount of carbon dioxide Respectively.

FIG. 7 is a graph showing adsorption amounts of carbon dioxide from 0 to 1 of P / P ₀ as a result of adsorption experiments using the adsorbents of Comparative Example 1 and Examples 1, 2 and 4. The adsorption amount at the initial P / P ₀ 0.1 shows that the amount of adsorbed carbon dioxide on the MCM-41 without grafting significantly increased on the basis of the above example. Also, the adsorption amount at P / P ₀ 1 was increased as compared with Comparative Example 1. Particularly, the adsorbent of Example 3 has a characteristic of binding carbon to carbon dioxide rather than hydrogen because the PKa value of the amine group of the terminal group is large as shown in FIG. 2, especially when the amine group is 2, and hydrogen moves to another amine group The oxygen of the carbon dioxide is substituted to form the bond, and the hydrogen and the attraction force having the characteristic of the positive charge and the other oxygen having the negative charge characteristic are operated, and the structure becomes very stable. Therefore, the bonding property with carbon dioxide becomes very strong and the amount of initial carbon dioxide adsorption becomes very high. The table below shows the amount of carbon dioxide adsorbed after the amines of the examples were methylated. It can be seen that it can be used as a carbon dioxide adsorbent by introducing various amine groups in addition to 3-aminopropyltriethoxysilane and further alkylating.

In addition to Comparative Example 1, there is a hysteresis indicating that the adsorption graph and the desorption graph are inconsistent, which means that the energy is high when desorbed, which indicates that the carbon dioxide and the adsorbent can be strongly bonded.

Table 1 below summarizes the measurement results of the carbon dioxide adsorption amount using the samples of Comparative Examples 1 and 2, 3 and 5.

[Table 1]

8 is a graph showing carbon dioxide adsorption amount at 1 atm while flowing carbon dioxide containing 6.3% water in the same manner as an inert gas such as 90% helium. Analyzing the carbon dioxide adsorption pattern in the presence of water actually confirmed that the adsorbent was actually effective in the presence of water. Compared with the conventional silica adsorbent, the initial adsorption amount of carbon dioxide is low in the presence of water, but it can be understood that the adsorption is good in competitive adsorption with water as time goes by.

Claims (12)

Providing a mesoporous support;
Treating the mesoporous support with an alkoxysilane compound having an amine terminal group to graft the alkoxysilane compound to the mesoporous support; And
Treating the grafted alkoxysilane compound with an alkylating agent to alkylate the amine terminal group to form a hydrophobic mesoporous organic / inorganic hybrid material. The method according to claim 1,
Wherein the mesoporous support comprises mesoporous silica. The method according to claim 1,
Wherein said alkoxysilane compound has a structure of H ₂ NL-Si (OR) ₃ , L is C ₁ to C ₁₂ alkylene or C ₆ to C ₂₀ arylene, or said alkylene and said arylene are optionally Wherein a part of the main chain of L is substituted with 0 to 4 -NH-, and R is hydrogen or C ₁ to C ₈ alkyl. The method according to claim 1,
Wherein the alkoxysilane compound is selected from the group consisting of aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and (3-trimethoxysilylpropyl) diethylenetriamine A method for producing a carbon dioxide adsorbent having at least one species. The method according to claim 1,
Wherein the alkoxysilane compound is an ionic liquid. The method according to claim 1,
Wherein the alkylated compound has a pKa of 10 to 30. The method according to claim 1,
Wherein the alkylating agent is at least one haloalkane selected from the group consisting of halomethane, haloethane, halopropane and halobutane. The method according to claim 1,
Wherein the amount of the alkylated compound is 1 to 10% by weight. Mixing a mesoporous silica, an alkoxysilane compound having an amine terminal group and an organic solvent to form a mixture;
Heating the mixture at 50 to 170 ° C. to react the alkoxysilane compound with the mesoporous silica to obtain an organic / inorganic hybrid;
Mixing the organic-inorganic hybrid material with an organic solvent containing an alkylating agent; And
And heating the mixture at 30 to 100 占 폚 to alkylate the amine terminal group of the organic / inorganic hybrid substance. A mesoporous support; And
1 to 10% by weight of an amine compound grafted to the mesoporous support,
The amine compounds, as having a _second terminal group, and the graft through the -Si-O- bond to said meso-porous support, said R 'having an alkylene main chain and -NR a C ₁ to C ₁₂ are C ₁ to of the C ₆ alkyl carbon dioxide adsorbent. 11. The method of claim 10,
Wherein the amine compound contains 1 to 4 -NH- in the main chain. Mesoporous silica; And
An amine compound grafted to the mesoporous silica,
The amine compounds, as having a _second terminal group, and the graft through the -Si-O- bond to said meso-porous support, said R 'having an alkylene main chain and -NR a C ₁ to C ₁₂ are C ₁ to and the C ₆ alkyl, the carbon dioxide adsorbent pKa of 10 to 30.

Images