JP2001302229A - Method for producing mesoporous inorganic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a mesoporous inorganic porous material having high specific surface area and useful for improving the performance of an adsorbent or a catalyst. SOLUTION: A silica source composed of an inorganic Si compound such as sodium silicate (Na2SiO2, etc.), is mixed with an alumina source such as aluminum oxide (Al2O3) and an aqueous solution of an organic template used as a material for determining the shape of the objective porous material, the mixture is subjected to crystallization reaction to obtain a precursor of a mesoporous inorganic polymer containing the organic template and removing the organic template from the product to obtain the objective mesoporous inorganic material. In the above process, a phosphorus compound is added to the organic template and the crystallization reaction is carried out at pH 0-6 and <=50 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a mesoporous inorganic porous material having a high specific surface area for improving the performance of an adsorbent or a catalyst.

[0002]

2. Description of the Related Art Mesoporous silicate is an aggregate of columnar structures having a hollow having an inner diameter of about 10 ° or more, and is a porous body having a specific surface area of up to 1500 m ² / g.
This porous body was first proposed in Mobil International Publication No. WO 91/11390, and n-dodecyltrimethylammonium chloride and sulfuric acid dissolved in an aqueous sodium hydroxide solution were alternately added little by little to a silica sol. After
The gel was prepared by adjusting the pH to about 13.5, and this was
After stirring for hours, hydrothermal synthesis is performed by standing at 140 ° C. for 48 hours in an autoclave, and the product is filtered, washed with water, dried, and then calcined at 550 ° C. for several hours to remove the remaining organic substances, thereby forming a mesoporous silicate. I'm trying to get

According to the above proposal, in a gel prepared at a pH of about 13.5, n-dodecyltrimethylammonium chloride forms rod-shaped micelles, silica is coordinated on the surface thereof, and the silica on the surface undergoes dehydration polymerization. Thus, a silica network is formed. The micelles of dodecyltrimethylammonium chloride are removed by baking at 550 ° C., leaving only a network of silica coordinated on the outer surface, and a porous silica body having a hollow is obtained. In recent years, synthesis has become possible even at room temperature under conditions of pH 0 to 10, and the synthesis method has been simplified.

The above-mentioned mesoporous silica has a skeleton of 3
By introducing aluminum (Al) or boron (B) which is a valence element, it is possible to improve the adsorption performance and the catalyst performance. In the synthesis, an aluminosilicate compound or boron silicate is obtained by using an aluminum compound or a boron compound as a raw material.

However, when the aluminum content increases, the coordination with the rod-shaped micelle as a skeleton does not proceed, and a porous body cannot be synthesized. This is because Si is tetravalent, Al is trivalent and the valence is different.
Cations enter the crystal. Al forms four coordination by the introduction of these cations, but there is a problem in the conventional synthesis method that if silica: alumina is less than 20: 1, the specific surface area decreases and crystallinity cannot be obtained.

The present invention solves the above-mentioned problems in the prior art. Even if an element other than Si is introduced into a mesoporous porous material, a silica network can be formed well, and the specific surface area is high and it can be used as an adsorbent. An object of the present invention is to provide a method for producing a mesoporous inorganic porous material.

[0007]

Means for Solving the Problems According to the invention of claim 1 which solves the above-mentioned problems, a silica source composed of an inorganic Si compound, an alumina source and an aqueous solution of an organic template are mixed, and a crystallization reaction is carried out. A method for producing a mesoporous inorganic porous material by obtaining a precursor of a mesoporous inorganic polymer containing a template, and then removing the organic template, wherein a phosphorus compound is added to the organic template, and the pH is adjusted to 0 to 6, It is characterized by stirring under a condition of 50 ° C. or less.

A second aspect of the present invention is characterized in that, in the first aspect, the phosphorus (P) / aluminum (Al) molar ratio is 1 or more.

A third aspect of the present invention is characterized in that, in the first aspect, the silica source is any one of sodium silicate, water glass and silica sol.

A fourth aspect of the present invention is characterized in that, in the first aspect, the alumina source is any one of alumina, aluminum ethoxide, sodium aluminate and aluminum isopropoxide.

The invention of claim 5 is the invention according to claim 1, wherein the organic template is hexadecylpyridinim chloride, dodecyltrimethylammonium chloride, hexadecylpyridinium bromide, hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide. , Tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, hexadecyldimethylbenzylammonium bromide, or hexadecyldimethylbenzylammonium chloride.

According to a sixth aspect of the present invention, in any one of the first to fifth aspects, the method for removing the organic template is a heat treatment.

[0013] The invention of claim 7 is characterized in that, in any one of claims 1 to 5, the method of removing the organic template is extraction with a solvent.

The invention of claim 8 is characterized in that, in claim 7, the solvent is alcohol.

A ninth aspect of the present invention is characterized in that, in the seventh aspect, the solvent is a fluid under supercritical conditions.

The invention of claim 10 is the invention of claim 7, 8,
9, wherein the extracted organic template is reused.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.

The method for producing a mesoporous inorganic porous material according to the present invention can be carried out, for example, using sodium silicate (such as Na ₂ Si).
A silica source composed of an inorganic Si compound such as O ₂ ) is mixed with an alumina source such as sodium aluminate (NaAlO ₂ ) and an aqueous solution of an organic template which is a material for determining the shape of the porous body, and subjected to a crystallization reaction. Obtaining a precursor of a mesoporous inorganic polymer containing an organic template, and then removing the organic template to produce a mesoporous inorganic porous material, wherein a phosphorus compound is added to the organic template, and a crystallization reaction is performed. Conditions are pH 0-6, temperature 50 ° C
The following is for producing a mesoporous inorganic porous material.

Here, the phosphorus compound to be added is added to the organic template. This is because, when sodium silicate is used as the silica source, if, for example, phosphoric acid is added as the phosphorus compound, it reacts because sodium silicate is alkaline, which is not preferable.

In addition, when aluminum sulfate is used as the alumina source when adding to the alumina source, if phosphoric acid is added as the phosphoric acid compound, the reaction may proceed and the silica may not enter the silica network. It is.

In the present invention, the molar ratio of phosphorus (P) / aluminum (Al) is 1 or more, preferably 1 ≦ [P].
/ [Al] ≦ 2. This is [P] / [A
When the [l] molar ratio is 2 or more, no further effect is exhibited.

The crystallization reaction conditions include a pH of 0 to 6, preferably pH 1, a temperature of 50 ° C. or lower, preferably about room temperature, and a reaction time of 3 hours or more, preferably about 6 hours. Is good.

Here, the silica source in the present invention is not particularly limited. For example, sodium silicate, water glass and silica sol, tetraethylorthosilicate (TEO)
It is preferable to use any of S) and tetramethyl orthosilicate (TMOS). Here, in order to form a silica network, the silica source is preferably in an ionic silica state in which polymerization has not progressed in a solution state.

In the present invention, the alumina source is not particularly limited. For example, it is preferable to use any one of alumina sol, aluminum ethoxide, sodium aluminate and aluminum isopropoxide. Particularly, sodium silicate is preferably used, and the concentration is preferably 3% or more.

In the present invention, the organic template is, for example, hexadecylpyridinim chloride, dodecyltrimethylammonium chloride, hexadecylpyridinium bromide, hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium chloride, tetradecyl It is preferable to use any one of trimethylammonium bromide, hexadecyldimethylbenzylammonium bromide and hexadecyldimethylbenzylammonium chloride.

According to the present invention, rod-shaped micelles can be formed from an organic template to form a silicon network. At this time, by adding a phosphorus compound, A can be formed during skeleton formation.
1 is compensated, and Si and Al are synthesized at the same mixing ratio.

That is, in the prior art, the mesoporous skeleton has a structure of Si—
A network is formed with O—Si—O—, and when Al is added to the network, the Al is trivalent, so that the tetravalent S
It is necessary to compensate for the valence when entering the arrangement of i. Therefore, cations (Na, K ions, etc.) enter near Al. However, when the amount of Al introduced is large, it is difficult for Al to have the same structure as Si, so that no skeleton is formed, and a good mesoporous silicate cannot be obtained. In the present invention, by introducing a phosphorus compound which is a pentavalent atom, the charge of Al is compensated during the formation of the skeleton, and the mixing ratio of Si and Al is almost the same. In principle, 5
Any element can be used as long as it is a valence atom, and for example, arsenic (As), antimony (Sb), or the like can be used.

The synthesis method uses a silicic acid source such as an aqueous solution of sodium silicate, an alumina source such as aluminum sulfate or alumina sol, and phosphoric acid as raw materials, and a surfactant such as cetyltrimethylammonium chloride as a template.

The organic template forming the rod-shaped micelles can be removed by baking at a high temperature. However, since the template can be reused, it can be removed by extraction with a solvent.

This extraction needs to be performed in the state of the precursor before firing into a mesoporous inorganic porous material. As a solvent for extracting the organic template from the precursor, a solvent having a high solubility for dissolving the organic template to be used is used. Any one can be used as long as it is used, but it is preferable to use, for example, various alcohols or fluids in a supercritical state. As the alcohols, lower aliphatic alcohols having up to about 5 carbon atoms are preferable, and methanol or ethanol is particularly preferable.

The fluid in the case of supercritical extraction is as follows:
CO ₂ or various fluorocarbons such as R-22 and R-123 can be used, and CO ₂ is particularly preferable.

The organic template extracted in this way can be reused as a raw material for synthesis again, and the amount of the new organic template used can be reduced to about 1/3 to 1/5.

According to the production method of the present invention, in the method for producing a mesoporous inorganic polymer using an organic template that forms micelles, it is possible to synthesize a mesoporous silicate having a low silica-alumina ratio by introducing a phosphorus compound. Was confirmed. In addition, by adopting a method of extracting with an alcohol or a liquid in a supercritical state as a method of removing the organic template after the formation of the skeleton of the mesoporous aluminosilicate, the organic template can be easily removed without destroying the silica-alumino network. A stable mesoporous aluminosilicate was obtained. In addition, since the organic template can be manufactured at low cost by collecting and reusing it, its industrial value is great.

[0034]

EXAMPLES In order to demonstrate the effectiveness of the present invention, a mesoporous inorganic polymer containing an organic template was synthesized using sodium silicate as a silica source and aluminum sulfate as an alumina source at room temperature. The material is calcined or treated with alcohol or supercritical C
The organic template was removed by contact with O ₂ , and the properties and adsorption performance of the mesoporous inorganic polymer after the removal were evaluated. In the following examples, the organic template solution
And the silicic acid solution as solution B and the alumina solution as solution C
Each will be described.

(Example 1) (1) Preparation of solution A: 4.4 g of hexadecylpyridinium chloride is dissolved in 50 ml of purified water, and 2.8 g of phosphoric acid is added. (2) Preparation of solution B: sodium silicate 2.
3 g are dissolved. (3) Preparation of solution C: 6.8 g of aluminum sulfate is sufficiently dissolved in purified water. While stirring the solution A, the solution B and the solution C are mixed, and p
H was adjusted to 1 and stirred at room temperature for 3 hours. The purified precipitate was filtered and washed with water to obtain about 10 g of a precursor of a mesoporous inorganic polymer containing hexadecylpyridinium chloride. After drying this precursor, it was calcined at 550 ° C. to remove the contained hexadecylpyridinium chloride to obtain a mesoporous silicate from which the organic substance was completely removed.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction, but there was no difference in the X-ray diffraction pattern. This confirmed the synthesis of mesoporous aluminosilicate. FIG. 2 shows its X-ray diffraction diagram of FIG. 1.

(Embodiment 2) In this embodiment, the amount of the phosphorus component and the amount of the aluminum component in the first embodiment are changed. (1) Preparation of solution A: Dissolve 4.4 g of hexadecylpyridinium chloride in 50 ml of purified water, and add 2.8 g of phosphoric acid. (2) Preparation of solution B: sodium silicate 4.
6 g are dissolved. (3) Preparation of solution C: 5 g of aluminum sulfate is sufficiently dissolved in purified water. While stirring the solution A, the solution B and the solution C are mixed, and p
H was adjusted to 1 and stirred at room temperature for 3 hours. The purified precipitate was filtered and washed with water to obtain about 10 g of a precursor of a mesoporous inorganic polymer containing hexadecylpyridinium chloride. After drying the precursor, the precursor was calcined at 550 ° C. to remove the contained hexadecylpyridinium chloride to obtain a mesoporous silicate from which organic substances were completely removed.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction, but there was no difference in the X-ray diffraction pattern. This confirmed the synthesis of mesoporous aluminosilicate. FIG. 3 shows its X-ray diffraction diagram of FIG. 2.

(Embodiment 3) In this embodiment, the reaction temperature is set to 50 ° C. by changing the amount of the aluminum component in the embodiment 1. (1) Preparation of solution A: 4.4 g of hexadecylpyridinium chloride is dissolved in 50 ml of purified water, and 2.5 g of phosphoric acid is added. (2) Preparation of solution B: sodium silicate 3.
5 g are dissolved. (3) Preparation of solution C: 6 g of aluminum sulfate is sufficiently dissolved in purified water. While the solution A was stirred, the solutions B and C were mixed to adjust the pH to 1, and the mixture was stirred at a temperature of 50 ° C. for 3 hours. The purified precipitate was filtered and washed with water to obtain about 10 g of a precursor of a mesoporous inorganic polymer containing hexadecylpyridinium chloride. After drying the precursor, the precursor was calcined at 550 ° C. to remove the contained hexadecylpyridinium chloride to obtain a mesoporous silicate from which organic substances were completely removed.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction, but there was no difference in the X-ray diffraction pattern. This confirmed the synthesis of mesoporous aluminosilicate.

(Embodiment 4) In this embodiment, the reaction temperature is set to 90 ° C. by changing the amount of the aluminum component in the embodiment 1. (1) Preparation of solution A: 4.4 g of hexadecylpyridinium chloride is dissolved in 50 ml of purified water, and 2.5 g of phosphoric acid is added. (2) Preparation of solution B: sodium silicate 3.
5 g are dissolved. (3) Preparation of solution C: 6 g of aluminum sulfate is sufficiently dissolved in purified water. While stirring the solution A, the solution B and the solution C are mixed, and p
H was adjusted to 1 and stirred at a temperature of 90 ° C. for 3 hours. The purified precipitate was filtered and washed with water, and about 10 g of a precursor of a mesoporous inorganic polymer containing hexadecylpyridinium chloride was used.
I got After drying the precursor, the precursor was calcined at 550 ° C. to remove the contained hexadecylpyridinium chloride to obtain a mesoporous silicate from which organic substances were completely removed.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction, but there was no difference in the X-ray diffraction pattern. This confirmed the synthesis of mesoporous aluminosilicate.

Example 5 In this example, the reaction temperature was set to 90 ° C. for 6 hours in Example 4. (1) Preparation of solution A: 4.4 g of hexadecylpyridinium chloride is dissolved in 50 ml of purified water, and 2.5 g of phosphoric acid is added. (2) Preparation of solution B: sodium silicate 3.
5 g are dissolved. (3) Preparation of solution C: 6 g of aluminum sulfate is sufficiently dissolved in purified water. While stirring the solution A, the solution B and the solution C are mixed, and p
H was adjusted to 1 and stirred at a temperature of 90 ° C. for 6 hours. The purified precipitate was filtered and washed with water to obtain about 10 g of a precursor of a mesoporous inorganic polymer containing hexadecylpyridinium chloride. After drying the precursor, the precursor was calcined at 550 ° C. to remove the contained hexadecylpyridinium chloride to obtain a mesoporous silicate from which organic substances were completely removed.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction, but there was no difference in the X-ray diffraction pattern. This confirmed the synthesis of mesoporous aluminosilicate.

(Embodiment 6) In this embodiment, the amount of the phosphorus component in Embodiment 4 is changed. (1) Preparation of solution A: 4.4 g of hexadecylpyridinium chloride is dissolved in 50 ml of purified water, and 4.3 g of phosphoric acid is added. (2) Preparation of solution B: sodium silicate 3.
5 g are dissolved. (3) Preparation of solution C: 6 g of aluminum sulfate is sufficiently dissolved in purified water. While stirring the solution A, the solution B and the solution C are mixed, and p
H was adjusted to 1 and stirred at a temperature of 90 ° C. for 3 hours. The purified precipitate was filtered and washed with water, and about 10 g of a precursor of a mesoporous inorganic polymer containing hexadecylpyridinium chloride was used.
I got After drying the precursor, the precursor was calcined at 550 ° C. to remove the contained hexadecylpyridinium chloride to obtain a mesoporous silicate from which organic substances were completely removed.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction, but there was no difference in the X-ray diffraction pattern. This confirmed the synthesis of mesoporous aluminosilicate.

(Embodiment 7) In this embodiment, the pH is changed to 6 in the embodiment 4. (1) Preparation of solution A: 4.4 g of hexadecylpyridinium chloride is dissolved in 50 ml of purified water, and 2.5 g of phosphoric acid is added. (2) Preparation of solution B: sodium silicate 3.
5 g are dissolved. (3) Preparation of solution C: 6 g of aluminum sulfate is sufficiently dissolved in purified water. While stirring the solution A, the solution B and the solution C are mixed, and p
H was adjusted to 6 and stirred at a temperature of 90 ° C. for 3 hours. The purified precipitate was filtered and washed with water, and about 10 g of a precursor of a mesoporous inorganic polymer containing hexadecylpyridinium chloride was used.
I got After drying this precursor, it was calcined at 550 ° C. to remove the contained hexadecylpyridinium chloride to obtain a mesoporous silicate from which the organic substance was completely removed.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction, but there was no difference in the X-ray diffraction pattern. This confirmed the synthesis of mesoporous aluminosilicate.

(Comparative Example 1) In this example, the amount of the phosphorus component in Example 1 was not added. (1) Preparation of solution A: 4.4 g of hexadecylpyridinium chloride is dissolved in 50 ml of purified water. (2) Preparation of solution B: sodium silicate 4.
6 g are dissolved. (3) Preparation of solution C: 5 g of aluminum sulfate is sufficiently dissolved in purified water. The solution A and the solution C were mixed while stirring the solution A, the pH was adjusted to 1, and the mixture was stirred at a temperature of 90 ° C. for 3 hours. The purified precipitate was filtered and washed with water to obtain about 10 g of a precursor of a mesoporous inorganic polymer containing hexadecylpyridinium chloride. After drying the precursor, the precursor was calcined at 550 ° C. to remove the contained hexadecylpyridinium chloride to obtain a mesoporous silicate from which organic substances were completely removed.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction, but a peak was observed in the X-ray diffraction pattern. However, there was no aluminum in the composition of the product, and the mesoporous silicate was synthesized. The mesoporous aluminosilicate could not be obtained.

(Comparative Example 2) In this example, the concentration of the phosphorus component in Example 1 was reduced. (1) Preparation of solution A: 4.4 g of hexadecylpyridinium chloride is dissolved in 150 ml of purified water, and 2.5 g of phosphoric acid is added. (2) Preparation of solution B: sodium silicate 3.45 ml in purified water 45 ml.
5 g are dissolved. (3) Preparation of solution C: 6 g of aluminum sulfate is sufficiently dissolved in purified water. The solution A and the solution C were mixed while stirring the solution A, the pH was adjusted to 1, and the mixture was stirred at a temperature of 90 ° C. for 3 hours. The purified precipitate was filtered and washed with water to obtain about 10 g of a precursor of a mesoporous inorganic polymer containing hexadecylpyridinium chloride. After drying the precursor, the precursor was calcined at 550 ° C. to remove the contained hexadecylpyridinium chloride to obtain a mesoporous silicate from which organic substances were completely removed.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction. However, no peak was observed in the X-ray diffraction pattern, and the synthesis of the mesoporous aluminosilicate could not be confirmed.

Comparative Example 3 In this example, the pH was changed to 10.5 in Example 4. (1) Preparation of solution A: 4.4 g of hexadecylpyridinium chloride is dissolved in 50 ml of purified water, and 2.5 g of phosphoric acid is added. (2) Preparation of solution B: sodium silicate 3.
5 g are dissolved. (3) Preparation of solution C: 6 g of aluminum sulfate is sufficiently dissolved in purified water. While stirring the solution A, the solution B and the solution C are mixed, and p
H was adjusted to 10.5 and stirred at 90 ° C. for 3 hours. The purified precipitate was filtered and washed with water, and about 1% of a precursor of a mesoporous inorganic polymer containing hexadecylpyridinium chloride was used.
0 g was obtained.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction. However, no peak was observed in the X-ray diffraction pattern, and the synthesis of the mesoporous aluminosilicate could not be confirmed.

Table 1 shows the specific surface area of the mesoporous aluminosilicate obtained from the above-mentioned test, the spacing between 100 XRD planes, and the blending ratio (mmol).

[0056]

[Table 1]

As shown in Table 1, a mesoporous aluminosilicate having a low silica-alumina ratio was obtained by adding phosphoric acid during the synthesis. It has been found that the silica-alumina ratio of the product can be controlled by changing the raw material ratio of sodium silicate and aluminum sulfate.

It was also found that room temperature does not replace room temperature up to a synthesis temperature of 90 ° C., but that if it exceeds 90 ° C., the specific surface area decreases and that a synthesis time of 3 hours is sufficient. In addition, increasing the amount of phosphoric acid further decreases the silica-alumina ratio,
Were obtained.

Comparative Example 2 is a test in which the concentration of each solution was reduced. Although a high specific surface area was obtained, the structure was considered to be insufficient, and no peak specific to mesoporous inorganic polymer was observed in the XRD pattern. Was.

Example 8 (1) Preparation of Solution A: A solution in which about 4 g of hexadecyltrimethylammonium chloride was dissolved in 50 ml of purified water instead of hexadecylpyridinium chloride was prepared, and 2.5 g of phosphoric acid was prepared. Add. (2) Preparation of solution B: sodium silicate 3.
5 g are dissolved. (3) Preparation of solution C: 6 g of aluminum sulfate is sufficiently dissolved in purified water. While stirring the solution A, the solution B and the solution C are mixed, and p
H was adjusted to 1 and stirred at a temperature of 50 ° C. for 3 hours. The purified precipitate was filtered and washed with water to obtain about 10 g of a precursor of a mesoporous inorganic polymer containing hexadecyltrimethylammonium chloride. After drying the precursor, the precursor was calcined at 550 ° C. to remove the contained hexadecyltrimethylammonium chloride to obtain a mesoporous silicate from which organic substances were completely removed.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction, but there was no difference in the X-ray diffraction pattern. This confirmed the synthesis of mesoporous aluminosilicate.

Example 9 (1) Preparation of Solution A: A solution in which about 3 g of dodecyltrimethylammonium chloride was dissolved in 50 ml of purified water instead of hexadecylpyridinium chloride was prepared, and phosphoric acid was prepared.
Add 2.5 g. (2) Preparation of solution B: sodium silicate 3.
5 g are dissolved. (3) Preparation of solution C: 6 g of aluminum sulfate is sufficiently dissolved in purified water. While stirring the solution A, the solution B and the solution C are mixed, and p
H was adjusted to 1 and stirred at a temperature of 50 ° C. for 3 hours. The purified precipitate was filtered and washed with water to obtain about 10 g of a precursor of a mesoporous inorganic polymer containing dodecyltrimethylammonium chloride. After drying the precursor, the precursor was calcined at 550 ° C. to remove the contained dodecyltrimethylammonium chloride to obtain a mesoporous silicate from which organic substances were completely removed.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction, but there was no difference in the X-ray diffraction pattern. This confirmed the synthesis of mesoporous aluminosilicate.

Example 10 (1) Preparation of solution A: 4.4 g of hexadecylpyridinium chloride was dissolved in 50 ml of purified water, and 3.6 g of phosphorus oxide was added. (2) Preparation of solution B: sodium silicate 3.
5 g are dissolved. (3) Preparation of solution C: 6 g of aluminum sulfate is sufficiently dissolved in purified water. While stirring the solution A, the solution B and the solution C are mixed, and p
H was adjusted to 1 and stirred at a temperature of 50 ° C. for 3 hours. The purified precipitate was filtered and washed with water, and about 10 g of a precursor of a mesoporous inorganic polymer containing hexadecylpyridinium chloride was used.
I got After drying the precursor, the precursor was calcined at 550 ° C. to remove the contained hexadecylpyridinium chloride to obtain a mesoporous silicate from which organic substances were completely removed.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction, but there was no difference in the X-ray diffraction pattern. This confirmed the synthesis of mesoporous aluminosilicate.

Example 12 (1) Preparation of solution A: 4.4 g of hexadecylpyridinium chloride was dissolved in 50 ml of purified water, and 2.5 g of phosphoric acid was added. (2) Preparation of solution B: About 6 g of about 30% water glass is dissolved in about 12 g of a 0.1 N aqueous sodium hydroxide solution. (3) Preparation of solution C: 6 g of aluminum sulfate is sufficiently dissolved in purified water. While stirring the solution A, the solution B and the solution C are mixed, and p
H was adjusted to 1 and stirred at a temperature of 50 ° C. for 3 hours. The purified precipitate was filtered and washed with water to obtain about 10 g of a precursor of a mesoporous inorganic polymer containing hexadecylpyridinium chloride. After drying the precursor, the precursor was calcined at 550 ° C. to remove the contained hexadecylpyridinium chloride to obtain a mesoporous silicate from which organic substances were completely removed.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction, but there was no difference in the X-ray diffraction pattern. This confirmed the synthesis of mesoporous aluminosilicate.

Example 13 (1) Preparation of Solution A: 4.4 g of hexadecylpyridinium chloride was dissolved in 50 ml of purified water, and 2.5 g of phosphoric acid was added. (2) Preparation of solution B: sodium silicate 3.
5 g are dissolved. (3) Adjustment of solution C: about 2.3 g of alumina sol is used.
H was adjusted to 1 and stirred at a temperature of 50 ° C. for 3 hours. The purified precipitate was filtered and washed with water, and about 10 g of a precursor of a mesoporous inorganic polymer containing hexadecylpyridinium chloride was used.
I got After drying the precursor, the precursor was calcined at 550 ° C. to remove the contained hexadecylpyridinium chloride to obtain a mesoporous silicate from which organic substances were completely removed.

Here, the difference from the structure of the conventional mesoporous silicate was compared by X-ray diffraction, but there was no difference in the X-ray diffraction pattern. This confirmed the synthesis of mesoporous aluminosilicate.

In the above examples, it was confirmed that the synthesis of mesoporous aluminosilicate was successfully performed even when various materials were changed.

(Embodiment 14) In this embodiment, the reuse of an organic template will be described. (1) Preparation of solution A: 4.4 g of hexadecylpyridinium chloride is dissolved in 50 ml of purified water, and 2.5 g of phosphoric acid is added. (2) Preparation of solution B: sodium silicate 3.
5 g are dissolved. (3) Preparation of solution C: 6 g of aluminum sulfate is sufficiently dissolved in purified water. While stirring the solution A, the solution B and the solution C are mixed, and p
H was adjusted to 1 and stirred at a temperature of 50 ° C. for 3 hours. The purified precipitate was filtered and washed with water, and about 10 g of a precursor of a mesoporous inorganic polymer containing hexadecylpyridinium chloride was used.
I got From this precursor, hexadecylpyridinium chloride was extracted and recovered using methanol.

FIG. 1 shows a schematic configuration of an apparatus used in the extraction and recovery apparatus. As shown in FIG. 1, the extraction and recovery apparatus includes a column 11 for filling a precursor 10, a solvent tank 13 for storing an extraction solvent 12 to be supplied into the column, and an intermediary between the tank 13 and the column 11. A heater 15 for heating the solvent 12 which is mounted and sent by the pump 14, and a recovery drum 16 for recovering the solvent from which the extracted organic template is extracted
It consists of and.

Then, the mesoporous silicate precursor 10 was packed in a column 11, and methanol, which was a solvent 12 heated to a temperature of about 50 ° C. by a heater 15, was flowed from the upstream side at a flow rate of 100 ml / min for 1 hour. . Since methanol has a very high solubility in the organic template, the hexadecylpyridinim chloride contained in the precursor is efficiently removed, and 95% of the hexadecylpyridinim chloride contained in the one-hour flow is removed. The above moved to the methanol phase. Thereafter, methanol is supplied to the channel 17.
, And enters the template collection drum 16, where hexadecylpyridinium chloride dissolved in methanol precipitates.
Hexadecylpyridinium chloride as an organic template was recovered from a flow path 18 connected to the lower end of the drum 16. The recovered solvent is sent to the solvent tank 13 through the flow path 19 and is reused. The recovered hexadecylpyridinium chloride was compared with the fresh product by FTIR and gas chromatography, but no deterioration such as thermal deterioration and deterioration due to dissolution in methanol was observed.

Next, this unfired product (after methanol extraction)
Was calcined at 450 ° C. to remove residual hexadecylpyridinium chloride to obtain a mesoporous silicate from which organic substances were completely removed.

Here, the difference in the structure of the mesoporous silicate between the unfired product and the fired product was compared by X-ray diffraction, but there was no difference in the X-ray diffraction pattern. This indicates that a structure peculiar to mesoporous silicate was formed after methanol extraction, and there was no significant change in the subsequent heat treatment.

[0076]

According to the production method of the present invention, a silica source composed of an inorganic Si compound, an alumina source and an aqueous solution of an organic template are mixed and subjected to a crystallization reaction, and then a precursor of a mesoporous inorganic polymer containing an organic template is produced. After obtaining the product, a method for producing a mesoporous inorganic porous material by removing the organic template, a phosphorus compound is added to the organic template, and the mixture is stirred under the conditions of pH 0 to 6 and a temperature of 50 ° C. or less. A mesoporous silicate having a low silica-alumina ratio can be synthesized.

According to the second aspect of the present invention, in the first aspect, since the phosphorus (P) / aluminum (Al) molar ratio is 1 or more, the charge of Al is compensated during the formation of the skeleton by the addition of the phosphorus compound. As a result, Si and Al are synthesized at substantially the same mixing ratio.

According to the third aspect of the present invention, in the first aspect, since the silica source is any one of sodium silicate, water glass and silica sol, it is possible to synthesize a mesoporous silicate having a good low silica-alumina ratio. is there.

The invention according to claim 4 is the method according to claim 1, wherein the alumina source is any one of alumina sol, aluminum ethoxide, sodium aluminate and aluminum isopropoxide. The synthesis of silicate is possible.

The invention of claim 5 is the invention according to claim 1, wherein the organic template is hexadecylpyridinim chloride, dodecyltrimethylammonium chloride, hexadecylpyridinium bromide, hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide. , Tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, hexadecyldimethylbenzylammonium bromide, or hexadecyldimethylbenzylammonium chloride, so that a mesoporous silicate having an excellent low silica-alumina ratio can be synthesized.

According to a sixth aspect of the present invention, in the method of any one of the first to fifth aspects, the organic template can be surely removed by heat-treating the method for removing the organic template.

The invention according to claim 7 is the method according to any one of claims 1 to 5, wherein the method for removing the organic template is extraction with a solvent, so that the silica-alumino network is not destroyed. A mesoporous aluminosilicate of stable quality was obtained.

According to the invention of claim 8, the extraction efficiency is improved because the solvent is alcohol in claim 7.

According to a ninth aspect of the present invention, in the seventh aspect, since the solvent is a fluid under supercritical conditions, the organic template can be easily removed without destroying the silica-alumino network, and the quality can be improved. A stable mesoporous aluminosilicate was obtained.

The invention of [Claim 10] relates to Claims 7, 8,
Since the organic template extracted in 9 is reused, it can be manufactured at low cost, and its industrial value is great.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an extraction and recovery apparatus used in this example.

FIG. 2 is an X-ray diffraction pattern diagram of the mesoporous silicate obtained in Example 1.

FIG. 3 is an X-ray diffraction pattern diagram of the mesoporous silicate obtained in Example 2.

4 is an X-ray diffraction pattern diagram of the mesoporous silicate obtained in Comparative Example 2. FIG.

FIG. 5 shows the X of the mesoporous silicate obtained in Comparative Example 3.
It is a line diffraction pattern figure.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Precursor 11 Column 12 Extraction solvent 13 Solvent tank 14 Pump 15 Heater 16 Recovery drum

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shigeyuki Asana Nagase Prefecture Nagasaki City, Nagasaki City 5-7-17-1 Fumihori-cho, Nagasaki Pref. No. 717-1 in the Nagasaki Laboratory, Mitsubishi Heavy Industries, Ltd. (72) Inventor Akinori Yasutake 5-717-1, Fukahori-cho, Nagasaki-shi, Nagasaki F-term in the Nagasaki Laboratory, Mitsubishi Heavy Industries, Ltd. 4D056 AB17 AC06 AC24 BA16 4G066 AA20A AA22A AA30A AA61B AB19D AB21D AB23A DA01 DA07 FA14 FA33 FA34 FA37 FA38 4G073 BB66 BD06 BD11 CB09 CE01 FB11 FB19 FB21 FB24 FB25 FB26 FB41 FF05 FF07 GA12 UA01 UA06

Claims (10)

[Claims] 1. A silica source comprising an inorganic Si compound, an alumina source, and an aqueous solution of an organic template are mixed and subjected to a crystallization reaction, and a precursor of a mesoporous inorganic polymer containing an organic template is obtained. A method for producing a mesoporous inorganic porous material by removing, wherein a phosphorus compound is added to the organic template,
6. A method for producing a mesoporous inorganic porous material, wherein stirring is performed at a temperature of 50 ° C. or less. 2. The method for producing a mesoporous inorganic porous material according to claim 1, wherein the molar ratio of phosphorus (P) / aluminum (Al) is 1 or more. 3. The method for producing a mesoporous inorganic porous material according to claim 1, wherein the silica source comprises any one of sodium silicate, water glass and silica sol. 4. The method for producing a mesoporous inorganic porous material according to claim 1, wherein the alumina source comprises any of alumina, aluminum ethoxide, sodium aluminate and aluminum isopropoxide. 5. The method according to claim 1, wherein the organic template is hexadecylpyridinim chloride, dodecyltrimethylammonium chloride, hexadecylpyridinium bromide, hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium chloride, A method for producing a mesoporous inorganic porous material, comprising any one of tetradecyltrimethylammonium bromide, hexadecyldimethylbenzylammonium bromide, and hexadecyldimethylbenzylammonium chloride. 6. The method for producing a mesoporous inorganic porous material according to claim 1, wherein the method for removing the organic template is heat treatment. 7. The method for producing a mesoporous inorganic porous material according to claim 1, wherein the method for removing the organic template is extraction with a solvent. 8. The method for producing a mesoporous inorganic porous material according to claim 7, wherein the solvent is an alcohol. 9. The method for producing a mesoporous inorganic porous material according to claim 7, wherein the solvent is a fluid under supercritical conditions. 10. A method for producing a mesoporous inorganic porous material, wherein the organic template extracted in claim 7, 8, 9 is reused.