JP3379353B2 - Mesopore material and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a catalyst support such as adsorbents such as hydrocarbons, the solid support such as an enzyme, the pores can be used as synthetic field such as the functional material, i.e., have a mesopore Rume Sopoa materials and Manufacturing method

[0002]

2. Description of the Related Art Conventionally, a mesopore material having pores, that is, mesopores, which can be used as a carrier for a catalyst or the like, an adsorbent for hydrocarbons or the like, a fixed carrier for enzymes or the like, or a synthesis site for functional substances, is known. The mesopore material is a substance formed by aggregating submicron-order primary particles having a large amount of pores (mesopores).

A substance containing silicon is generally used as a raw material for producing the mesopore material. As such a substance containing silicon, various layered silicates or various silicon-containing substances other than layered silicates have been disclosed in JP-A-8-067578.

As the layered silicate, kanemite, sodium disilicate crystal, macatite, ilaite, magadiite, kenyaite, etc. are disclosed, and silicon-containing substances other than the layered silicate include powdered sodium silicate, tetraethyl orthosilicate. , Water glass, glass, amorphous sodium silicate, silica, silica-alumina, mixed substances of silica and alumina, silica oxide, silica-metal composite oxide, etc. have been disclosed.

By the way, it has been conventionally known that it is easier to obtain an excellent mesopore material having a more uniform pore diameter and high crystallinity by using a sheet-like layered silicate as a raw material for producing the above-mentioned mesopore material. ing. And, as such sheet-like layered silicate, three kinds of kanemite, sodium disilicate crystal, and macatite have a structure composed of a silicon dioxide tetrahedral sheet which is easily bent, so that more mesopore material can be produced. Suitable for raw materials.

The mesopore material having a uniform pore diameter and high crystallinity has excellent properties such as "shape selectivity" such as "selective catalytic reaction" and "selective adsorption separation function". The above "selective catalytic reaction" means that when the above mesopore material is used as a carrier or a synthesis site, only reactive molecules having a size smaller than the diameter of the pore can be selectively reacted, or It means that only a reaction product having a size smaller than the diameter can be produced.
This allows you to react only the target reactive molecules,
It is possible to generate only the reaction product.

Further, the above-mentioned "selective adsorption separation function" means
When adsorbing or desorbing a gas on the mesopore material or fixing the gas, only a specific gas in the mixed gas is adsorbed, desorbed or desorbed depending on the size of the gas molecules with respect to the pore diameter of the pores. It means that it can be fixed.

Therefore, the mesopore material has a uniform size of mesopores having a specific pore size in the range of 2 nm to 10 nm when used as a catalyst carrier for a catalytic reaction or an adsorbent having an adsorptive separation function. The excellent performance of shape selectivity for molecules smaller than the pore size can be exhibited.

[0009]

However, the mesopore material produced from the above layered silicate has the following problems. That is, the size of the silicon dioxide tetrahedral sheet that constitutes these three types of layered silicate, that is, the sheet diameter is 1 μm.
Greater than above. Therefore, the major axis diameter of the primary particles of the mesopore material produced from the layered silicate is about 2 μm or more, which is very large. Furthermore, the naturally-occurring layered silicates with the same size of the above-mentioned sheets have low versatility and are limited in availability.

As the above-mentioned layered silicate, not a natural product,
It is more common to use kanemite or sodium disilicate crystals artificially synthesized from water glass. However,
Since the artificially synthesized layered silicate silicon dioxide tetrahedral sheet is not uniform in size, it is difficult to obtain a mesopore material in which primary particles are uniform in size, and the mesopore material obtained from the above layered silicate is difficult to obtain. The major axis diameter of primary particles is 1
The particles are scattered in a wide range of 0 nm to 5 μm (by observation with a transmission electron microscope photograph).

Further, in the artificially synthesized layered silicate, the size of the silicon dioxide tetrahedral sheet is as large as 1 μm or more. In view of the above points, conventional mesopore materials are often composed of large and irregular primary particles, and the ratio of the surface area inside the pores to the surface area outside the particles is not uniform among the particles, and the length of the pores is not uniform. Because of the non-uniformity, it was difficult to obtain a catalyst carrier or an adsorbent that exhibits a sufficient stable action when used in the field of application.

Further, in the mesopore material composed of the above layered silicate, the sizes of the primary particles are likely to be uneven, so that the uniformity of the pores is easily deteriorated and the mesopore material having low crystallinity is likely to be obtained.

When the mesopore material is produced from the above-mentioned three types of layered silicate, it is possible to hydrolyze the layered silicate to subdivide the layered silicate. According to this operation, even if the sheet diameter of the layered silicate is large, it is smaller,
It is considered that primary particles of uniform size can be obtained. However, the p of the dispersion of the above three types of layered silicate in water is
Since H is 11 or more, in order to hydrolyze the layered silicate, it is necessary to add an alkali to the dispersion liquid and use a special reactor. Therefore, it is difficult to manufacture the mesopore material using the above layered silicate, and the manufacturing cost is high.

As described above, it is difficult to easily synthesize a conventional mesopore material produced from a layered silicate having a uniform pore diameter, high crystallinity, and a small primary particle size. Met.

Further, in the case where the size of the primary particles is smaller, there are more short pores in a given weight, that is, the number of pore inlets is larger and the number of molecules entering the pores is shorter. There is a field of application such as catalyst carriers and adsorbents that utilize the length of the pores generated in the above. On the other hand, for larger primary particles, there are fewer long pores in a given weight. , Ie the number of pore inlets is smaller,
In addition, it is thought that there is a field of application such as catalyst carriers and adsorbents that utilize the existence of long pores that take more time for the molecules entering inside to exit, but it consists of primary particles of a size according to the purpose No method has previously been disclosed for producing mesopore materials.

In view of the above problems, the present invention is composed of primary particles having a small size and uniform size, the pore diameter of the pores (mesopores) is uniform, and the crystallinity is high. optionally can be selected, manufacturability and manufacturing cost is inexpensive, is intended to provide a main Sopoa materials and manufacturing method thereof.

[0017]

The invention of claim 1 has a pore diameter of 2 to
A mesopore material having pores (mesopores) in the range of 10 nm and having primary axis particles having a major axis diameter in the range of 10 nm to 1 μm and also composed of a layered silicate obtained from a clay mineral. The above-mentioned pores have a maximum peak in the pore distribution curve in a pore diameter range of 2 to 10 nm, and 75% or more of all pores exhibit the maximum peak in the pore distribution curve. in the characteristic and to Rume Sopoa material that has a pore diameter in the range of -40 to + 40% of the pore diameter.

The mesopore material of the present invention is formed by assembling submicron-order primary particles having a large number of pores (mesopores). The major axis diameter is 10
When it is less than nm, the pore diameter is 2 nm to 10 nm, and therefore a sufficient number of pores cannot be present in the primary particles, so that there is a possibility that a porous body cannot be obtained. On the other hand, when the major axis diameter exceeds 1 μm, the difference between the major axis diameter of the smallest primary particles is widened, and the primary particles may be uneven in size.

When the pore diameter is less than 2 nm, there is a possibility that the pore diameter is too small and the pore diameter enters the region of the micropore material instead of the mesopore material. On the other hand, when the pore diameter exceeds 10 nm,
The difference between the smallest pore diameter may open and the homogeneity and crystallinity of the pores may decrease.

Further, if the pore diameter of 75% or more of all the pores is not within the range of -40 to + 40% of the pore diameter showing the maximum peak in the above-mentioned pore distribution curve, the uniformity of the pores. If so, the crystallinity may decrease.

The operation of the present invention will be described below. In the mesopore material of the present invention, the pore diameter and the major axis diameter of the primary particles are within the above specified range, and the pore diameter of 75% or more of all the pores satisfies the above condition. Therefore, the mesopore material according to the present invention is small and is composed of primary particles of uniform size. Therefore, the ratio of (external surface area of particle / internal surface area of pore) in each primary particle is particularly large as compared with the conventional mesopore material (see Embodiment 10).

Therefore, even when the supported catalyst occludes the pores, the large surface area of the mesopore material can be effectively used for the catalytic reaction, and more pores that are reaction fields or adsorption fields can be provided in a given weight. The effect of being present can be obtained. Also, because the size of the primary particles is small,
It is possible to obtain the effect that the length of the pores becomes shorter, and the molecules that have entered the pores are immediately released.

Furthermore, since the sizes of the primary particles are uniform, the ratio of (particle outer surface area / pore inner surface area) becomes substantially constant among the respective primary particles. Therefore, the ratio of the catalytic reaction and the adsorption reaction by the outer surface of the particles and the inner surface of the pores can be made substantially constant between the primary particles, so that the reaction can be stably performed as a whole. Furthermore, since the primary particles have the same size, it is possible to prevent the generation of secondary particles due to aggregation of the primary particles. Therefore, the mesopore material according to the present invention has excellent dispersibility in an organic solvent (see Embodiment 13), and the degree of association of primary particles in the organic solvent is low. Even in the reaction, it is possible to obtain a new industrial use method that exerts an excellent action as a catalyst carrier or an adsorbent.

Furthermore, the mesopore material according to the present invention has excellent uniformity of pore diameter and high crystallinity. Therefore, the mesopore material of the present invention has high heat resistance, and has excellent properties such as "selective catalytic reaction" and "selective adsorption separation function" such as "shape selectivity". The effect of being able to be used for the reaction and the effect of higher shape selectivity based on the high uniformity of the pore diameter can be obtained.

As described above, according to the present invention, it is possible to provide a mesopore material which is composed of primary particles of small size and uniform, and has a uniform pore diameter (mesopore) and high crystallinity. .

Further, the mesopore material according to the present invention can be produced by utilizing the layered silicic acid prepared from clay mineral as described later, and in that case, it is produced by promoting the hydrolysis of the layered silicic acid. You can That is, the concentration of the alkali metal compound with respect to the layered silicic acid is increased,
It can be produced by increasing the reaction temperature and increasing the reaction time.

Next, the invention of claim 2 has a pore diameter of 2 to
A mesopore material which has pores (mesopores) in the range of 10 nm and has primary particles whose major axis diameter is in the range of 50 nm to 2 μm and which is composed of a layered silicate obtained from a clay mineral. The pores have a maximum peak in the pore distribution curve in a diameter range of 2 to 10 nm, and 60% or more of all pores exhibit the maximum peak in the pore distribution curve. in the characteristic and to Rume Sopoa material that has a pore diameter in the range of -40 to + 40% of the pore diameter.

The mesopore material of the present invention, like the mesopore material described in claim 1, is composed of primary particles having a small size and uniform size, and has a uniform pore diameter and high crystallinity. Have

When the major axis diameter of the primary particles is less than 50 nm, the difference between the major axis diameter of the largest primary particles and the major axis diameter of the largest primary particles may open, and the sizes of the primary particles may become uneven. On the other hand, when the major axis diameter of the primary particles exceeds 2 μm, the difference between the smallest major axis diameter and the major axis diameter of the primary particles is increased, and the primary particles may be uneven in size. Others are the same as those in claim 1.

The mesopore material according to claim 2 is
As will be described later, the layered silicic acid prepared from a clay mineral can be used for the production, and the hydrolysis can be suppressed by suppressing the hydrolysis of the layered silicic acid. That is, it can be produced by reducing the concentration of the alkali metal compound relative to the layered silicic acid, lowering the reaction temperature, and shortening the reaction time.

Next, according to the third aspect of the present invention, an acid is applied to the clay mineral to form a layered silicic acid, and then an alkali metal compound is allowed to act on the layered silicic acid to form a layered silicate, and then the layered. Applying a surfactant to the silicate,
To form a silicate three-dimensional structure, without a condensate that includes a surfactant therein, and then in the production method of the characteristics and to Rume Sopoa material to remove the surfactant from the condensate .

In the production method of the present invention, layered silicic acid produced from clay mineral is used as a raw material for producing the mesopore material. The layered silicic acid is a substance composed of a silicon dioxide tetrahedral sheet, as shown in FIG. 1 described later, and can be obtained by subjecting a clay mineral to an acid treatment. The layered silicic acid is in a state in which the skeleton of the silicon dioxide tetrahedral sheet existing in the raw material clay mineral remains.

Furthermore, the layered silicic acid becomes a layered silicate by the action of the alkali metal compound while maintaining its skeleton. Further, due to the action of the surfactant, the layered silicate becomes a condensate. However, as shown in FIG. 1 to be described later, this condensate is formed between the layered silicate and each layer of the silicon dioxide tetrahedral sheet of the layered silicate. It is composed of the included surfactant and has a structure and size that reflects the state of the original layered silicate.
And in the present invention, as shown in FIG.
A final product, a mesopore material, is obtained from the above condensate.

The clay minerals have many kinds naturally and their structures are also diverse. The layered silicic acid according to the present invention can be obtained by acid treatment in any of these various clay minerals. Therefore, by using different clay minerals as raw materials, layered silicic acid having different structures can be easily obtained.

Therefore, according to the present invention, it is possible to obtain a mesopore material according to the type of clay mineral as a starting material, and by selecting the clay mineral, it is possible to obtain a variety of primary particles having a desired size. Various mesopore materials can be manufactured.

Further, in the production method of the present invention, an alkali metal compound is allowed to act on layered silicic acid to form a layered silicate. Depending on the conditions for producing the layered silicate, it is possible to cause or suppress hydrolysis of the layered silicic acid. When hydrolysis occurs, the mesopores having a small primary particle size and uniform size, a high uniformity of pore diameters, and excellent crystallinity as described in claim 1 are obtained. The material can be obtained.

On the other hand, when hydrolysis is suppressed, it is possible to obtain a mesopore material having small and uniform primary particles, high pore uniformity and high crystallinity as described in claim 2. . The mesopore material according to claim 1 is
It can be used as a catalyst carrier or adsorbent, etc., and it has high catalytic activity even in liquid phase reaction because it has low association in addition to the catalytic ability and adsorption ability based on short pores, and it supports catalysts larger than the pore diameter. Even if it has a high surface area, it exhibits excellent properties.

The mesopore material according to claim 2 is
It can be used as a catalyst carrier, an adsorbent, etc. and provides pores longer than the mesopore material of claim 1 but shorter than the conventional mesopore material in which kanemite was synthesized,
It has the excellent property of exerting a moderate degree of catalytic reaction and adsorption. According to the present invention, any mesopore material can be obtained in this way.

Further, although the details of the manufacturing method of the present invention will be described later, all the operations are operations with low difficulty,
And it can be achieved by a general device. Therefore, the present invention is easy to manufacture. In addition, the manufacturing cost is low because there is no need to do anything special.

As described above, according to the present invention, the size of the primary particles to be obtained can be arbitrarily selected, and the mesopore material and the method for producing the mesopore material, which are easy to produce and inexpensive to produce, are provided. can do.

The above manufacturing method will be described in detail below. The layered silicic acid obtained by the acid treatment of the clay mineral includes layered silicic acid having no crystallographic regularity and layered silicic acid having crystallographic regularity. In the present invention, both can be used. In addition, these layered silicic acids take various sheet shapes by leaving the remains of the silicon dioxide tetrahedral sheet in the clay mineral.

The clay mineral is not particularly limited, but for example, a clay mineral having a 1: 1 layer or a 2: 1 layer structure of a silicon dioxide tetrahedral sheet and an octahedral sheet of another metal oxide is used. can do. And as such a clay mineral, the following three types can be used.

The first is a clay mineral having a 1: 1 layer structure of a silicon dioxide tetrahedral sheet having no inversion, A
Kaolinite, dickite, nacrite, halloysite, etc. having an octahedral sheet of 1; chrysotile and lizardite having an octahedral sheet of Mg can be mentioned.

The second is a clay mineral having a 2: 1 layer structure of a silicon dioxide tetrahedral sheet having no inversion, A
Pyrophyllite with l-octahedral sheet, muscovite mica,
Montmorillonite, beidellite, dioctahedral vermiculite, talc having Mg octahedral sheet, phlogopite, saponite, hectorite, Mg vermiculite, etc., octahedral vermiculite having Fe octahedral sheet, nontronite, etc. Can be mentioned.

The third is a clay mineral consisting of a silicon dioxide tetrahedral sheet with inversion, an octahedral sheet of Mg and a sepiolite, palygorskite, and an octahedral sheet of Mg having a 2: 1 layer structure and a 1: 1 ratio. Examples thereof include antigorite having a layered structure.

In the above description of "no reversal" in the silicon dioxide tetrahedral sheet, the directions of the vertices of the tetrahedra in the silicon dioxide tetrahedral sheet are aligned in one direction, and the polarity distribution on the surface of the silicon dioxide tetrahedral sheet is It means that the back and front are in different states. On the contrary, "there is a reversal" means that the vertices of the tetrahedron are alternately face-up and face-down in the adjacent tetrahedron, and the polarity distribution on the surface of the silicon dioxide tetrahedron sheet is shown. Means that the whole is in a uniform state.

The acid used in the above acid treatment is preferably one having a high solubility in water so that the aluminum salt or magnesium salt formed as a result of the reaction can be taken in the post-treatment step. Specifically, an aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like or a mixture thereof can be used. Further, the concentration of the acid is not particularly limited, but it is preferable to use 3N (normal) or more because the reaction rate becomes faster. The amount of acid used for this acid treatment is preferably an aqueous solution of the aforementioned acid in which at least 2 mol or more of acid is dissolved in 100 g of clay mineral.

The above-mentioned acid treatment can be carried out under either normal pressure conditions or pressure conditions. As a method of acid treatment under normal pressure conditions, it is preferable to immerse the clay mineral in these aqueous acid solutions and heat and stir under normal pressure conditions in a reactor equipped with a cooling concentrator. As a method of acid treatment under pressure, it is preferable to immerse clay mineral in these acid aqueous solutions and heat and stir under pressure. After completion of the reaction, it is preferable that the reaction mixture is thoroughly washed with 1N hydrochloric acid and water and freeze-dried to obtain layered silicic acid.

Next, the step of reacting the layered silicic acid obtained from the above clay mineral with an alkali metal compound to form a layered silicate will be described. The above step is a step of exchanging the proton of the silanol group of the layered silicic acid with an alkali metal cation to form a layered silicate. At this time, alkaline hydrolysis of the silicon dioxide tetrahedron sheet occurs as a side reaction, so that a layered silicate which is a small fragment is obtained. Such alkaline hydrolysis of the silicon dioxide tetrahedral sheet is unlikely to occur in the layered silicate.

The alkali metal compound used here is preferably one in which the acidity of the compound consisting of the anion portion and the proton of the alkali metal compound formed as a result of the reaction is sufficiently low. Specific examples thereof include hydroxides, carbonates, hydrogen carbonates and acetates of alkali metals.

Since the degree of the above-mentioned side reaction can be controlled by selecting the reaction conditions with the alkali metal compound, it can be used as a means for arbitrarily selecting the size of the primary particles of the finally obtained mesopore material. It is possible. Also,
The size of the primary particles of the obtained mesopore material also depends on the type of layered silicic acid used.

In the reaction of the layered silicic acid with the alkali metal compound, the layered silicic acid which leaves the skeleton of the band-shaped clay mineral is used, or the reaction condition with the alkali metal compound is made more strict (for example, the alkali metal compound). Can be prepared by increasing the concentration of the above and reacting at a higher temperature for a longer period of time). As a result, the size of the primary particles of the finally obtained mesopore material can be reduced, and the pore size of the mesopore material can be made more uniform and the crystallinity can be made higher than before.

In order to produce the mesopore material according to claim 1, it is preferable to carry out a reaction with the alkali metal compound as described below. First, it is preferred to promote hydrolysis of the silicon dioxide skeleton of layered silicic acid to prepare small pieces of layered silicate. Then, the concentration of the alkali metal compound is set to 1 N or more, the ratio of the alkali metal ion to silicon atoms is set to 0.3 to 3 mol / mol, the reaction temperature is set to room temperature or more and 100 ° C. or less, and the reaction time is set. Is preferably 30 minutes or more.

Further, it is particularly preferable to use a band-shaped layered silicic acid having a band width of 200 nm or less. Examples of such layered silicic acid include layered silicic acid obtained by acid treatment such as sepiolite and chrysotile. As a result, as described in claim 1, it is possible to obtain an excellent mesopore material having a small size and uniform size of primary particles, a uniform pore diameter, and high crystallinity.

On the other hand, in order to produce the mesopore material according to the second aspect, it is preferable to carry out a reaction with the alkali metal compound as shown below. First, it is preferable to suppress the hydrolysis of the silicon dioxide skeleton of the layered silicic acid. Then, the concentration of the alkali metal compound is set to 1 N or less, the ratio of alkali metal ion to silicon atom is set to 0.1 to 1.2 mol / mol, the reaction temperature is set to room temperature or lower, and the reaction time is set. It is preferably within 30 minutes.

It is particularly preferable to use layered silicic acid having a sheet diameter of the silicon dioxide tetrahedral sheet of 3 μm or more. Examples of such layered silicic acid include layered silicic acid obtained by acid treatment such as vermiculite and kaolinite. As a result, as shown in claim 2, an excellent mesopore material in which the size of primary particles is small and uniform can be obtained.

Next, the step of acting a surfactant on the layered silicate to form a condensate and removing the surfactant from the condensate will be described. First, in the above process, an aqueous dispersion of a layered silicate is mixed with an aqueous solution in which a surfactant is dissolved, and the temperature is set to 50 ° C. or higher, thereby forming a condensate of the layered silicate and the surfactant. Form.

The concentration of the aqueous solution of the above surfactant is 0.0
It is preferably 1 to 1 M (mol / liter).
Further, the amount of the layered silicate dispersed is 8 to 200 g with respect to 1000 ml of the aqueous surfactant solution having a concentration of 0.02M.
Is preferred. Further, in this step, it is preferable to heat the aqueous solution (dispersion liquid) containing the layered silicate and the surfactant, because the introduction of the surfactant into the layered silicate is promoted. The heating temperature of the aqueous solution (dispersion) is preferably 40 to 100 ° C.

As the above-mentioned surfactant, for example, a substance having an ammonium group at the terminal such as alkyltrimethylammonium, dimethyldialkylammonium, alkylammonium, benzyltrimethylammonium can be used. Alternatively, terminal sulfonic acid group (-SO ₃ H), carboxyl (-CO ₂ H), can be used at least one selected from the group of compounds having a phosphoric acid group (-O-PO ₃ H), etc. .

The pH of the aqueous solution (dispersion) is adjusted to 10
It is preferable that the temperature is less than 50 ° C. and the temperature is 50 ° C. or higher. As a result, as shown in FIG. 1 described later, dehydration condensation of silanol groups existing on the surface of the adjacent layer of the layered silicate occurs, and each layer can partially bond with each other. As a result, as shown in FIG. 1 described later, the layered silicate forms a three-dimensional structure (honeycomb structure) made of silicate, and the inside of the three-dimensional structure (holes of the honeycomb structure)
It becomes a condensate in which a surfactant is included.

It is more preferable to maintain the pH of the above dispersion in the range of 6 to 8.5. By maintaining the temperature of the dispersion liquid at 50 ° C. or higher, the dehydration condensation of the silanol groups can be further promoted. Further, the ripening of the dispersion is preferably carried out by adjusting the pH of the dispersion and until the pH becomes stable. When the temperature is kept at 50 ° C or higher,
It is preferable to hold for 2 hours or more.

Finally, as shown in FIG. 1 described later, the surfactant is removed from the obtained condensate. By this removal,
The above-mentioned three-dimensional structure becomes the mesopore material according to the present invention, and the pores after removal of the surfactant become pores (mesopores).

As a method for removing the above-mentioned surfactant, a method by firing or ion exchange can be mentioned.
In the firing method, the surfactant in the condensate is
It is decomposed and removed by combustion. The firing temperature at that time is 500
It is preferably ˜1000 ° C.

On the other hand, in the ion exchange method, the surfactant in the condensate is ion-exchanged with hydrogen ions for removal. Although hydrogen ions remain in the pores (pores) formed by removing the surfactant, the ionic radius of hydrogen ions is 0.1 nm or less, which is sufficiently larger than the size of the pores. small. Therefore, the problem of blockage of the pores due to the hydrogen ions does not occur.

It is also possible to add a step of removing the water-soluble component after mixing the aqueous dispersion of the layered silicate with the aqueous solution of the surfactant to form a condensate of the layered silicate and the surfactant. it can. By this step, it is possible to remove a part of the water-soluble component eluted from the layered silicate as silicate ions. The above water-soluble component is a component that becomes amorphous silica gel and precipitates at a pH around neutral.

The step of removing the water-soluble component can be carried out by forming a condensate of the layered silicate and the surfactant and then separating the solid content from the aqueous solution (dispersion). Specifically, the separated solid content is dispersed again in distilled water to obtain a dispersion liquid. Then, the condensate is formed by adjusting the pH of the dispersion to less than 10 and the temperature to 50 ° C. or higher. Furthermore, the solid content can be separated by filtration, centrifugation or the like. By performing this water-soluble component removal step, the crystallinity of the mesopore material can be further enhanced.

[0067]

DETAILED DESCRIPTION OF THE INVENTION

Embodiment 1 A mesopore material and a method for producing the same according to an embodiment of the present invention will be described with reference to FIG. As shown in FIG. 1, the mesopore material 1 of this example has a pore diameter of 2 to 10 nm.
Is a mesopore material composed of primary particles having pores (mesopores) 10 in the range of 10 and having a major axis diameter in the range of 10 nm to 1 μm. The pores 10 have a pore diameter of 2 to 10 n, which shows the maximum peak in the pore distribution curve.
m, and 75% or more of all pores show the maximum peak in the above-mentioned pore distribution curve.
Pore diameters in the range of + 40%.

The mesopore material 1 is manufactured by the following method. As shown in FIG. 1, acid is made to act on clay mineral to form layered silicic acid, and then alkali metal compound is made to act on the layered silicic acid to form layered silicate 11. Next, a surfactant 15 is allowed to act on the layered silicate 11 to form a honeycomb-shaped three-dimensional silicate structure 14, and a condensate 13 containing the surfactant 15 therein.
And eggplant The three-dimensional structure 14 has a large number of holes 1
40, and the surfactant 15 is placed in the hole 140.
Form rod-shaped micelles 150. Then, the surfactant 15 is removed from the condensate 13. As a result, the three-dimensional structure 14 becomes the mesopore material 1 and the voids 14
0 is the pore 10.

In this example, as the clay mineral, sepiolite, which is a clay mineral having a striped morphology and a 2: 1 layer structure of a silicon dioxide tetrahedral sheet with inversion and an octahedral sheet of magnesium oxide, was used. . An aqueous solution of NaOH was used as the alkali metal compound. Furthermore, cetyl trimethyl ammonium chloride (CTMA-Cl) was used as the surfactant.

Next, the mesopore material and the manufacturing method thereof will be described in detail. First, an acid was allowed to act on the clay mineral sepiolite under normal pressure to produce a layered silicic acid in which the band-shaped bodies of silicate in sepiolite remained. As the sepiolite, β-sepiolite produced in Turkey was coarsely crushed with a jaw crusher, and then 10 m
An average particle size of 10 μm was obtained by crushing with a ball mill using m-diameter steel balls.

250 g and 3 of the above ground crushed sepiolite
2000 ml of N hydrochloric acid was placed in a 2 liter separable flask equipped with a condenser, and heated in a water bath at a water bath temperature of 90 ° C. for 10 hours while stirring with a stirring motor. The contents of the flask were filtered by hot filtration, and the obtained solid product was warmed to about 70 to 90 ° C with 1.2N hydrochloric acid (1N).
It wash | cleaned on the funnel using 000 ml and 2000 ml of warm ion-exchange water.

Washed solid product and 1N hydrochloric acid 200
0 ml was placed in a 2 liter separable flask equipped with a condenser and heated in a water bath at a water bath temperature of 90 ° C. for 1 hour while stirring with a stirring motor. After heating, the solid product filtered off from the contents of the flask was washed on the funnel with 10000 ml of warm ion-exchanged water, 8
The crude product was obtained by vacuum drying at 0 ° C. for 3 days 115.
4 g was obtained. The crude product contains humic acid as an impurity.

Next, in order to remove humic acid, 110 g of the above crude product and 600 ml of 30% hydrogen peroxide solution were placed in a 2 liter separable flask equipped with a condenser, and the water bath temperature was 90 ° C. for 4 hours. The mixture was heated in a water bath while stirring with a stirring motor for a period of time. The solid product filtered from the contents of the flask by hot filtration was washed on a funnel with 2000 ml of warm ion-exchanged water at about 70 to 90 ° C.

Washed solid product and deionized water 2
000 ml was placed in a 2 liter separable flask equipped with a cooling tube, and the water bath temperature was 90 ° C. for 1 hour.
The mixture was heated in a water bath while stirring with a stirring motor. The solid product filtered from the contents of the flask was washed. The same heat washing operation was repeated using 1000 ml of 1N hydrochloric acid. The solid product finally filtered off was heated at 80 ° C.
The product was vacuum dried for 3 days to obtain 105.3 g of a product. This product is called NS-1a.

The above product NS-1a is a silicic acid mainly composed of silicon from the result of elemental analysis, and it is a layered silicic acid in the form of a band in which a band-shaped body of the silicate in sepiolite remains from the observation of a transmission electron micrograph. I knew it was.

Next, the layered silicic acid NS-1a having the above-mentioned strip shape is formed.
Then, an aqueous solution of NaOH, which is an alkali metal compound, is made to act. At this time, a molar ratio of Na / Si = about 0.02 between Si atoms in the layered silicic acid and Na ions in the NaOH aqueous solution.
There is a relationship of 3 (mol / mol).

10 g of the layered silicic acid NS-1a and 200 ml of ion-exchanged water were placed in a 1-liter plastic beaker and heated in a water bath at a water bath temperature of 95 ° C. while stirring with a stirring motor. Into the beaker, 50 ml of a 1N NaOH aqueous solution was added, and the dispersion was heated in a water bath for 30 minutes while stirring with a stirring motor while maintaining the temperature of the dispersion at about 70 ° C. The pH of the dispersion at this time
Was 10.7-10.2.

Next, 4.0 g of cetyltrimethylammonium chloride (CTMA-Cl) was added to ion-exchanged water 4
A warm aqueous solution dissolved in 00 ml was mixed with the layered silicic acid dispersion, and the dispersion was heated in a water bath for 1 hour while stirring with a stirring motor while maintaining the temperature at about 70 ° C.

2N HCl was further added dropwise to the above dispersion to adjust the pH to 8.5, and the temperature of the dispersion was adjusted to about 70.
The mixture was heated in a water bath while stirring at a stirring motor for 2 hours while maintaining the temperature at ℃. The solid product filtered off from the contents of the beaker by hot filtration was washed on a funnel with 2000 ml of warm ion-exchanged water at about 70 to 90 ° C,
Vacuum dried at 110 ° C. overnight. The obtained solid product is
By calcination in air at 650 ° C. for 4 hours, 6.8 g of mesopore material was obtained. This mesopore material is called FS-1.

From the observation of the X-ray diffraction pattern and the observation of the transmission electron micrograph of the above mesopore material FS-1 (see Embodiments 8 and 12 described later), it was found that the crystals had a hexagonal structure and were excellent in the uniformity of the pores. Being a highly mesopore material, and having a major axis of primary particles of 10 nm-
It was found that the size was in the range of 1 μm and the sizes were uniform.

From the above, it was found that the mesopore material according to the present invention is composed of primary particles of small size and uniform size, the pore diameter of the pores (mesopores) is uniform, and the crystallinity is high. Therefore, it was found that the mesopore material according to this example is a suitable material in the application field of catalyst carriers and adsorbents. Further, it has been found that the manufacturing method according to the present invention does not require a special operation or device, so that the manufacturing is easy and the manufacturing cost is low.

Embodiment 2 In this embodiment, the strip-like layered silicate NS-1a prepared in Embodiment 1 was reacted with an aqueous NaOH solution at 70 ° C. for 30 minutes to produce primary particles having a major axis of 10 nm to
The mesopore material in the range of 1 μm and its manufacturing method will be described. However, Si atoms and NaOH in layered silicic acid
The molar ratio between Na ions in the aqueous solution is Na / Si =
There is a relationship of about 1.0 (mol / mol).

Using the same manufacturing method as in Embodiment 1, 150 ml of a 1N NaOH warm aqueous solution was used to prepare a mesopore material from 10 g of layered silicic acid NS-1a.
5 g was obtained. This mesopore material is called FS-2. The pH of the layered silicic acid dispersion added with 150 ml of a 1N NaOH aqueous solution was about 12.

From the observation of the X-ray diffraction pattern and the transmission electron micrograph of the above mesopore material FS-2 (see Examples 8 and 12 described later), it was found that this was a crystal having a hexagonal structure with excellent pore uniformity. Being a highly mesopore material, and having a major axis of primary particles of 10 nm-
It was found that the size was in the range of 1 μm and the sizes were uniform.

Embodiment 3 In this example, a clay mineral chrysotile having a 1: 1 layer structure of a non-inverted silicon dioxide tetrahedral sheet and an octahedral sheet of magnesium oxide and having a tubular morphology was subjected to acid treatment under normal pressure. The method for producing a layered silicic acid in which tubular skeletons of silicate in the chrysotile remain, and a method for producing a mesopore material using the layered silicic acid, and the mesopore material will be described.

As the above chrysotile, Calidria Asbestos manufactured by Union Carbide is used.
H. P. P. Was used. 200 g of the chrysotile crushed in a mortar and 2000 ml of 3N hydrochloric acid were placed in a 2 liter separable flask equipped with a cooling tube and heated in a water bath at a water bath temperature of 90 ° C. for 4 hours while stirring with a stirring motor.

The contents of the flask were filtered by hot filtration, and the obtained solid product was washed on a funnel with 1000 ml of warm 1N hydrochloric acid at about 70 to 90 ° C. and 2000 ml of warm deionized water. did. The washed solid product and 1200 ml of 1N hydrochloric acid were placed in a 2 liter separable flask equipped with a condenser and heated in a water bath at a water bath temperature of 90 ° C. for 1 hour while stirring with a stirring motor. The solid product filtered off from the contents of the flask was washed with 2000 ml of warm deionized water on the funnel. The washed solid product was freeze-dried to obtain 84.5 g of the product. This product is NC
-3a.

From the results of elemental analysis, the above product NC-3a was found to be silicic acid mainly composed of silicon, and from the observation of transmission electron micrographs, it was found to be tubular silicic acid in which the silicate bodies in chrysotile remained. Do you get it.

Next, the tubular layered silicate NC-3a was
Aqueous NaOH solution is applied. At this time, S in the layered silicic acid
There is a molar ratio Na / Si = about 2.0 (mol / mol) between the i atom and the Na ion in the aqueous NaOH solution. 10 g of the layered silicic acid NC-3a and 200 ml of ion-exchanged water were placed in a 1-liter plastic beaker and heated in a water bath at a water bath temperature of 95 ° C. while stirring with a stirring motor. Into the beaker, add 1N NaO
300 ml of H-warm aqueous solution was added, and the dispersion was heated in a water bath for 30 minutes while being stirred with a stirring motor while maintaining the temperature of the dispersion at about 70 ° C. At this time, the pH of the dispersion is
It was 11.7-11.3.

Next, 4.0 g of cetyltrimethylammonium chloride (CTMA-Cl) was added to ion-exchanged water 4
A warm aqueous solution dissolved in 00 ml was mixed with the layered silicic acid dispersion, and the dispersion was heated in a water bath for 1 hour while stirring with a stirring motor while maintaining the temperature at about 70 ° C.

2N HCl was further added dropwise to the above dispersion to adjust the pH to 8.5, and the temperature of the dispersion was adjusted to about 70.
The mixture was heated in a water bath while stirring at a stirring motor for 2 hours while maintaining the temperature at ℃. The contents of the beaker were filtered off by hot filtration, and the obtained solid product was washed on a funnel with 2000 ml of warm ion-exchanged water at about 70 to 90 ° C. The washed solid product was vacuum dried at 110 ° C. overnight. The obtained solid product was heated in air at 650 ° C. for 4 hours.
By firing for an hour, 8.4 g of mesopore material was obtained.
This mesopore material is called FC-3.

From the observation of the X-ray diffraction pattern and the transmission electron micrograph of the above mesopore material FC-3 (see Embodiments 8 and 12 described later), it was found that the crystals had a hexagonal structure and were excellent in the uniformity of the pores. Being a highly mesopore material, and having a major axis of primary particles of 10 nm-
It was found that the size was in the range of 1 μm and the sizes were uniform.

Embodiment 4 In this embodiment, the tubular layered silicic acid NC-3a prepared in Embodiment 3 is reacted with an aqueous solution of NaOH for 30 minutes at room temperature so that the major axis of the primary particles is in the range of 10 nm to 1 μm. The method of manufacturing the mesopore material and the mesopore material described in 1. However, the Si atom in the layered silicic acid and the Na ion in the NaOH aqueous solution have a relationship of molar ratio Na / Si = about 2.0 (mol / mol).

10 g of the layered silicic acid NC-3a and 200 ml of ion-exchanged water were placed in a 1-liter plastic beaker and stirred with a stirring motor at room temperature. 300 ml of a 1N NaOH aqueous solution was added to the beaker, and the mixture was stirred with a stirring motor at room temperature for 30 minutes. In addition,
At this time, the pH of the dispersion was 12.2 (27 ° C).

Next, 4.0 g of cetyltrimethylammonium chloride (CTMA-Cl) was added to ion-exchanged water 4
A warm aqueous solution dissolved in 00 ml was mixed with the layered silicic acid dispersion, and a beaker containing the dispersion was immersed in a water bath maintained at 90 ° C. Then, the temperature of the dispersion liquid is set to about 7
The mixture was heated in a water bath while stirring at a stirring motor for 1 hour while maintaining the temperature at 0 ° C. Furthermore, 2N HCl was added dropwise to the above dispersion liquid to adjust the pH to 8.5.

Then, while maintaining the temperature of the above dispersion liquid at about 70 ° C., it was heated in a water bath for 2 hours while being stirred by a stirring motor. The above-mentioned dispersion is filtered by hot filtration, and the obtained solid product is heated to about 70 to 90 ° C. in warm ion-exchanged water 2000.
Wash on funnel with mL. The washed solid product was vacuum dried at 110 ° C. overnight. The solid product was calcined in air at 650 ° C. for 4 hours to obtain 8.4 g of a mesopore material. This mesopore material is called FC-4.

From observation of the X-ray diffraction pattern and transmission electron micrograph of FC-4 of the above mesopore material (see Embodiments 8 and 12 to be described later), it was confirmed that the mesopore material had a hexagonal structure with excellent pore uniformity. It is a highly crystalline mesopore material, and the major axis of the primary particles is 10 nm.
It was found that the size was in the range of up to 1 μm and the sizes were uniform.

Embodiment 5 In this example, a 2: 1 layer structure of a non-inverted silicon dioxide tetrahedral sheet and an octahedral sheet of magnesium oxide, a hectorite, which is a clay mineral having a small sheet-like morphology, is subjected to normal pressure. A method for producing a layered silicic acid in which sheet-like bodies of silicate in the hectorite remain, and a method for producing a mesopore material using the layered silicate, and the mesopore material will be described.

A standard sample of the American Clay Society was used as the hectorite. Hectorite 200.5g and 3 above
1600 ml of N hydrochloric acid was placed in a 2 liter separable flask equipped with a condenser, and the water bath temperature was 30 ° C.
For 0.5 hours, and further at a water bath temperature of 90 ° C. for 4 hours while heating with a stirring motor in a water bath.

The contents of the flask were filtered off by hot filtration, and the solid product obtained was washed on a funnel with 1000 ml of warm 1N hydrochloric acid at about 70 to 90 ° C. and 2000 ml of warm deionized water. did. The washed solid product and 1600 ml of 1N hydrochloric acid were placed in a 2 liter separable flask equipped with a condenser and heated in a water bath at a water bath temperature of 90 ° C. for 1 hour while stirring with a stirring motor. Then, the contents of the flask are filtered off,
The obtained solid product is heated on a funnel and warmed with ion-exchanged water 300.
Washing with 0 ml followed by lyophilization gave 72.6 g of product. This product is called NH-5a.

From the results of elemental analysis, the above-mentioned product NH-5a was found to be silicic acid containing silicon as a main component, and from observation by a transmission electron microscope photograph, it was found that silicic acid containing silicate particles in hectorite remained. It was

Next, the small sheet-like layered silicate NH
An aqueous solution of NaOH is applied to -5a. At this time, a molar ratio Na / Si between the Si atoms in the layered silicic acid and the Na ions in the NaOH aqueous solution was about 1.7 (mol / mo).
There is a relationship of l). The layered silicic acid NH-5a (10 g) and ion-exchanged water (200 ml) were placed in a 1-liter plastic beaker and heated in a water bath at a water bath temperature of 95 ° C. while stirring with a stirring motor. Into the beaker,
250 ml of a 1N NaOH warm aqueous solution was added, and the dispersion was heated in a water bath for 30 minutes while stirring with a stirring motor while maintaining the temperature of the dispersion at about 70 ° C. At this time, the pH of the dispersion was 12.2 to 11.7.

Next, 4.0 g of cetyltrimethylammonium chloride (CTMA-Cl) was added to ion-exchanged water 4
A warm aqueous solution dissolved in 00 ml was mixed with the layered silicic acid dispersion, and the dispersion was heated in a water bath for 1 hour while stirring with a stirring motor while maintaining the temperature at about 70 ° C.

2N HCl was further added dropwise to the above dispersion to adjust the pH to 8.5, and the temperature of the dispersion was adjusted to about 70.
The mixture was heated in a water bath while stirring at a stirring motor for 2 hours while maintaining the temperature at ℃. The content of the beaker was filtered off by hot filtration, and the obtained solid product was washed on the funnel with 3000 ml of warm ion-exchanged water at about 70 to 90 ° C. The washed solid product was vacuum dried at 110 ° C. overnight. The obtained solid product was heated in air at 650 ° C. for 4 hours.
By firing for an hour, 7.6 g of mesopore material was obtained.
This mesopore material is called FH-5.

From the observation of the X-ray diffraction pattern and the transmission electron micrograph of the above mesopore material FH-5 (see Embodiments 8 and 12 described later), it was found that these crystals have a hexagonal structure and are excellent in the uniformity of pores. Being a highly mesopore material, and having a major axis of primary particles of 10 nm-
It was found that the size was in the range of 1 μm and the sizes were uniform.

Embodiment 6 This embodiment is based on kaolinite which is a clay mineral having a 1: 1 layer structure of a non-inverted silicon dioxide tetrahedron sheet and an aluminum oxide octahedron sheet and having a large sheet-like morphology. A method for producing a layered silicic acid in which a sheet-shaped body of silicate in kaolinite remains by applying an acid under pressure and a method for producing a mesopore material using this layered silicic acid, and this mesopore material will be described.

Georgia kaolin was used as the kaolinite. A mixture of 25 g of kaolin and 100 ml of 12N sulfuric acid was placed in two autoclaves each having a 300 ml container made of tetrafluoroethylene. After sealing both, they were heated at 120 ° C. for 19 hours in a constant temperature drying oven with stirring.

After allowing the container to cool, the contents of the container were filtered off,
The obtained solid product is deionized water 100 on a funnel.
Washed with 0 ml. The washed solid product and 500 ml of 1N hydrochloric acid were placed in a 1 liter separable flask equipped with a condenser, and the water bath temperature was 9
The mixture was heated in a water bath at 0 ° C. for 1 hour while stirring with a stirring motor. The contents of the flask were filtered off and the solid product obtained was washed on the funnel with 2000 ml of warm ion-exchanged water. The washed solid product was freeze-dried to obtain 24.0 g of the product. This product is NK-6p
Call.

The above product NK-6p is a silicic acid mainly composed of silicon from the result of elemental analysis, and it is a large sheet-like silicic acid in which the silicate bodies in kaolinite remain from the observation by transmission electron micrograph. I knew it was.

Next, the large sheet-like layered silicate NK
An aqueous NaOH solution is applied to -6p. At this time, a molar ratio Na / Si = about 1.3 (mol / mo) between Si atoms in the layered silicic acid and Na ions in the NaOH aqueous solution.
There is a relationship of l). The layered silicic acid NK-6p (10 g) and ion-exchanged water (200 ml) were placed in a 1-liter plastic beaker and heated in a water bath at a water bath temperature of 95 ° C. while stirring with a stirring motor. Into the beaker,
200 ml of a 1N NaOH hot aqueous solution was added, and the dispersion was heated in a water bath for 30 minutes while stirring with a stirring motor while maintaining the temperature of the dispersion at about 70 ° C. The pH of the dispersion at this time was 11.2.

Next, 4.0 g of cetyltrimethylammonium chloride (CTMA-Cl) was added to ion-exchanged water 4
A warm aqueous solution dissolved in 00 ml was mixed with the layered silicic acid dispersion, and the dispersion was heated in a water bath for 1 hour while stirring with a stirring motor while maintaining the temperature at about 70 ° C.

2N HCl was further added dropwise to the above dispersion to adjust the pH to 8.5, and the temperature of the dispersion was adjusted to about 70.
The mixture was heated in a water bath while stirring at a stirring motor for 2 hours while maintaining the temperature at ℃. The content of the beaker was filtered off by hot filtration, and the obtained solid product was washed on the funnel with 3000 ml of warm ion-exchanged water at about 70 to 90 ° C. The washed solid product was vacuum dried at 110 ° C. overnight. The obtained solid product was heated in air at 650 ° C. for 4 hours.
By firing for an hour, 8.8 g of mesopore material was obtained.
This mesopore material is called FK-6.

From the observation of the X-ray diffraction pattern and the transmission electron micrograph of the above mesopore material FK-6 (see Embodiments 8 and 11 described later), it was found that this was a crystal having a hexagonal structure with excellent pore uniformity. Being a highly mesopore material, and having a major axis of primary particles of 10 nm-
It was found that the size was in the range of 1 μm and the sizes were uniform.

Embodiment 7 This example is a clay mineral having a large sheet-like morphology with a 2: 1 layer structure of a non-inverted silicon dioxide tetrahedral sheet and an octahedral sheet of an oxide of aluminum / iron / magnesium. A method for producing a layered silicic acid in which a sheet of silicate in the vermiculite remains by producing an acid on a certain vermiculite to produce a mesopore material using the layered silicic acid, and the mesopore material will be described.

A vermiculite from China was used as the vermiculite. First, the vermiculite is oxidized. 40.0 g of the above vermiculite is placed in a 500 ml beaker, and 10% of 30% hydrogen peroxide solution is added to the beaker.
0 ml was added. Then, heat was generated and the volume of vermiculite expanded. After leaving this beaker at room temperature for 1 hour, it was placed in a constant temperature dryer at 55 ° C. for 3 days to age the above reaction. The expansion phenomenon due to the above reaction is
It is considered that the heat of oxidation of iron in the vermiculite composition causes boiling of interlayer water, resulting in expansion of the layer spacing and delamination.

[0116] Vermiculite that had been subjected to the above-mentioned oxidation treatment and 1200 ml of 3N hydrochloric acid were provided in a cooling tube.
In a liter separable flask, water bath temperature 95
The mixture was heated in a water bath at 8 ° C. for 8 hours while stirring with a stirring motor. The solid product separated by hot filtration of the contents of the flask was washed on a funnel with 600 ml of warm 1N hydrochloric acid at about 70 to 90 ° C. and 800 ml of warm deionized water.

Washed solid product and 1N hydrochloric acid 40
0 ml was placed in a 2 liter separable flask equipped with a condenser and heated in a water bath at a water bath temperature of 90 ° C. for 1 hour while stirring with a stirring motor. The contents of the flask were filtered off and the solid product obtained was washed on the funnel with 2000 ml of warm ion-exchanged water. The washed solid product is freeze-dried to give the product 1
4.7 g was obtained. This product is called NV-7a.

The above-mentioned product NV-7a is a silicic acid mainly composed of silicon based on the result of elemental analysis, and is a large sheet-like silicic acid in which vermiculite remains as skeleton of silicate from observation by a transmission electron micrograph. I found out.

Next, the large sheet-like layered silicate NV
An aqueous NaOH solution is applied to -7a. At this time, a molar ratio Na / Si = about 1.3 (mol / mo) between Si atoms in the layered silicic acid and Na ions in the NaOH aqueous solution.
There is a relationship of l). The layered silicic acid NV-7a (10 g) and ion-exchanged water (200 ml) were placed in a 1-liter plastic beaker and heated in a water bath at a water bath temperature of 95 ° C. while stirring with a stirring motor. Into the beaker,
200 ml of a 1N NaOH hot aqueous solution was added, and the dispersion was heated in a water bath for 30 minutes while stirring with a stirring motor while maintaining the temperature of the dispersion at about 70 ° C. The pH of the dispersion liquid at this time was 11.8 to 11.1.

Next, 4.0 g of cetyltrimethylammonium chloride (CTMA-Cl) was added to ion-exchanged water 4
A warm aqueous solution dissolved in 00 ml was mixed with the layered silicic acid dispersion, and the dispersion was heated in a water bath for 1 hour while stirring with a stirring motor while maintaining the temperature at about 70 ° C.

2N HCl was further added dropwise to the above dispersion to adjust the pH to 8.5, and the temperature of the dispersion was adjusted to about 70.
The mixture was heated in a water bath while stirring at a stirring motor for 2 hours while maintaining the temperature at ℃. The content of the beaker was filtered off by hot filtration, and the obtained solid product was washed on the funnel with 3000 ml of warm ion-exchanged water at about 70 to 90 ° C. The washed solid product was vacuum dried at 110 ° C. overnight. The obtained solid product was heated in air at 650 ° C. for 4 hours.
By firing for an hour, 7.6 g of mesopore material was obtained.
This mesopore material is called FV-7.

From the observation of the X-ray diffraction pattern and the transmission electron micrograph of the mesopore material FV-7 (see Examples 8 and 11 described later), it was found that the crystals had a hexagonal structure and were excellent in the uniformity of pores. Being a highly mesopore material, the major axis of the primary particles is 50 nm
It was found that the size was in the range of 2 μm and the sizes were uniform.

Example 8 of the present example This example describes the observation of the X-ray diffraction patterns of the mesopore materials obtained in the examples of the 1st to 7th embodiments with reference to FIGS. The X-ray diffraction patterns of each of the above mesopore materials are shown in FIGS. In each of the figures, 3 to 4 peaks based on the hexagonal structure were observed, and it was found that each of the above mesopore materials had high crystallinity of the hexagonal structure.

Further, when comparing FIG. 2 and FIG. 3, the FS-2 (embodiment example 2) according to FIG. 3 has a hexagonal structure than the FS-1 (embodiment example 1) according to FIG. It was found that the diffraction intensities of 3 to 4 peaks based on the above are strong. This shows that the crystallinity of the mesopore material can be made higher by increasing the proportion of the alkali metal compound if the other reaction conditions are the same in the reaction between the layered silicic acid and the alkali metal compound. It was

Further, comparing FIG. 4 and FIG. 5, FC-
FC-4 (Embodiment 4) rather than 3 (Embodiment 3)
It was found that the peak diffraction intensity was stronger in the case of. Thus, it was found that the crystallinity of the mesopore material can be further increased by increasing the reaction temperature in the reaction between the layered silicic acid and the alkali metal compound under the same other reaction conditions.

Embodiment 9 In this embodiment, the specific surface area of each mesopore material obtained in Embodiments 1 to 7 was determined by using the BET method by nitrogen adsorption and summarized in Table 1. According to the table, it was found that the specific surface area of each mesopore material was 800 m ² / g or more. From this, it was found that the mesopore material was a porous body having many pores.

[0127]

[Table 1]

Embodiment 10 In this embodiment, as shown in FIGS. 9 and 10, the pore distribution by nitrogen adsorption was determined for the mesopore materials FS-2 and FV-7 according to Embodiments 2 and 7, and The results will be described.

The method for measuring the above pore distribution will be described below. First, a nitrogen adsorption isotherm was created using the following equipment and method. The device is an absolute pressure type transducer (Bartron 127A manufactured by Nippon MKS Co., Ltd.).
A) and control valve (Nippon MKS Co., Ltd.)
248A) manufactured by the company. Using this device, measurement was performed by a quantitative method.

In the measurement, first, about 50 mg of sample was weighed into a sample tube and vacuum degassed at 150 ° C. for 2 hours. The degree of vacuum after 2 hours was 10 ⁻³ torr. Then, while immersing the sample tube in liquid nitrogen,
Nitrogen adsorption was measured to obtain a nitrogen adsorption isotherm.

From the obtained nitrogen adsorption isotherm, Cran
The pore distribution curves calculated by the Ston-Inclay method are shown in FIGS. 9 and 10. The central pore diameter obtained from the peak position of the pore distribution curve, that is, the pore diameter showing the maximum peak, was 2.8 nm for both.

Next, the integral curve of the specific surface area of the above mesopore material with respect to the pore diameter was calculated by the Cranston-Inclay method. -40% of central pore diameter ~
When the ratio of the specific surface area within the range of + 40% to the total surface area (+ -40% porosity) was obtained, FS-7 was 9
6%.

It is this value that is shown in the claims,
"The maximum peak diameter in the pore distribution curve is 2
Is a ratio of all pores having a "pore diameter in the range of -40 nm to + 40% of the pore diameter showing the maximum peak in the pore distribution curve" in the range of -10 nm. . This value was higher than that of the mesopore material obtained from the layered silicate shown in the prior art. On the other hand, FV-7 was 67%, which was equivalent to the conventional one in the pore size.

Further, FS-1, FC-3, FH-5, F
For K-6, the central pore diameter of -40
When the ratio of the specific surface area to the total surface area (+ -40% porosity) within the range of 40% to + 40% was determined, it was higher than that of the conventional product (75% or more).

Embodiment 11 As shown in FIG. 11, this embodiment is for explaining an adsorption isotherm curve by water vapor adsorption for the mesopore material FS-2 according to Embodiment 2 and explaining the result.

First, the method for measuring the adsorption isotherm will be described below. As the apparatus used for the above measurement, the same apparatus as that used in Example 9 was used, and the measurement was performed by the quantitative method. First, about 50 mg of sample was weighed into a sample tube and vacuum degassed at 150 ° C. for 2 hours. The degree of vacuum after 2 hours was 10 ⁻³ torr. Then, the water vapor adsorption measurement was performed while keeping the sample tube at 25 ° C. to obtain the water vapor adsorption isotherm.

Also, for the conventional mesopore material prepared from the synthetic layered silicate kanemite according to the conventional example, the water vapor adsorption isotherm curve was obtained by the same measurement as above. Both of the above two isothermal curves are shown in FIG.

According to the figure, the FS according to the second embodiment
For -2, the rise of the water vapor adsorption isotherm was sharper and closer to vertical than that of the conventional mesopore material. From this, it was found that the mesopore material of FS-2 had a uniform pore diameter and higher crystallinity.

Embodiment 12 In this example, the results of observation with a transmission electron microscope (TEM) of the mesopore materials obtained in Examples 1 to 7 will be described. 12 to 25 show TEM photographs of the above mesopore materials. 12 and 13 are the mesopore material FS-1 obtained in the first embodiment. Similarly, FIG.
4, FIG. 15 is the same as the mesopore material FS-2 obtained in the second embodiment (see the detailed description of the drawings).

Note that, in FIGS. 12 to 25, in addition to the particulate mesopore material, a mesh-like object is present in some of the drawings. This mesh object is a magnified image of the stage on which the sample to be observed in the transmission electron microscope is placed, and is generally generated when the magnification is increased in the transmission electron microscope. It is a phenomenon.

As shown in FIGS. 12 and 13, the major axis diameter of the primary particles of the mesopore material FS-1 according to the first embodiment is 10 nm to 1 μm, and as shown in FIGS. The major axis diameter of the primary particles of FS-2 according to Example 2 was found to be 10 nm to 500 nm.

Each major axis diameter is in the range of 10 nm to 1 μm, but FS-1 contains primary particles having a major axis diameter larger than that of FS-2. That is, it was found that in the reaction between the layered silicic acid and the alkali metal compound, if the other reaction conditions were the same, the particle size of the obtained mesopore material was smaller when the proportion of the alkali metal compound was increased.
Note that FIG. 13 is an enlarged image of FIG. 12. According to the figure, it was found that the high crystallinity of the mesopore material is remarkable.

Next, as shown in FIGS. 16, 17, and 20 to 23, the major axis diameter of the primary particles of FC-3, FH-5 and FK-6 is also in the range of 10 nm to 1 μm. It was found that the particles were mainly composed of small particles having a particle diameter of 200 nm or less.

Further, as shown in FIGS. 24 and 25, the major axis diameter of the primary particles of FV-7 according to the seventh embodiment is 50.
It was found to be in the range of nm to 2 μm. This is because the sheet diameter of the layered silicate NV-7a used as a raw material is 7μ.
This is because hydrolysis of the silicon dioxide tetrahedral sheet was mitigated due to the size of m or more. Therefore, it was found that a layered silicate having a larger sheet diameter than in the case of the other embodiments is produced, and thus a mesopore material having a primary particle major axis diameter in the range of 50 nm to 2 μm can be obtained.

Further, as shown in FIGS. 18 and 19, the major axis diameter of the primary particles of FC-4 according to the fourth embodiment is 10
It was found to be in the range of nm to 1 μm. Figure 1
6, When compared with FC-3 shown in FIG. 17, it was found that FC-4 contained primary particles having a larger major axis than FC-3. That is, it was found that, in the reaction between the layered silicic acid and the alkali metal compound, if the other reaction conditions were the same, the reaction temperature was raised to obtain a mesopore material having a smaller major axis of primary particles.

Embodiment 13 This embodiment compares the FS-2 according to Embodiment 2 and the mesopore material obtained from the conventional layered silicate with reference to Table 2 to compare the dispersibility in organic solvents. It is a good thing. The mesopore material according to the conventional example is made of kanemite, which is a synthetic layered silicate.

In the above-mentioned dispersibility test, about 10 mg of a solid sample and about 1 ml of an organic solvent were placed in a test tube of 10 ml, deaerated under reduced pressure of an aspirator, and then heated.
While agitating, the dispersion state was visually determined and the different organic solvents S1 to S9 were tested. The results are summarized in Table 2.

According to the table, organic solvents S1, S5, S7
In regard to, the conventional products and the products of the present invention have equivalent dispersibility. However, other organic solvents S2 to S4, S
Regarding 6, S8 and S9, it was found that the mesopore material according to the present invention was superior to the conventional product. Therefore, it was found that the mesopore material according to the present invention is excellent in dispersibility in an organic solvent.

[0149]

[Table 2]

[0150]

As described above, according to the present invention, the primary particles having a small size and uniform size, the pore diameter of the pores (mesopores) are uniform, the crystallinity is high, and the primary particles to be obtained are It is possible to provide a mesopore material that can be arbitrarily selected in size, is easy to manufacture, and has a low manufacturing cost and a manufacturing method thereof.

[Brief description of drawings]

FIG. 1 is an explanatory view of a process of obtaining a mesopore material from a layered silicate through a condensate according to the first embodiment.

FIG. 2 is a mesopore material FS-1 according to the eighth embodiment.
The diagram which shows the X-ray-diffraction pattern of (Embodiment 1).

FIG. 3 is a mesopore material FS-2 according to the eighth embodiment.
The figure which shows the X-ray-diffraction pattern of (Embodiment example 2).

FIG. 4 is a mesopore material FC-3 according to Embodiment 8;
The diagram showing the X-ray diffraction pattern of (Embodiment 3).

FIG. 5 is a mesopore material FC-4 according to the eighth embodiment.
The diagram which shows the X-ray diffraction pattern of (Embodiment 4).

FIG. 6 is a mesopore material FH-5 according to the eighth embodiment.
The line diagram which shows the X-ray diffraction pattern of (Embodiment example 5).

FIG. 7 is a mesopore material FK-6 according to the eighth embodiment.
The diagram which shows the X-ray-diffraction pattern of (Embodiment example 6).

FIG. 8 is a mesopore material FV-7 according to the eighth embodiment.
The diagram which shows the X-ray-diffraction pattern of (Embodiment 7).

FIG. 9 is a mesopore material FS- according to the tenth embodiment.
2 is a diagram showing a pore distribution curve of No. 2 (Embodiment 2).

FIG. 10 is a mesopore material FV according to the tenth embodiment.
7 is a diagram showing a pore distribution curve of -7 (Embodiment 7). FIG.

FIG. 11 is a mesopore material FS according to the eleventh embodiment.
2 (Embodiment 2) and a diagram showing water vapor adsorption isotherms of conventional mesopore materials.

FIG. 12 is a mesopore material FS according to Embodiment 12;
-1 (Embodiment 1) Substitute for Drawing (24000)
Times).

FIG. 13 is a mesopore material FS according to the twelfth embodiment.
-1 (Embodiment 1) Substitute for Drawing (120,000
Times).

FIG. 14 is a mesopore material FS according to the twelfth embodiment.
-2 (Embodiment 2) substitute for a drawing (24000
Times).

FIG. 15 is a mesopore material FS according to Embodiment 12;
-2 (Embodiment 2) substitute for drawing (120,000
Times).

FIG. 16 is a mesopore material FC according to Embodiment 12;
-3 (embodiment example 3) as a drawing substitute photograph (24000)
Times).

FIG. 17 is a mesopore material FC according to Embodiment 12;
-3 (embodiment example 3) as a substitute for a drawing (120,000
Times).

FIG. 18 is a mesopore material FC according to Embodiment 12;
-4 (Embodiment 4) Substitute for Drawing (24000
Times).

FIG. 19 is a mesopore material FC according to Embodiment 12;
-4 (Embodiment 4) substitute drawings (120,000
Times).

FIG. 20 is a mesopore material FH according to the twelfth embodiment.
-5 (Embodiment 5) Substitute for Drawing (24000
Times).

FIG. 21 is a mesopore material FH according to the twelfth embodiment.
-5 (Embodiment 5) Substitute for Drawing (120,000
Times).

FIG. 22 is a mesopore material FK according to the twelfth embodiment.
-6 (Embodiment 6) Substitute Drawing (24000)
Times).

FIG. 23 is a mesopore material FK according to the twelfth embodiment.
-6 (Embodiment example 6) drawing substitute photograph (120,000
Times).

FIG. 24 is a mesopore material FV according to the twelfth embodiment.
-7 (Embodiment 7) substitute drawings (24000)
Times).

FIG. 25 is a mesopore material FV according to Embodiment 12;
-7 (Seventh embodiment) as a drawing substitute photograph (120,000
Times).

[Explanation of symbols]

1. ． ． Mesopore material, 10. ． ． Pores (mesopores), 11. ． ． Layered silicate, 12. ． ． Silicon dioxide tetrahedral sheet, 13. ． ． Condensate, 15. ． ． Surfactant,

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-9-313950 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C01B 33/12-29/54 B01J 20 / 00 B01J 21/00-38/74 JISST file (JOIS) WPI (DIALOG)

Claims (3)

(57) [Claims] 1. Pore diameters in the range of 2 to 10 nm (mesopores) are provided, and the major axis diameter is 10 nm to 1
together consisting of primary particles in the range of μm, clay minerals
A mesopore material composed of a layered silicate obtained by the above method, wherein the pores have a maximum peak in the pore distribution curve in the range of 2 to 10 nm,
Features and to Rume Sopoa material that% or more with a pore diameter in the maximum range of -40 to + 40% of the pore diameter showing a peak in the pore distribution curve. 2. Pore (mesopore) having a pore diameter in the range of 2 to 10 nm and having a major axis diameter of 50 nm to 2
together consisting of primary particles in the range of μm, clay minerals
A mesopore material consisting of a layered silicate obtained by the above method, wherein the pores have a maximum peak in a pore distribution curve in the range of 2 to 10 nm, and 60
Features and to Rume Sopoa material that% or more with a pore diameter in the maximum range of -40 to + 40% of the pore diameter showing a peak in the pore distribution curve. 3. A clay mineral is treated with an acid to form a layered silicic acid, then an alkali metal compound is reacted with the layered silicic acid to form a layered silicate, and then a surfactant is applied to the layered silicate. , to form a silicate three-dimensional structure, without a condensate that includes a surfactant therein, and then the production method of the characteristics and to Rume Sopoa material to remove the surfactant from the condensate.