JP3005678B2 - Method for producing mesoporous silica material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is based on the fact that the former is based on the macro-form regularity based on the ability to form an emulsion containing silica-dissolved species formed from silicon alkoxide and the order to form alkylamine in an acidic aqueous solution. By utilizing the fact that microstructure regularity is obtained from the latter, silica mesoporous materials having regularly arranged pores of uniform diameter and having a regular morphology of microns are used.
Regarding the production method , more specifically, for shape-selective catalysts, useful gases, ion adsorption / separation / storage agents, harmful gases, ion separation / adsorbents, and materials useful for industrial and environmental conservation as decomposition catalysts, etc. A method for producing a suitable mesoporous silica material .

[0002]

2. Description of the Related Art In 1992, MCM-
Since the discovery of 41, many studies on mesoporous materials have been reported. Recently, it has been reported that based on the synthesis method, it is possible to have mesopores arranged regularly and to control the structure at a micron or millimeter period. For example, (1) by controlling the mixing ratio of a surfactant and water and the condensation rate of silica under highly alkaline conditions, a hollow fiber having a diameter of 3 μm and a length of 20 μm and a cylindrical shell portion is formed. A mesoporous silica material in which the mesopores are arranged in a honeycomb shape is produced. (2) When tetraethylorthosilicate (TEOS) containing mesitylene is added dropwise to an aqueous solution of CTAB (cetyltrimethylammonium bromide) to which hydrochloric acid has been added, fibrous, sheet-like or hollow spherical porous silica particles are dispersed at a rate of stirring depending on the stirring speed. Manufactured with a macroscopic form of order. (3) Tetrabutyl orthosilicate (TBOS) is added to a solution obtained by adding water, NaOH, and the like to CTAB, and the mixture is stirred to produce a spherical porous silica having a particle size of 0.1 to 2 mm. However, in the above-mentioned mesoporous silica material, for example, in (1), since the film-like substance having mesopores changes into a cylindrical shape, defects exist in the pore structure, and crystallization of small particles cannot be suppressed. . In (2), the macroscopic morphology of the mesoporous silica material is sensitive to the stirring speed, and it is difficult to efficiently obtain monodispersed spherical particles, and it is necessary to add mesitylene or the like. (3) is tetramethyl orthosilicate (TMOS) as a silicon alkoxide.
And the use of a more expensive TBOS instead of TEOS is indispensable.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a mesoporous silica material having macroscopic morphology such as spherical or plate-like micron order and simultaneously having regularly arranged pores.
It is an object of the present invention to provide a method which can be manufactured at normal temperature, normal pressure and in a short time .

[0004]

Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems, and as a result, has a regularly arranged pores having a uniform diameter as well as a regular micron meter as disclosed below. A method for producing a mesoporous silica material having a morphology has been discovered. That is, according to the present invention, tetraalkyl
Luosilicate, inorganic acid and water
Solution and then add a linear alkyl
The resulting solid product is dried and heat-treated.
The tetraalkyl orthosilicate 1
Per mole of the inorganic acid is 0.05 to 0.6 mol,
0.2 to 1.0 mol of luamine and 10 to 100 of water
There is provided a method for producing a mesoporous silica material in molar.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION A mesoporous silica material (hereinafter, also simply referred to as a porous material) of the present invention is prepared in an acidic aqueous solution.
Based on the ability to form an emulsion containing silica-dissolved species generated from silicon alkoxide (tetraalkyl orthosilicate) and the ability to form an order of alkylamine, the former has macroscopic regularity and the latter has microstructural regularity. Are synthesized using the fact that The synthesis procedure will be described with reference to FIGS. As shown in FIG. 1 (a), the silica-dissolved species A generated from the alkoxide and the alkylamine (B) form an emulsion having a size on the order of microns on the basis of the acidic aqueous solution phase (C) as a boundary phase.
Here, when the emulsion is stable and the silica-dissolved species A interacts with the alkylamine based on the electrostatic force in the boundary phase that is the acidic aqueous solution phase (C), FIG.
As shown in (c) and (d), a meso aggregate regularly arranged along the boundary phase is formed. That is, when the solid product is dried after centrifugation and the alkylamine is removed, spherical silica mesoporous bodies (b), (c) and (d) having a diameter of several microns and having a spherical shell with mesopores are formed. . Octylamine is effective as an alkylamine for producing a mesoporous silica material having this form. Also, the type of acid solution,
By changing the concentration and the volume, it is possible to introduce the thin plate-shaped mesoporous silica into the thick part or hollow part of the spherical shell.

On the other hand, FIG. 2 (a) shows a case where an alkylamine (B) and a silica-dissolved species (A) rapidly interact with each other in an acidic aqueous solution phase as a boundary phase, so that an emulsion is not formed stably. Yes, thin plate-like crystal pieces having mesopores aggregate to form one particle, and macroscopically, these particles aggregate and are observed as flat particles. That is, after centrifugation, the solid product is dried to remove the alkylamine, and as shown in FIG. 2 (b), a plate-like crystal piece having a size of several microns in which mesopores are regularly arranged as shown in FIG. A mesoporous silica body (referred to as a flat porous silica body in which lamellar crystal pieces having mesopores are aggregated) is produced. For the production of this kind of mesoporous silica, decylamine or dodecylamine is preferably used as the alkylamine. Also, the type, concentration,
The size of the mesopores can be controlled by the capacity and the type of alkylamine.

The mesoporous silica produced by the above method is
As a new mesoporous silica material, it has pores that are periodically arranged and its size is easily controllable. Can be classified.
In addition, this porous body can be synthesized at room temperature, normal pressure and in a short period of time,
A major feature is that it is thermally stable.

FIG. 3 shows a scanning electron micrograph (a) and a transmission electron micrograph (b) of the spherical mesoporous silica obtained by the production method. FIG. 4 shows a scanning electron micrograph (a) and a transmission electron micrograph (b) of the plate-shaped mesoporous silica obtained by the above method. FIG.
(A) and (B) are X-ray diffraction diagrams corresponding to the mesoporous material shown in FIGS. 3 and 4, respectively, and the presence of bottom reflection indicates that the arrangement of the pores is not irregular. I have. FIG. 6 is a nitrogen adsorption isotherm, and (A) and (B) correspond to the mesoporous silica material shown in FIGS. 3 and 4, respectively. The shape is an IV type, and in (B), a remarkable step is observed near a relative pressure of 0.4. Each of the t curves had a shape unique to the presence of mesopores. Further, from the pore diameter distribution curve obtained by the Horvath-Kawazoe method, the average effective diameter of the pores is 2.2 nm in the porous body of FIG. 3, while it is 4.0 in the porous body of FIG.
It was found that the distribution was relatively sharp in nm. The porous body has pores that are periodically arranged. That is, 0.8 to 4.5 nm, preferably 2 to 4 nm.
Have a microstructure in which hexagonal pores are regularly arranged. The periodically arranged pores are XR
It means having a hexagonal mesh-like wall structure with a regular SiO ₄ tetrahedron as a unit that gives (001) reflection as D diffraction lines.

The average pore diameter, surface area and pore volume referred to in this specification are measured by a nitrogen adsorption method at a temperature of -196 ° C., and the measuring apparatus is “BELSORP28A” manufactured by Bell Japan Co., Ltd. Was used. The bottom distance d ₀₀₁ was measured at room temperature by a powder X-ray diffraction method, and the measuring device was manufactured by Rigaku Corporation.
"Rotaflex RU-300" was used.

The synthesis of a mesoporous silica material is performed according to the following procedure. In this case, as the starting material, a Si-alkoxide having a lower alkoxy group having 1 to 4 carbon atoms such as tetramethyl orthosilicate, tetraethyl orthosilicate, tetraisopropyl orthosilicate, tetra-n-butylorthosilicate, etc. is used. Preferably, tetraethyl orthosilicate (hereinafter abbreviated as TEOS) is used. As the linear alkylamine, one having 8 to 12 carbon atoms is used. As the inorganic acid, hydrochloric acid, sulfuric acid, nitric acid or the like can be used.

The preferred method of synthesizing a mesoporous silica material will be specifically described using an example in which TEOS and HCl are used as raw materials.
An emulsion was formed by stirring at 600 to 1000 rpm for 10 minutes, and after adding an alkylamine, 600 to 1000 rpm.
The reaction is carried out at room temperature for 15 minutes or more, preferably 15 to 120 minutes, while stirring at 00 rpm. The mixing molar ratio of the starting materials was TEOS: HCl: alkylamine: water = 1: 0.
2 to 0.6: 0.4 to 1.0: 5 to 80. Also,
(A) In the case of a hollow spherical silica mesoporous material having mesopores, octylamine is particularly preferably used as an alkylamine, and TEOS: HCl: alkylamine: water = 1: 0.25-0. 5: 0.6-0.
7: 20 to 50. In the case of (b) a plate-like mesoporous silica material in which thin plate-like crystal pieces having mesopores are aggregated, decylamine or dodecylamine is particularly effective as an amine, and the mixing molar ratio of the starting materials is preferably TEOS. : HCl: alkylamine: water = 1:
0.2 to 0.4: 0.45 to 0.55: 20 to 30. Next, the suspension after the reaction is centrifuged, and the solid product is dried at room temperature to 100 ° C, preferably at 50 ° C for 12 hours or more. Finally, in order to remove the organic compound and produce a porous body, at least 400 ° C. for 1 hour or more, preferably 450 ° C.
Heat treatment at ~ 800 ° C for 2 hours.

[0012]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The mixing ratios shown below are molar ratios.

Example 1 A mixed solution of TEOS and an aqueous hydrochloric acid solution was prepared at 600 rpm for 5 minutes.
Then, hexylamine was added to the mixture, and the mixture was reacted at room temperature for 60 minutes. TEOS: HC
1: molar ratio of hexylamine: water is 1: 0.223:
0.842: 24.802. After the reaction, the suspension is centrifuged, and the resulting solid is dried at room temperature for 1 day and further at 50 ° C. for 1 day, and finally heated at 500 ° C. for 2 hours to remove an organic compound, thereby producing a porous silica material. The resulting porous body is a spherical particle, and the pore characteristics such as the specific surface area are shown in Table 1.

[0014]

[Table 1]

Example 2 A mixed solution of TEOS and an aqueous hydrochloric acid solution was mixed at 600 rpm for 5 minutes.
Then, octylamine was added, and the mixture was reacted at room temperature for 60 minutes (TEOS: HC).
l: octylamine: water = 1: 0.223: 0.67
4: 24.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound was removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous body is a hollow spherical particle, and the pore characteristics such as the specific surface area are shown in Table 2.

[0016]

[Table 2]

Example 3 A mixed solution of TEOS and an aqueous hydrochloric acid solution was prepared at 600 rpm for 5 minutes.
Then, octylamine was added, and the mixture was reacted at room temperature for 60 minutes (TEOS: HC).
l: octylamine: water = 1: 0.281: 0.67
4: 24.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound was removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous body is a hollow spherical particle, and the pore characteristics such as the specific surface area are shown in Table 3.

[0018]

[Table 3]

Example 4 A mixed solution of TEOS and an aqueous hydrochloric acid solution was prepared at 600 rpm for 5 minutes.
Then, octylamine was added, and the mixture was reacted at room temperature for 60 minutes (TEOS: HC).
l: octylamine: water = 1: 0.335: 0.67
4: 24.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound was removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous body is a hollow spherical particle, and the pore characteristics such as the specific surface area are shown in Table 4.

[0020]

[Table 4]

Example 5 A mixed solution of TEOS and an aqueous hydrochloric acid solution was prepared at 600 rpm for 5 minutes.
Then, octylamine was added, and the mixture was reacted at room temperature for 60 minutes (TEOS: HC).
l: octylamine: water = 1: 0.393: 0.67
4: 24.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound was removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous body is a hollow spherical particle, and the pore characteristics such as the specific surface area are shown in Table 5.

[0022]

[Table 5]

Example 6 A mixed solution of TEOS and an aqueous hydrochloric acid solution was prepared at 600 rpm for 5 minutes.
Then, octylamine was added, and the mixture was reacted at room temperature for 60 minutes (TEOS: HC).
l: octylamine: water = 1: 0.447: 0.67
4: 24.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound was removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous body is a hollow spherical particle, and the pore characteristics such as the specific surface area are shown in Table 6.

[0024]

[Table 6]

Example 7 A mixed solution of TEOS and an aqueous hydrochloric acid solution was prepared at 600 rpm for 5 minutes.
Then, octylamine was added, and the mixture was reacted at room temperature for 60 minutes (TEOS: HC).
l: octylamine: water = 1: 0.279: 0.67
4: 31.002). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound was removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous body is a hollow spherical particle, and the pore characteristics such as the specific surface area are shown in Table 7.

[0026]

[Table 7]

Example 8 A mixed solution of TEOS and an aqueous hydrochloric acid solution was mixed at 600 rpm for 5 minutes.
Then, octylamine was added, and the mixture was reacted at room temperature for 60 minutes (TEOS: HC).
l: octylamine: water = 1: 0.335: 0.67
4: 37.202). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound was removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous body is a hollow spherical particle, and the pore characteristics such as the specific surface area are shown in Table 8.

[0028]

[Table 8]

Example 9 A mixed solution of TEOS and an aqueous hydrochloric acid solution was mixed at 600 rpm for 5 minutes.
Then, octylamine was added, and the mixture was reacted at room temperature for 60 minutes (TEOS: HC).
l: octylamine: water = 1: 0.391: 0.67
4: 43.403). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound was removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous body is a hollow spherical particle, and the pore characteristics such as the specific surface area are shown in Table 9.

[0030]

[Table 9]

Example 10 A mixed solution of TEOS and an aqueous hydrochloric acid solution was mixed at 600 rpm for 5 minutes.
Then, octylamine was added, and the mixture was reacted at room temperature for 60 minutes (TEOS: HC).
l: octylamine: water = 1: 0.446: 0.67
4: 49.603). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound was removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous body is a hollow spherical particle as shown in the scanning electron micrograph and the transmission electron micrograph shown in FIGS. 3A and 3B, and the pore characteristics such as specific surface area are shown in Table 10.

[0032]

[Table 10]

Example 11 A mixed solution of TEOS and an aqueous hydrochloric acid solution was prepared at 600 rpm for 5 minutes.
Then, octylamine was added, and the mixture was reacted at room temperature for 60 minutes (TEOS: HC).
l: octylamine: water = 1: 0.056: 0.67
4: 6.200). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day, and finally heated at 500 ° C. for 2 hours to remove organic compounds, thereby producing a mesoporous silica material. The resulting porous body is a hollow spherical particle, and the pore characteristics such as the specific surface area are shown in Table 11.

[0034]

[Table 11]

Example 12 A mixed solution of TEOS and an aqueous hydrochloric acid solution was prepared at 600 rpm for 5 minutes.
Then, octylamine was added, and the mixture was reacted at room temperature for 60 minutes (TEOS: HC).
l: octylamine: water = 1: 0.558: 0.67
4: 62.004). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound was removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous body is a hollow spherical particle, and the pore characteristics such as the specific surface area are shown in Table 12.

[0036]

[Table 12]

Example 13 A mixed solution of TEOS and an aqueous hydrochloric acid solution was prepared at 600 rpm for 5 minutes.
Then, while stirring, decylamine was added thereto and reacted at room temperature for 60 minutes (TEOS: HCl:
Decylamine: water = 1: 0.045: 0.563: 2
4.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day, and finally heated at 500 ° C. for 2 hours to remove organic compounds, thereby producing a mesoporous silica material. The resulting porous body is a flat particle formed by assembling thin plate-shaped crystal pieces. Table 13 shows pore characteristics such as specific surface area.

[0038]

[Table 13]

Example 14 A mixed solution of TEOS and an aqueous hydrochloric acid solution was prepared at 600 rpm for 5 minutes.
Then, while stirring, decylamine was added thereto and reacted at room temperature for 60 minutes (TEOS: HCl:
Decylamine: water = 1: 0.179: 0.563: 2
4.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day, and finally heated at 500 ° C. for 2 hours to remove organic compounds, thereby producing a mesoporous silica material. The resulting porous body is a tabular particle in which thin plate-like crystal pieces are aggregated, and the pore characteristics such as the specific surface area are shown in Table 14.

[0040]

[Table 14]

Example 15 A mixed solution of TEOS and an aqueous hydrochloric acid solution was mixed at 600 rpm for 5 minutes.
Then, while stirring, decylamine was added thereto and reacted at room temperature for 60 minutes (TEOS: HCl:
Decylamine: water = 1: 0.223: 0.563: 2
4.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day, and finally heated at 500 ° C. for 2 hours to remove organic compounds, thereby producing a mesoporous silica material. The resulting porous body is a thin plate-like crystal fragment aggregate spherical particle, and the pore characteristics such as the specific surface area are shown in Table 15.

[0042]

[Table 15]

Example 16 A mixed solution of TEOS and an aqueous hydrochloric acid solution was prepared at 600 rpm for 5 minutes.
Then, while stirring, decylamine was added thereto and reacted at room temperature for 60 minutes (TEOS: HCl:
Decylamine: water = 1: 0.268: 0.563: 2
4.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day, and finally heated at 500 ° C. for 2 hours to remove organic compounds, thereby producing a mesoporous silica material. The resulting porous body is a flat particle formed by assembling thin plate-shaped crystal pieces. Table 16 shows pore characteristics such as specific surface area.

[0044]

[Table 16]

Example 17 A mixed solution of TEOS and an aqueous hydrochloric acid solution was prepared at 600 rpm for 5 minutes.
Then, while stirring, decylamine was added thereto and reacted at room temperature for 60 minutes (TEOS: HCl:
Decylamine: water = 1: 0.446: 0.563: 2
4.802). After the reaction, the suspension is centrifuged, and the resulting solid is dried at room temperature for 1 day and further at 50 ° C. for 1 day, and finally heated at 500 ° C. for 2 hours to remove an organic compound, thereby producing a mesoporous silica material. The resulting porous body is a tabular particle in which thin plate-shaped crystal pieces are aggregated, and the pore characteristics such as the specific surface area are shown in Table 17.

[0046]

[Table 17]

Example 18 A mixed solution of TEOS and an aqueous hydrochloric acid solution was prepared at 600 rpm for 5 minutes.
Then, while stirring, decylamine was added thereto and reacted at room temperature for 60 minutes (TEOS: HCl:
Decylamine: water = 1: 0.446: 0.563: 4
9.603). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day, and finally heated at 500 ° C. for 2 hours to remove organic compounds, thereby producing a mesoporous silica material. The resulting porous body is a tabular particle in which thin plate-like crystal pieces are aggregated, and the pore characteristics such as the specific surface area are shown in Table 18.

[0048]

[Table 18]

Example 19 A mixed solution of TEOS and an aqueous hydrochloric acid solution was mixed at 600 rpm for 5 minutes.
Then, while stirring, dodecylamine was then added and reacted at room temperature for 60 minutes (TEOS: HC
l: dodecylamine: water = 1: 0.045: 0.48
4: 24.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound was removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous material is a tabular particle in which thin plate-shaped crystal fragments are aggregated, and has a pore characteristic such as a specific surface area.
It is shown in FIG.

[0050]

[Table 19]

Example 20 A mixed solution of TEOS and an aqueous hydrochloric acid solution was mixed at 600 rpm for 5 minutes.
Then, while stirring, dodecylamine was then added and reacted at room temperature for 60 minutes (TEOS: HC
l: dodecylamine: water = 1: 0.179: 0.48
4: 24.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound is removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous material is a flat particle formed by assembling thin plate-shaped crystal fragments, and the pore characteristics such as specific surface area are shown in Table 2.
0 is shown.

[0052]

[Table 20]

Example 21 A mixed solution of TEOS and an aqueous hydrochloric acid solution was prepared at 600 rpm for 5 minutes.
Then, while stirring, dodecylamine was then added and reacted at room temperature for 60 minutes (TEOS: HC
l: dodecylamine: water = 1: 0.223: 0.48
4: 24.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound is removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous material is a flat particle formed by assembling thin plate-shaped crystal fragments, and the pore characteristics such as specific surface area are shown in Table 2.
It is shown in FIG.

[0054]

[Table 21]

Example 22 A mixed solution of TEOS and an aqueous hydrochloric acid solution was mixed at 600 rpm for 5 minutes.
Then, while stirring, dodecylamine was then added and reacted at room temperature for 60 minutes (TEOS: HC
l: dodecylamine: water = 1: 0.268: 0.48
4: 24.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound was removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous material is a flat particle formed by assembling thin plate-shaped crystal fragments, and the pore characteristics such as specific surface area are shown in Table 2.
It is shown in FIG.

[0056]

[Table 22]

Example 23 The solid produced by drying in Example 1 was heated at 800 ° C. for 1 hour to remove organic compounds, thereby producing a mesoporous silica material. Table 23 shows the pore characteristics such as the specific surface area of the produced porous body.

[0058]

[Table 23]

Example 24 The solid produced by drying in Example 6 was heated at 800 ° C. for 1 hour to remove organic compounds, thereby producing a mesoporous silica material. Table 24 shows the pore characteristics such as the specific surface area of the resulting porous body.

[0060]

[Table 24]

Example 25 The solid produced by drying in Example 8 was heated at 800 ° C. for 1 hour to remove organic compounds, thereby producing a mesoporous silica material. Table 25 shows the pore characteristics such as the specific surface area of the resulting porous body.

[0062]

[Table 25]

Example 26 The dried product solid of Example 10 was heated at 800 ° C. for 1 hour to remove organic compounds, thereby producing a mesoporous silica material. Table 26 shows the pore characteristics such as the specific surface area of the produced porous body.

[0064]

[Table 26]

Example 27 The dried product solid of Example 15 was heated at 800 ° C. for 1 hour to remove the organic compound, thereby producing a mesoporous silica material. Table 27 shows the pore characteristics such as the specific surface area of the resulting porous body.

[0066]

[Table 27]

Example 28 The solid produced by drying in Example 21 was heated at 800 ° C. for 1 hour to remove organic compounds, thereby producing a mesoporous silica material. Table 28 shows the pore characteristics such as the specific surface area of the produced porous body.

[0068]

[Table 28]

Example 29 A mixed solution of TEOS and an aqueous nitric acid solution was mixed at 600 rpm for 5 minutes.
Then, octylamine was added and the mixture was reacted at room temperature for 60 minutes (TEOS: HNO
₃ : octylamine: water = 1: 0.447: 0.67
4: 24.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day.
Finally, the organic compound was removed by heating at 500 ° C. for 2 hours to produce a mesoporous silica material. The resulting porous body is a spherical particle,
Table 29 shows the pore characteristics such as the specific surface area.

[0070]

[Table 29]

Example 30 A mixed solution of TEOS and an aqueous sulfuric acid solution was mixed at 600 rpm for 5 minutes.
Then, octylamine was added, and the mixture was reacted at room temperature for 60 minutes (TEOS: H ₂ S).
O ₄ : octylamine: water = 1: 0.2235: 0.6
74: 24.802). After the reaction, the suspension was centrifuged, and the resulting solid was dried at room temperature for 1 day and further at 50 ° C. for 1 day, and finally heated at 500 ° C. for 2 hours to remove organic compounds, thereby producing a mesoporous silica material. Partially spherical particles were observed in the resulting porous body, and the pore characteristics such as the specific surface area are as shown in Table 30.

[0072]

[Table 30]

[0073]

The mesoporous silica material of the present invention has a microstructure in which hexagonal mesh-like pores having an average pore diameter of 0.8 to 4.5 nm are regularly arranged, and has a particle diameter of 0.2.
It is a high specific surface area porous material having a macro form of up to 5 μm and excellent in heat resistance. Even when heat treatment is performed at 800 ° C. for 1 hour in the air, the specific surface area is at least 500 m ² / g. Furthermore, since it has a large number of pores of an appropriate diameter, it can exhibit various shapes and efficiently trap various useful or harmful molecules and ions, and is useful in both industrial and environmental conservation. It can be used as a molecular sieve or a catalyst carrier. In addition, the mesoporous silica of the present invention is formed by utilizing the ability to form an alkylamine at the emulsion interface on the order of several microns, so that not only the microstructure but also the regularity of the macro form can be controlled under normal temperature and normal pressure. It can also be applied to the production of porous silica meso thin films and fibers.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a process of producing a mesoporous spherical silica material of the present invention.

FIG. 2 is a schematic view showing a process of producing a flat-plate-shaped mesoporous silica material of the present invention.

FIG. 3 is a scanning electron micrograph (a) and a transmission electron micrograph (b) of the mesoporous silica shown in Example 10.
Is shown.

FIG. 4 is a scanning electron micrograph (a) and a transmission electron micrograph (b) of the mesoporous silica shown in Example 21.
Is shown.

FIG. 5 is a powder X-ray diffraction chart of the mesoporous silica material shown in Examples 10 and 21. A: Example 10, B:
Example 21

FIG. 6 is a nitrogen adsorption isotherm of the mesoporous silica material shown in Examples 10 and 21. A: Example 10, B:
Example 21

Claims (3)

(57) [Claims] 1. Tetraalkyl orthosilicate, inorganic
The acid and water are mixed to form an emulsion and then the
Reaction of linear alkylamine with marjon
Drying and heat treating the solid product;
The inorganic acid is added in an amount of 0.1 mol per mol of alkyl orthosilicate.
0.5 to 0.6 mol, the alkylamine is 0.2 to 1.0 mol.
Mole and silica mesoporous using 10 to 100 moles of water
How to make the body. 2. A mesoporous silica material having a spherical shape.
A method for producing a mesoporous silica material. 3. The mesoporous silica material has a flat plate shape.
1. A method for producing a mesoporous silica material.