JP2008056545A - Inorganic porous body and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic porous body having a pore size in an intermediate region between a microregion and a mesoregion and having a narrow pore size distribution, and also being an adsorption/catalyst material having excellent heat resistance and used for a catalyst and an adsorbent with molecules having high molecular weight and molecules having high bulk as objects. <P>SOLUTION: Regarding the inorganic porous body, the interlayer of layered silicic acid composed of magadiite or kenyaite is bridged by metal oxide, and also, it comprises the main peak of a pore size distribution in the range of 20 to 40Å; wherein, the metal oxide is preferably one or more kinds selected from the group consisting of silica, alumina, titania and zirconia. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an inorganic porous material having a pore size intermediate between micropores and mesopores and having a narrow pore size distribution and a method for producing the same, a catalyst for high molecular weight molecules and bulky molecules, The present invention relates to a heat-resistant adsorption and catalyst material that can be used for an adsorbent.

  Conventionally, crystalline porous bodies represented by zeolite have been used in a wide range of industrial fields as catalysts, ion exchangers, etc., depending on the physical and chemical characteristics of the pore surface of the porous body. However, in the case of such a crystalline porous body, since it has a uniform structure with a pore size of 3 to 10 mm, it exhibits an excellent function for highly selective catalytic reactions such as low molecular weight compounds, ZSM-5 and Y-type zeolites have been modified to accommodate larger molecules.

On the other hand, development of mesoporous materials such as mesoporous silica synthesized with a silica source and a surfactant has been actively conducted. A method of manufacturing a hexagonal columnar porous body (honeycomb porous body) having mesopores using a cationic surfactant molecular assembly as a template has been proposed. The following two methods according to the type of silica source are proposed. Are known. The first method uses layered silicate as a starting silica source. For example, kanemite (NaHSi ₂ O ₅ .3H ₂ O), which is one of layered silicates, and alkyltrimethylammonium (hereinafter “ATMA”) are used. A composite body of the following is proposed to obtain a porous mesoporous silica having a specific surface area of 1000 m ² / g or more by firing and removing the organic matter (see Patent Document 1). In this method, the kanemite is curved like a corrugated sheet so that the unit sheet of silicic acid surrounds the ATMA, and the vertices of the corrugated sheets are bonded together to form a porous precursor. The second method uses amorphous silica powder or alkaline silicate aqueous solution as the starting silica source. For example, a mixture of precipitated silica and tetramethylammonium silicate aqueous solution is reacted with ATMA at 150 ° C. to form a non-layered composite. An obtaining method has been proposed (see Patent Document 2). In this method, a regular structure is formed in the silicic acid layer by the polycondensation of the porous precursor on the surface of the ATMA micelles, and the porous material is obtained by removing organic substances.

Further, a porous body has been proposed in which SiO ₂ interlayer cross-linking is formed between crystalline layered silicic acids by dehydration condensation of silicic acid, and metal atoms different from silicon are bonded (see Patent Document 3).

  On the other hand, in order to control the pore structure of a crystalline porous body, many pillar compounds such as pillared clay in which layers of layered compounds such as clay minerals are cross-linked (with struts between the layers) have been proposed (non- (See Patent Document 1). Such a pillar compound introduces an organic cation, a polynuclear inorganic cation or the like as a pillar precursor between layers, and forms a space similar to a pore by crosslinking between layers, By controlling various reaction conditions, those having a pore diameter of up to about 40 mm have been obtained.

  In addition, a porous body in which a silica column is raised using a liquid polyamine and tetraalkoxysilane as an acid-treated product of a layered polysilicate has been proposed (see Patent Document 4).

Japanese Patent Laid-Open No. 6-24867 Japanese National Patent Publication No. 5-503499 JP-A-4-238810 JP-A-9-2813 Chemical Review, p. 39-47, no. 21, 1994, The Chemical Society of Japan

However, crystalline porous bodies represented by zeolite have been modified to ZSM-5 and Y-type zeolite, but cannot exceed about 10 mm, and have a bulky molecular structure. There was a problem that it could not be used as a catalyst or adsorbent.
The silica porous material described in Patent Document 1 is a method in which kanemite is used as a silica source, and kanemite is a layered silicic acid composed of a single silicic acid sheet, and since it is a thin silicic acid sheet, the unit sheet surrounds ATMA. Are curved like corrugated plates, and the vertices of a plurality of corrugated plates are combined to form a porous precursor. For this reason, the structural strength of the porous body is low, and there is a drawback in that structural breakdown is easily caused by mechanical impact such as kneading into a resin or pulverization. Similarly, there is a problem that it is vulnerable to thermal shock and is susceptible to structural destruction.
In the porous material described in Patent Document 2, the silicic acid layer is polycondensed on the surface of the ATMA micelles, but the layer is only one layer thick, and the mechanical strength is low, and the thermal shock is also weak. There is.
Patent Document 3 exemplifies three-layered magadiaite and four-layered Kenyaite as crystalline layered sodium silicate, but the interlayer cross-linking of SiO ₂ in the porous body described in Patent Document 3 is bent. Since the hydroxyl group of the layer itself is formed by dehydration condensation, it can actually be formed only on layered sodium silicate having a single layer structure such as kanemite. And the porous body of patent document 3 obtained using kanemite has the subject that mechanical strength is low similarly to said patent document 1, and it is weak also to a thermal shock.
Non-Patent Document 1 describes that a pillar compound having a pore size of 40 mm was obtained by interlayer crosslinking of a layered compound. Examples of pillar compounds that have been studied so far include montmorillonite and hectorite. The use of clay minerals such as this improves the amount of adsorption of gas molecules, but the crystal structure changes at around 500 ° C, and the high-temperature heat resistance is poor, making it unsuitable for the above catalysts. There is.
As is clear from the examples, the porous material described in Patent Document 4 is a tremendous production method using 28 ml of alkylamine and 50 ml of tetraethoxysilane for 1 g of magadiite. The obtained porous body has a pore diameter of about 11 mm and does not exceed the pore area of zeolite.
Non-patent document 1 introduces many cases, and it is described that a porous body having a pore diameter of 40 mm was obtained by interlayer crosslinking of layered silicate, but has been studied so far. As the pillar compound, clay minerals such as montmorillonite and hectorite have been used, so the amount of adsorption of gas molecules is improved, but the crystal structure changes at about 500 ° C. There is a problem that it cannot be applied to catalysts.

By the way, inserting a guest such as an atom, molecule, or ion between layers of a layered crystal that is a host is well known as an intercalation technique. Due to the variety of combinations of host and guest types, an extremely wide variety of substances are known as intercalation compounds. Silicate is one of them, such as layered clay minerals formed with multiple elements such as montmorillonite and kaolinite, layered silicic acid or layered silicate formed only with SiO ₂ units such as magadiite and kenyaite. Are known.

The layered compound is attracting attention because it can be expected to change or control physical properties by intercalation of guest species, and has the possibility of developing new functions. In particular, layered silicic acid or layered silicate such as magadiite or kenyanite has a structure composed only of SiO ₂ units, and a silanol group (≡Si—O—H) exists on the surface of the layer. In these respects, the layered silicic acid or the layered silicate is different from the layered clay mineral, and the present inventors have been paying attention for some time. The present inventors, for example, in Japanese Patent Application Laid-Open No. 2000-128521, selectively adsorbed alcohol by ion exchange of quaternary ammonium ions to magadiite and kenyaite to expand the layer and bond a silane compound between the expanded layers. Proposed layered silicic acid.

  As described above, it is widely known that a layered compound is ion-exchanged with a quaternary ammonium ion to expand the layer, and atoms, molecules, and ions are introduced between the expanded layers. There is no actual example of forming oxide pillars to form pores of 20 to 40 mm.

  The present invention has been made in view of the above circumstances, has a pore diameter intermediate between micropores and mesopores to which zeolite and mesoporous materials could not be applied, and has high mechanical strength, thermal shock resistance and It aims at providing the novel porous body excellent in heat resistance, and its manufacturing method.

  As a result of intensive studies to achieve the above object, the present inventor used layered silicic acid composed of magadiite or kenyaite instead of the conventionally used clay mineral, and in the range of 20 to 40% by interlayer crosslinking of metal oxides. It was possible to obtain an inorganic porous material having a peak of pore size distribution.

That is, the present invention is an inorganic porous material characterized in that the layered silicic acid layer composed of magadiite or kenyanite is crosslinked with a metal oxide and has a main peak of pore size distribution in the range of 20 to 40%. is there.
The metal oxide is preferably at least one selected from the group consisting of silica, alumina, titania and zirconia, and is most preferably silica. This silica is preferably a hydrolysis product of alkoxysilane, especially tetraalkoxysilane.
The inorganic porous body according to the present invention preferably contains no alkali metal or alkaline earth metal component.
The specific surface area of the inorganic porous body is preferably 300 to 600 m ² / g. Moreover, it is preferable to have at least one diffraction peak in the range of 33 to 50 mm in X-ray diffraction.

Further, the present invention is a method for producing the above inorganic porous body, and after introducing a quaternary ammonium ion by ion exchange between layers of a layered silicic acid composed of magadiite or kenyaite, In a method for producing an inorganic porous material, the method further comprises introducing a metal oxide and then firing the layered silicic acid to remove quaternary ammonium ions and to crosslink the layered silicic acid layer with the metal oxide. is there.
The metal oxide is preferably silica, and the silica is preferably a hydrolysis product of tetraalkoxysilane.
When tetraalkoxysilane is used to place silica pillars between layers, it is preferable to use a long-chain dialkyldimethylammonium ion or a long-chain alkylaryldimethylammonium ion as the quaternary ammonium ion. The long chain alkyl group of the quaternary ammonium ion preferably has 8 to 24 carbon atoms.
The pore size distribution in the present invention is calculated by the Dollimore-Heal method [J. Appl. Chem., 14, 108 to (1964)] using a Sorpmatic 1800 manufactured by Carlo Erba Strumentazione as a measuring device. The specific surface area in the present invention is calculated by the BET multipoint method in the relative pressure P / P ₀ = 0.05 to 0.20 range. The X-ray diffraction pattern (XRD) in the present invention uses a RINT2400 model made by Rigaku as an X-ray diffractometer, and measures a peak corresponding to a surface interval d appearing at 2θ in a low angle region in a powder X-ray diffraction pattern. It is a thing.

  According to the present invention, a novel porous material having an intermediate pore size between micropores and mesopores to which zeolite and mesoporous materials cannot be applied, high mechanical strength, and excellent thermal shock resistance and heat resistance. The body and the manufacturing method thereof can be provided.

Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.
The inorganic porous body according to the present invention has a high mechanical strength, a thermal shock resistance, and a layer of layered silicic acid made of magadiite or kenyaite, which are cross-linked with a metal oxide, and metal oxide pillars are provided between the layers. It has the feature of excellent heat resistance. The pores formed by the layered silicic acid and the metal oxide pillar have a main peak of pore diameter distribution in the range of 20 to 40%. Such an inorganic porous material according to the present invention is obtained by introducing a quaternary ammonium ion between layers of a layered silicic acid composed of magadiite or kenyanite by ion exchange to widen the layer spacing, and then a metal as an interlayer crosslinking agent between the layers. By further introducing an oxide and then firing the layered silicic acid, the quaternary ammonium ions can be removed and the layers of the layered silicic acid can be crosslinked with a metal oxide.

(1) The magadiite and kenyaite layered silicate, kanemite _{(NaHSi 2 O 3 · 3H 2} O), KHSi 2 O 5, makatite _{(Na 2 Si 4 O 9 ·} xH 2 O), magadiite, and the like Kenyaite . In Of these the present invention, since it is excellent in mechanical strength for it and the multilayer structure fabrication is easy, magadiite _{(Magadiite: Na 2 Si 14 O} 29 · xH 2 O) and kenyaite (Kenyaite: Na are used _{2 Si 22 O 41 · xH 2} O). Although magadiite and kenyaite also have natural products, synthetic products are preferred from the standpoint of few impurities. The synthesis method is described in detail in J. Ceramic Society of Japan, Vol. 100, No. 3, 326-331 (1991).

Magatiite can be obtained, for example, by treating a suspension of SiO ₂ : NaOH: H ₂ O = 1: 0.23: 18.5 (molar ratio) in an autoclave at 150 ° C. for 48 hours. Kenyaite can be obtained, for example, by treating a suspension of SiO ₂ : NaOH: H ₂ O = 1: 0.23: 18.5 (molar ratio) in an autoclave at 170 ° C. for 48 hours. When NaOH and K ₂ CO ₃ are used, it is easy to synthesize Kenyaite.

  There are many other synthesis methods besides the above, and there is no limitation on the synthesis method. Some synthetic methods use potassium instead of sodium. In that case, the chemical formula of the compound is the one in which Na in the above chemical formula is replaced with K. Magadiite and Kenyaite obtained by the above synthesis method have a spherical form in which scaly crystals are gathered into petals, cabbages or accordions. The scale shape referred to here includes not only a narrow scale shape but also a plate shape. An example of an SEM image of magadiite is shown in FIG. The thickness of one plate (petal) is about 0.05 μm, and the size of one side of the surface is approximately square of 1 to 3 μm. Such plates aggregate to form agglomerated particles of several microns. This agglomerate can be separated by chemical treatment as described in, for example, J. Ceramic Society of Japan, Vol. 100, No. 6, 872-875 (1992). It can also be formed into a plate shape by pulverization.

  As a synthesis method different from the above, for example, a synthesis method described in JP-A No. 2003-531801 can be used. In this case, a non-aggregated plate-like crystal shape is obtained. In the synthesis method described in this publication, in the step of heating the colloidal silica suspension, the molar ratio of sodium hydroxide / silica is in the range of 0.4 to 0.5, and the molar ratio of water / silica is 5 to 5. The range is 39. The heating temperature is 140-170 ° C. An example of an SEM image of magadiite synthesized by this method is shown in FIG. This magadiite has a scaly (plate-like) form in the same manner as shown in FIG. However, unlike what is shown in FIG. 1, the scale-like (plate-like) crystals do not form aggregates and are in a disjointed state.

  As for the X-ray diffraction pattern, magadiite is registered in JCPDS # 42-1350, and Kenyaite is registered in JCPDS # 20-1157.

  In the present invention, an inorganic porous material can be constituted using either one of magadiite or kenyaite, or both of them.

The structural model of magadiite is shown in FIGS. 3 (a) and 3 (b). FIG. 3A is a diagram of the magadiite structural model viewed from the c-axis direction, and FIG. 3B is a diagram viewed from the lateral direction. As shown in FIGS. 3 (a) and 3 (b), in magadiite, three unit sheets of silicic acid composed of four basic units of four SiO ₂ tetrahedrons, _two each upward and downward, overlap each other. One silicate layer is formed, and hydrated sodium ions exist between the silicate layer and the silicate layer. In Kenyaite, four unit sheets overlap to form one silicate layer, and hydrated sodium ions exist between the silicate layer and the silicate layer. In other words, magadiite and kenyaite are layered silicic acid or layered silicate whose layered structure is composed only of SiO ₂ units, and belong to the category of clay minerals such as synthetic fluorine mica containing metal elements such as aluminum. It is something that does not.

In as-synthesized magadiite and kenyaite, the ion-exchangeable ion is the sodium ion in FIG. When potassium is used during synthesis, the sodium ions in FIG. 3 are replaced with potassium ions. The ion exchange capacity is 1.9 mmol / g for magadiite and 1.3 mmol / g for Kenyaite. Unlike compounds with counter ions due to electrostatic fields generated by substitution of tetravalent or trivalent or trivalent or divalent elements in the structure, which are composed of multiple metal oxides such as the clay mineral montmorillonite and silica alumina zeolite In magadiite and kenyaite, since the silicate layer has a single structure of SiO ₂ , the ion-capturing ability of ions that can be exchanged with ions is weak, and exchange with other types of ions is easy. Similarly, the bond between the silicate layer and the silicate layer is weak, and the distance between the layers easily changes depending on the size of the exchange ion species.

(2) Quaternary ammonium salt First, the sodium ion of layered silicic acid composed of magadiite or kenyaite (or potassium: hereinafter, representatively described by sodium) and quaternary ammonium ion are ion-exchanged. As a quaternary ammonium salt used for introducing a quaternary ammonium ion, an aliphatic quaternary ammonium salt is commercially available as a cationic surfactant and is preferable because it is readily available. The quaternary ammonium salt has the general formula [R _n N (CH ₃ ) _4-n ] ⁺ [X] ⁻ (wherein R is a long-chain alkyl group or aryl group, n is an integer of 1 to 3, X is A long-chain alkyltrimethylammonium salt, a long-chain dialkyldimethylammonium salt or an alkylaryldimethylammonium salt represented by (representing a halogen or OH group). Quaternary ammonium salts include those in which the long-chain alkyl group is mono- or di-, but in dialkyldimethylammonium salts, the gap between layers is larger than that of mono, but mono is preferable because the gap between layers is uniform. . However, when a silica pillar is provided between the layers using tetraalkoxysilane, a dialkyldimethylammonium salt or an alkylaryldimethylammonium salt is preferable. Dialkyl can increase the hydrophobicity of the layered silicate particles, and can attract hydrophobic tetraalkoxysilane to the particle surface.

In general, the distance between the layers can be set by the number of carbon atoms of the long-chain alkyl group. When the number of carbon atoms is 25 or more, it is insoluble and difficult to handle. The surfactant is a mixture of alkyl ammonium salts having a plurality of chain lengths corresponding to the raw material fat (coconut oil or beef tallow). A coconut oil system is preferable because the chain length is uniform. Stearyl trimethyl ammonium chloride, which is a disinfectant, is preferable because the stearyl group is a mixture of 16 and 18 carbon atoms and has two chain lengths approximated. Alkylaryldimethylammonium chloride, which is a mixture of alkyl having 12 to 24 carbon atoms and having a benzyl group as an aryl group, has a general name of benzalkonium chloride and is commercially available as a disinfectant and is preferable because it is easily available. Similarly, pyridiniums such as sterilizing disinfectants such as benzethonium chloride and cetylpyridinium chloride are preferable. Quaternary ammonium salts are preferred because of their high basicity and excellent reactivity, but amines can also be used. Of the amines, salts of primary amines having one long chain alkyl group [RNH ₂ .X] (wherein R represents a long chain alkyl group, X represents an inorganic acid or an organic acid) are preferred. Examples of commercially available products include coconut amine acetate, stearylamine acetate, stearylamine hydrochloride and the like.

(3) Ion-exchange method A suspension of magadiite or kenyaite is filtered and washed to remove excess sodium and dispersed again in deionized water to obtain an aqueous suspension having a concentration of 5 to 35% by weight. Stir well until evenly dispersed. The aqueous suspension exhibits an alkalinity of about pH 10 due to sodium ions.
Although there is no restriction | limiting in particular in ion exchange conditions, Generally temperature is 10-90 degreeC. A batch type is preferable to a column type, and in the case of a batch type, it can be carried out once or multiple times. The salt concentration at this time is generally in the range of 0.01 to 1 mol / L.

By ion exchange, quaternary ammonium ions are introduced into magadiite and kenyaite. That is, in the magadiite and / or kenyaite after ion exchange, ions capable of ion exchange other than quaternary ammonium ions are preferably sodium ions and protons. Alternatively, in the magadiite and / or kenyaite after ion exchange, it is most preferable that all of the ion-exchangeable sodium ions are exchanged with quaternary ammonium ions and consist only of quaternary ammonium ions and silicic acid.
In order to improve the thermal stability of the inorganic porous material at a high temperature, the content of the alkali metal such as sodium and potassium and the alkaline earth metal in the inorganic porous material is 0.1% by weight or less, preferably 0.01 It is desirable to perform ion exchange so that the amount is less than or equal to wt%, most preferably 0 wt%.

  After completion of ion exchange, magadiite and kenyaite are filtered and washed with water if necessary, and then dried at room temperature to 120 ° C. to obtain powder. Heating at 250 ° C. or higher is not preferable because structural destruction occurs. In the case where the interlayer crosslinking agent is continuously added, it may be filtered and washed with water and then dispersed in pure water, and drying is not necessary.

  The particle shape of magadiite and kenyaite after the introduction of quaternary ammonium ions changed greatly from the particle shape before ion exchange (see FIGS. 1 and 2), and scaly (plate-like) crystals were laminated. It has a shape. An example of the SEM image of magadiite after ion exchange is shown in FIGS. The magadiite after ion exchange shown in FIG. 4 is made from magadiite shown in FIG. The magadiite after ion exchange shown in FIG. 5 is made from magadiite shown in FIG. As is apparent from the SEM images shown in FIGS. 4 and 5, the scaly crystals are densely stacked so that their surfaces are parallel to each other. Further, the crystals are firmly fixed to each other. The adhesion between the scaly (plate-like) crystals is observed so that the one shown in FIG. 4 is stronger than the one shown in FIG. The strong sticking is presumed to be due to drying. It is presumed that the particles are loosely fixed before drying, even though the particles are aggregated. In any case, by changing from the shape of FIG. 1 to such a particle shape, the inorganic porous material according to the present invention has good dispersibility in, for example, a resin, a paint, and a cosmetic.

(4) Interlayer cross-linking agent and inter-layer cross-linking method In the present invention, metal oxide pillars are set up between layers of layered silicic acid made of magadiite or kenyaite, and metal oxide is a precursor thereof. It penetrates between layers in the form of polynuclear metal hydroxide ions having a positive valence, or is replaced by quaternary ammonium ions between layers by ion exchange. Depending on the type of polynuclear metal hydroxide ions, internuclear quaternary ammonium ions can enter without releasing quaternary ammonium ions between layers, or quaternary ammonium ion between layers can be ion-exchanged with polynuclear metal hydroxide ions. Seems to be.

As an example, in order to form pillars of alumina (Al ₂ O ₃ ), polynuclear aluminum hydroxide ions [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ are introduced by ion exchange as precursor ions. To produce polynuclear aluminum hydroxide ions, a basic aluminum chloride aqueous solution (Al ₂ (OH) ₅ Cl · nH ₂ O) is diluted with water and hydrolyzed, or further heated to hydrolyze. In the hydrolysis, acid or alkali is added as necessary to adjust the pH. When the pH is lowered with an acid, hydrolysis proceeds slowly, and a homogeneous polymer can be obtained. On the contrary, when alkali is added, the hydrolysis is accelerated, but homogeneous polymerization is difficult to carry out, and hydroxide is likely to precipitate. This hydrolysis reaction is usually performed at room temperature to 60 ° C. for 1 to 10 days, and sufficient agitation is performed during the reaction. In the case of forming a titania (TiO ₂ ) or zirconia (ZrO ₂ ) pillar, similarly to alumina, a polynuclear titanium hydroxide ion or a polynuclear zirconium hydroxide ion may be prepared from a titanium tetrachloride aqueous solution or a zirconium oxychloride aqueous solution.
Commercially available products can be used as basic aluminum chloride aqueous solution, zirconium oxychloride aqueous solution, titanium tetrachloride aqueous solution and the like. These are hydrolyzed to produce polynuclear metal hydroxide ions, which are introduced between layers by ion exchange. Alternatively, a commercially available colloid product is used as it is.
For silica (SiO ₂ ), tris (acetylacetone) silicon complex (Si (acac) ₃ ⁺ ) or sol particles positively charged by adding Ti ⁴⁺ or Fe ³⁺ can be used. In the prior art, it was considered that “silica is an anion and therefore does not enter between layers” (described on page 44 of Non-Patent Document 1). However, in the present invention, it has been found that silica pillars made of alkoxysilane hydrolyzable organisms greatly expand the layers by using alkoxysilane as the silica source. Thus, the inorganic porous body which consists of a silica single component can be obtained by standing the silica pillar between layers. This inorganic porous material has a heat resistance of 900 ° C., which has been considered impossible to achieve with conventional silica-based porous materials. When alkoxysilane is used, it is not necessary to add Ti ⁴⁺ or Fe ³⁺ , but it may be added. The alkoxysilane may be diluted with a solvent such as alcohol, or may be added as a stock solution. As the alkoxysilane, tetraethoxysilane or tetramethoxysilane is preferable. Alkoxysilane does not replace the quaternary ammonium ions between the layers, but penetrates the columns of quaternary ammonium ions and the column spaces. It is not ion exchange. This fact was confirmed by measuring the amount of quaternary ammonium ions before and after the insertion of the alkoxysilane and not changing it.

The amount of the interlayer crosslinking agent used is about 2 to 10 mol, more preferably about 4 to 8 mol, and still more preferably about 6 mol as a metal oxide such as SiO ₂ and Al ₂ O _{3 with} respect to the magadiite 1 composition formula amount. This reaction is performed at room temperature to 60 ° C. for 1 to 24 hours, and sufficient stirring is performed during the reaction.
Magadiite and Kenyaite into which the pillar precursor is introduced are filtered and washed with water if necessary, and then dried at a temperature of room temperature to 120 ° C. to obtain a powder. Grind if necessary.
In order to remove quaternary ammonium ions from the composite powder containing the pillar precursor, the inorganic porous body of the present invention is obtained by baking treatment. The firing temperature is a temperature range from the temperature at which the quaternary ammonium ions disappear to approximately 500 ° C. or more. Firing at a higher temperature is effective for stabilizing the structure of silica and improving the mechanical strength. However, when the temperature exceeds 900 ° C., it no longer contributes to the stabilization of the structure. The firing time is appropriately set in relation to the treatment temperature, but is generally about 10 minutes to 10 hours. Therefore, a preferable baking condition is a baking temperature of 600 to 700 ° C. and a baking time of 5 hours or less. If necessary, pulverization is performed after firing. In addition, when firing after introducing a polynuclear metal hydroxide ion, a method of obtaining a porous body having a strong catalytic activity by firing at a slightly lower temperature than a metal oxide and leaving the hydroxyl group in the polynuclear metal hydroxide ion Is also preferable. The firing temperature for this is 400 to 600 ° C., and carbon remains as a decomposition residue of quaternary ammonium ions, but pores can be formed.

The specific surface area measured by the BET method of the inorganic porous material thus obtained is preferably 300 to 600 m ² / g, more preferably 400 to 600 m ² / g. If the specific surface area is in the range of 300 to 600 m ² / g, the porous body is preferable because sufficient performance can be obtained for use as an adsorbent. The inorganic porous body preferably has at least one peak in the range of 33 to 50 mm in X-ray diffraction. The numerical value of this peak represents the surface spacing of the silicate layer. By subtracting the thickness of the silicate layer from this numerical value, the distance in the height direction of the interlayer space can be calculated, and the shape of the pores can be specified. can do. Therefore, having at least one peak in the narrow numerical range as described above can be said to be an inorganic porous body having a uniform pore diameter with a uniform crystal form.

Inorganic porous bodies made of metal oxide pillars by introducing polynuclear metal hydroxide ions are expected to have strong catalytic activity as well as molecular sieves. Catalyst carriers, catalysts, chromatographic carriers, deodorizers, decolorizers Used in application fields such as In addition, it exhibits excellent functions as a material with high temperature durability and high macromolecular separation ability in application fields such as gas and liquid separation membranes, catalyst carriers such as exhaust gas, protein separation, immobilized enzyme carrier, and ion selective electrode. .
Inorganic porous bodies with silica as a pillar are a single component of silica, low catalytic activity, and durability at higher temperatures. In addition to the above uses, food, cosmetics, medical products, electronic Applications such as materials and automotive materials are expected. Further, the low catalytic activity is suitable for a selective catalyst and can be used in a wide range of fields.

Hereinafter, the present invention will be specifically described based on examples. Each measured value in the examples was determined by the following method.
(A) Composition analysis:
Component analysis of sodium and the like was quantified by ICP (Varian LIBERTY type II). The quaternary ammonium ion was quantified by measuring the carbon amount with a total organic carbon meter (manufactured by Shimadzu Corporation, TOC-5000A) and converting it to a molecular weight.
(B) Particle shape:
Observation was performed with an SEM (S-4500, manufactured by Hitachi, Ltd.).
(C) X-ray diffraction pattern (XRD):
An X-ray diffractometer (RINT 2400, manufactured by Rigaku) was used. In the powder X-ray diffraction pattern, a peak corresponding to the surface interval d appearing at 2θ in the low angle region was measured.
(D) Moisture measurement Using TG / DTA (Thermogravimetric differential thermal analysis; TG / DTA6300 type manufactured by Seiko Instruments Inc.), a weight change of 40 to 800 ° C. was measured at a temperature rising rate of 10 ° C./min. The weight loss up to ° C. was defined as the amount of water.
(E) Specific surface area simple measurement It measured by the flow Sorb II2300 by Shimadzu Corporation by the BET 1 point method using 30% nitrogen-helium mixed gas.
(F) Pore size distribution measurement The average pore size, pore size distribution, specific surface area and other values of the pore structure of the porous body were determined from the nitrogen adsorption isotherm by the known BET method. It is calculated from the pore volume and specific surface area by a cylindrical model, and the pore size distribution is calculated using the Dollimore-Heal method [J. Appl. Chem., 14, 108 to (1964)] (hereinafter referred to as “DH method”). The specific surface area is calculated by the BET multipoint method in the range of relative pressure P / P ₀ = 0.05 to 0.20. As the measuring device, Soapmatic 1800 manufactured by Carlo Erba Strumentazione was used.

(Synthesis of magadiite)
First, according to the method described in J. Ceramic Society of Japan Vol.100, No.3, 326-331 (1992), SiO ₂ : NaOH: H ₂ O = 1: 0.23: 18.5 (molar ratio) Magadiite was synthesized with the following raw material composition. That is, 200 parts by weight of colloidal silica (Nihon Kagaku Kogyo Co., Ltd. product Silica Doll 30) having a SiO ₂ content of 30% by weight, 9.2 parts by weight of reagent NaOH and 193 parts by weight of water were charged into an autoclave for 48 hours at 150 ° C. Hydrothermal synthesis of was performed. After synthesis, the solid was washed with filtered water and dried at 120 ° C. to obtain magadiite (Na ₂ Si ₁₄ O ₂₉ · xH ₂ O). As shown in FIG. 1, the SEM image was a spherical crystal in which plate-like crystals having a plate thickness of 0.05 μm and a side of 3 μm on a side gathered in a petal shape. The particle size was 7.0 μm, Na ₂ O was 5.8% by weight, and the heat loss to 170 ° C. was 13% by weight. XRD coincides with JCPDS # 42-1350, surface distance d ₀₀₁ was 15.6A. When the thickness of the silicate layer is reduced to 12.8 mm (the value described in Clay Science, Vol. 36, No. 1, No. 22-34 (1996)) from the surface distance d ₀₀₁ of 15.6 mm, the distance between the layers is 2. There is no space available. Moreover, the specific surface area by a simple measuring method is as small as 23 m < ² > / g, and is not a porous body. The low angle and high angle XRD diffraction patterns of this magadiite are shown in FIGS. 6 (a) and 6 (b).

[Example 1]
(1) Benzalkonium ion exchange of magadiite (preparation of sample A)
100 g of synthesized magadiite is benzalkonium chloride equivalent to 0.5 times the amount of Na (manufactured by Kanto Chemical Co., Inc. [RN (CH ₃ ) ₂ CH ₂ C ₆ H ₅ ] Cl, R is C _{8 to} C ₁₈ ) Was dispersed in 1000 ml of an aqueous solution and stirred at room temperature for 24 hours to ion exchange Na and benzalkonium. The solid was separated from the dispersion by filtration and washed with water. This magadiite was again dispersed in 1000 ml of an aqueous solution of 0.5 times equivalent of benzalkonium chloride and stirred at room temperature for 24 hours to ion exchange Na and benzalkonium. The solid was separated from the dispersion by filtration, washed with water, dried at 110 ° C., and pulverized with an KA-10 MF-10 tabletop pulverizer to obtain a powder. When a part of the powder was taken out and SEM observation was performed, the particle shape in which the scaly crystals were laminated could be observed. The average particle size by SEM observation was 3 μm. Moreover, the heat loss to 170 degreeC was 1.9 weight%. In XRD, the original d ₀₀₁ 15.6． disappears, the new d ₀₀₁ 32.9Å large peak and its d ₀₀₂ appear at 16.5Å, and benzalkonium is introduced between the magadiite layers. It has been confirmed that. Further, it was confirmed by chemical analysis that Na was not present and (benzalkonium) ₂ .Si ₁₄ O ₂₉ .xH ₂ O was obtained. This powder was bulky and fluffy and showed water repellency to water. The powder obtained here is designated as Sample A.

(2) Preparation of Inorganic Porous Material Using Sample A 140 g of room temperature pure water was placed in a 300 ml glass beaker and stirred using a propeller-type stirrer, and 15 g of sample A was added. Sample A was water-repellent and did not adapt to water, but became so-called lumps and dispersed. Next, 15 g of tetraethoxysilane (hereinafter referred to as TEOS) was added. Since TEOS does not dissolve in water, it was stirred at the beginning of addition while floating like an oil layer above the water surface. With continued stirring, TEOS moved from the surface of the water to the crumbly powder, and there was no TEOS on the surface of the water. When the stirring was further continued, the lumps gradually became smaller, and finally a suspension with good dispersion of the powder without lumps was obtained. This reaction was performed at room temperature and took 8 hours to complete. The solid was separated from the dispersion by filtration, washed with water, dried at 110 ° C., and baked at 600 ° C. to remove organic substances. Subsequently, it was pulverized by an KA-10 type table pulverizer manufactured by IKA to obtain a powder. When a part of the powder was taken out and observed by SEM, a particle shape similar to Sample A was observed. The average particle size by SEM observation was 3 μm. In XRD, 32.9Ａ of d ₀₀₁ of sample A disappears, and a new broad peak of 35.5Å of d ₀₀₁ and a peak of 12.9Å appear, and silica is introduced between the layers of magadiite. It was confirmed that the structure was an interlayer cross-linked structure. When the thickness of the silicate layer is reduced by 12.8 mm from the surface distance d ₀₀₁ of 35.5 mm, the distance between the layers is 22.7 mm. The DH method pore size distribution by nitrogen adsorption was measured and shown in FIG. As shown in FIG. 7, the silica crosslinked porous material has a pore width of 13 to 30 cm and a peak of pore distribution at 21.2 cm. This value is in good agreement with 22.7 mm calculated from XRD. The specific surface area calculated at the same time was 448 m ² / g. In the simple measurement method, it was 349 m ² / g. Moreover, the specific surface area after conducting a heat resistance test at 900 ° C. for 1 hour in an electric furnace was 363 m ² / g in the simple measurement method, and showed good heat resistance without any decrease. Moreover, the composition of the inorganic porous material obtained in Example 1 was calculated to be (crosslinked SiO ₂ ) ₇ · Si ₁₄ O ₂₉ from the material balance of the chemicals used.

[Example 2]
Instead of TEOS in Example 1, a basic aluminum chloride aqueous solution (Al ₂ (OH) ₅ Cl · nH ₂ O, Takibine # 1500, Al ₂ O ₃ = 23.5%, manufactured by Taki Chemical Co., Ltd.) was used. . In a 300 ml glass beaker, 140 g of room temperature pure water was added, stirred using a propeller-type stirrer, and 15 g of sample A was added. Then 25.7 g of basic aqueous aluminum chloride solution was added. This reaction was carried out at room temperature for 24 hours, solids were separated from the dispersion by filtration, washed with water, dried at 110 ° C., and baked at 600 ° C. to remove organic substances. Subsequently, it was pulverized by an KA-10 type table pulverizer manufactured by IKA to obtain a powder. When a part of the powder was taken out and observed by SEM, a particle shape similar to Sample A was observed. The average particle size by SEM observation was 3 μm. In XRD, 32.9 mm of d ₀₀₁ of sample A disappears, and 35.3 mm of large new peak of d ₀₀₁ appears at 11.5 mm. Alumina is introduced between the layers of magadiite and interlayer cross-linking is observed. The structure was confirmed. When the thickness of the silicate layer is reduced by 12.8 mm from the surface distance d ₀₀₁ of 35.3 mm, the distance between the layers is 22.5 mm. The specific surface area was 58 m ² / g by a simple measurement method. The composition of the inorganic porous material obtained in Example 2 was confirmed to be (crosslinked Al ₂ O ₃ ) ₆ .Si ₁₄ O ₂₉ by chemical analysis.

Example 3
Instead of TEOS in Example 1, zirconia sol (ZSL-10A, ZrO ₂ = 10%, sold by Daiichi Elemental Chemical Co., Ltd.) was used. In a 300 ml glass beaker, 140 g of room temperature pure water was added, stirred using a propeller-type stirrer, and 15 g of sample A was added. Then 72.9 g of zirconia sol aqueous dispersion was added. This reaction was carried out at room temperature for 18 hours, solids were separated from the dispersion by filtration, washed with water, dried at 110 ° C., and baked at 600 ° C. to remove organic substances. Subsequently, it was pulverized by an KA-10 type table pulverizer manufactured by IKA to obtain a powder. When a part of the powder was taken out and observed by SEM, a particle shape similar to Sample A was observed. The average particle size by SEM observation was 3 μm. In XRD, 32.9Ａ of d ₀₀₁ of sample A disappears, and a new broad peak of 46.2Å of d ₀₀₁ and a peak of 12.0Å appear, and zirconia is introduced between the layers of magadiite. It was confirmed that the structure was an interlayer cross-linked structure. When the thickness of the silicate layer is reduced by 12.8 mm from the surface distance d ₀₀₁ of 46.2 mm, the distance between the layers is 33.4 mm. The specific surface area was 80.5 m ² / g by a simple measurement method. The composition of the inorganic porous material obtained in Example 3 was confirmed to be (crosslinked ZrO ₂ ) ₆ · Si ₁₄ O ₂₉ by chemical analysis.

[Comparative Example 1]
Instead of sample A, the same operation as in Examples 1 to 3 was carried out using as-synthesized Magatiite containing no benzalkonium and using Na as an exchangeable ion. In any of the obtained powders, no expansion of the interplanar spacing was observed by XRD, and the same interplanar spacing as that of the as-synthesized Magatiite was shown.

[Comparative Example 2]
100 g of commercially available ion-exchangeable fluorine mica (Somasif ME100 manufactured by Corp Chemical Co., Ltd., specific surface area 9 m ² / g) is benzalkonium chloride (manufactured by Kanto Chemical Co., Inc., [RN (CH ₃ ) ₂ CH ₂ C ₆ H ₅ ] Cl, R was dispersed in 1000 ml of an aqueous solution of C _{8 to} C ₁₈ ) and stirred at room temperature for 24 hours to ion exchange Na and benzalkonium. The solid was separated from the dispersion by filtration, washed with water, dried at 110 ° C., and pulverized with an KA-10 MF-10 tabletop pulverizer to obtain a powder. The obtained powder contained 25% by weight of benzalkonium.
A 300 ml glass beaker was charged with 140 g of pure water at room temperature and stirred using a propeller-type stirrer, and 15 g of the powder obtained above was added. Then, 7.44 g of TEOS corresponding to 3 times equivalent of benzalkonium was added. Stirring was continued at room temperature for 8 hours, and the solid was separated from the dispersion by filtration, washed with water, dried at 110 ° C, and calcined at 600 ° C. The fired powder was black, and the organic matter was removed by firing at a firing temperature of 800 ° C. to remove carbon. Subsequently, it was pulverized by an KA-10 type table pulverizer manufactured by IKA to obtain a powder. This powder had a gray color due to a slight carbon remaining. In XRD, a large broad peak of d ₀₀₁ of d ₀₀₁ appeared, and it was confirmed that silica was introduced between the layers of fluorine mica to form an interlayer crosslinked structure. When the thickness of the smectite layer is reduced to 9.4 mm from the surface distance d ₀₀₁ of 33.4 mm, the distance between the layers is 24.0 mm. However, the specific surface area in the simple measurement method is 28 m ² / g, and it is estimated that the smectite sheet was deformed. Further, the specific surface area after conducting a heat resistance test at 900 ° C. for 1 hour in an electric furnace was 9 m ² / g by a simple measurement method, and it was found that the heat resistance was poor. Further, XRD after the heat resistance test confirmed enstatite (MgSiO ₃ ) crystals.

Example 4
(1) Magadiite stearyltrimethylammonium ion exchange (Preparation of sample B)
An aqueous solution of stearyltrimethylammonium chloride (Lion Co., Ltd., ARCARD T-800, [RN (CH ₃ ) ₃ ] Cl, R is C ₁₆ and C ₁₈ ) equivalent to Na equivalent to 100 g of synthesized magadiite The mixture was dispersed in 1000 ml and stirred at room temperature for 24 hours to ion-exchange Na and stearyltrimethylammonium. The solid was separated from the dispersion by filtration and washed with water. This magadiite was again dispersed in 1000 ml of a 0.6 times equivalent aqueous solution of stearyltrimethylammonium chloride and stirred at room temperature for 24 hours to ion-exchange Na and stearyltrimethylammonium. The solid was separated from the dispersion by filtration, washed with water, dried at 110 ° C., and pulverized with an KA-10 MF-10 tabletop pulverizer to obtain a powder. When a part of the powder was taken out and SEM observation was performed, the particle shape in which the scaly crystals were laminated could be observed. The average particle size by SEM observation was 3 μm. Moreover, the heat loss to 170 degreeC was 1.9 weight%. In XRD, 15.6ｄ of the original d ₀₀₁ disappears, a new peak of 32.6Å of d ₀₀₁ and d ₀₀₂ appear at 16.6Å, and stearyltrimethylammonium is introduced between the layers of magadiite. It has been confirmed that. Chemical analysis confirmed that Na was not present and (stearyltrimethylammonium) ₂ .Si ₁₄ O ₂₉ .xH ₂ O was obtained. The powder obtained here is designated as Sample B.
(2) Preparation of Inorganic Porous Material Using Sample B The same operation as in Example 1 was performed except that Sample B was used instead of Sample A in Example 1. The obtained powder could observe a particle shape similar to that of Sample B by SEM observation. The average particle size by SEM observation was 3 μm. In XRD, 32.6 mm of d ₀₀₁ of sample B disappears, and a large and broad diffraction pattern having a peak at 37.6 mm of new d ₀₀₁ appears, and silica is introduced between the layers of magadiite to form an interlayer cross-linked structure. It was confirmed that When the thickness of the silicate layer is reduced by 12.8 mm from the surface distance d ₀₀₁ of 37.6 mm, the distance between the layers is 24.8 mm. The DH method pore size distribution by nitrogen adsorption was measured and shown in FIG. From FIG. 8, the silica crosslinked porous material has a pore width of 20 to 40 mm and a peak of pore distribution at 27.4 mm. This value almost coincides with 24.8 cm calculated from XRD. The specific surface area calculated at the same time was 182 m ² / g. In the simple measurement method, it was 177 m ² / g. The low-angle and high-angle XRD diffraction patterns of this inorganic porous material are shown in FIGS. 9 (a) and 9 (b).

Example 5
(1) Magadiite distearyldimethylammonium ion exchange (preparation of sample C)
100 g of synthesized magadiite is 0.5 times the amount of Na distearyldimethylammonium chloride (manufactured by Lion Corporation, Arcard 2HT-75, [R ₂ N (CH ₃ ) ₂ ] Cl, R is C _{14 to} C ₁₅ ) Was dispersed in 1000 ml of an aqueous solution and stirred at room temperature for 24 hours to ion-exchange Na and distearyldimethylammonium. The solid was separated from the dispersion by filtration and washed with water. This magadiite was again dispersed in 1000 ml of an aqueous solution of 0.5 times equivalent of distearyldimethylammonium chloride and stirred at room temperature for 24 hours to ion-exchange Na and distearyldimethylammonium. The solid was separated from the dispersion by filtration, washed with water, dried at 110 ° C., and pulverized with an KA-10 MF-10 tabletop pulverizer to obtain a powder. When a part of the powder was taken out and SEM observation was performed, the particle shape in which the scaly crystals were laminated could be observed. The average particle size by SEM observation was 2 μm. The heat loss up to 170 ° C. was 1.3% by weight. In XRD, the original d ₀₀₁ 15.6Å disappears, the new d ₀₀₁ 45.2Å large peak, its d ₀₀₂ appears at 23.7Å, and d ₀₀₃ appears at 16.0 マ, magadiite It was confirmed that distearyldimethylammonium was introduced between these layers. Further, it was confirmed by chemical analysis that Na was not present and (distearyldimethylammonium) ₂ .Si ₁₄ O ₂₉ .xH ₂ O was obtained. The powder obtained here is designated as Sample C.
(2) Preparation of Inorganic Porous Material Using Sample C The same operation as in Example 1 was performed except that Sample C was used instead of Sample A in Example 1. The obtained powder could observe a particle shape similar to that of Sample C by SEM observation. The average particle size by SEM observation was 2 μm. In XRD, 45.2Ｃ of d ₀₀₁ of sample C disappears, and a new broad diffraction pattern with a peak at 39.3Å of d ₀₀₁ and a shoulder at 23.2Å appears, It was confirmed that silica was introduced into the structure to form an interlayer crosslinked structure. When the thickness of the silicate layer is reduced by 12.8 mm from the surface distance d ₀₀₁ of 39.3 mm, the distance between the layers is 26.5 mm. The specific surface area calculated at the same time was 537 m ² / g. The specific surface area was 499 m ² / g by a simple measurement method.

Example 6
(1) Magadiite dicoco alkyldimethylammonium ion exchange (Preparation of sample D)
100 g of synthesized magadiite is 0.5 times equivalent of Na amount of dicoco alkyldimethylammonium chloride (manufactured by Lion Corporation, ARCARD 2C-75, [R ₂ N (CH ₃ ) ₂ ] Cl, R is C ₈ -C ₁₈ ) was dispersed in 1000 ml of an aqueous solution and stirred at room temperature for 24 hours to ion exchange Na and dicoco alkyldimethylammonium. The solid was separated from the dispersion by filtration and washed with water. This magadiite was again dispersed in 1000 ml of a 0.5-fold equivalent aqueous solution of dicoco alkyldimethylammonium chloride and stirred at room temperature for 24 hours to ion exchange Na and dicoco alkyldimethylammonium. The solid was separated from the dispersion by filtration, washed with water, dried at 110 ° C., and pulverized with an KA-10 MF-10 tabletop pulverizer to obtain a powder. When a part of the powder was taken out and SEM observation was performed, the particle shape in which the scaly crystals were laminated could be observed. The average particle size by SEM observation was 2 μm. Moreover, the heat loss to 170 degreeC was 1.4 weight%. In XRD, the original d ₀₀₁ of 15.6 な く な り disappears, the new d ₀₀₁ 's large peak of 38.4Å, its d ₀₀₂ appears at 19.9Å, d ₀₀₃ appears at 13.4Å, and magadiite It was confirmed that dicoco alkyldimethylammonium was introduced between these layers. Further, it was confirmed by chemical analysis that Na was not present and (disidium alkyldimethylammonium) ₂ .Si ₁₄ O ₂₉ .xH ₂ O was obtained. The powder obtained here is designated as sample D.
(2) Preparation of Inorganic Porous Material Using Sample D The same operation as in Example 1 was performed except that Sample D was used instead of Sample A in Example 1. The obtained powder could observe a particle shape similar to that of Sample D by SEM observation. The average particle size by SEM observation was 2 μm. In XRD, 38.4 mm of d ₀₀₁ of sample D disappears, and a broad diffraction pattern having a peak at 34.5 mm of new d ₀₀₁ appears, and a smaller broad diffraction pattern appears at 13.1 mm. It was confirmed that silica was introduced between the layers of magadiite to form an interlayer crosslinked structure. When the thickness of the silicate layer is reduced by 12.8 mm from the surface distance d ₀₀₁ of 34.5 mm, the distance between the layers is 21.7 mm. The specific surface area calculated at the same time was 423 m ² / g. The specific surface area was 386 m ² / g by a simple measurement method. The DH method pore size distribution by nitrogen adsorption was measured and shown in FIG. From FIG. 10, the silica crosslinked porous material has a pore width of 20 to 40 mm and a peak of pore distribution at 22.9 mm. FIG. 11 shows low-angle and high-angle XRD diffraction patterns of this inorganic porous material.

It is a SEM image of magadiite. It is a SEM image of magadiite. It is a figure which shows the structural model of magadiite. It is a SEM image of magadiite after ion exchange. It is a SEM image of magadiite after ion exchange. 2 is a low-angle and high-angle XRD diffraction pattern of magadiite used in Example 1. FIG. 3 is a DH method pore size distribution measurement result by nitrogen adsorption of the inorganic porous material obtained in Example 1. FIG. It is a DH method pore diameter distribution measurement result by nitrogen adsorption of the inorganic porous material obtained in Example 4. It is the XRD diffraction pattern of the low angle and high angle of the inorganic porous body obtained in Example 4. It is a DH method pore size distribution measurement result by nitrogen adsorption of the inorganic porous material obtained in Example 6. It is the XRD diffraction pattern of the low angle and high angle of the inorganic porous material obtained in Example 6.

Claims (13)

  An inorganic porous material characterized in that a layered silicic acid layer composed of magadiite or kenyaite is crosslinked with a metal oxide and has a main peak of pore size distribution in a range of 20 to 40%.   The inorganic porous body according to claim 1, wherein the metal oxide is at least one selected from the group consisting of silica, alumina, titania and zirconia.   The inorganic porous body according to claim 2, wherein the metal oxide is silica.   The inorganic porous body according to claim 3, wherein the silica is a hydrolysis product of alkoxysilane.   The inorganic porous body according to claim 4, wherein the alkoxysilane is tetraalkoxysilane.   The inorganic porous body according to any one of claims 1 to 5, which does not contain an alkali metal or alkaline earth metal component. It has a specific surface area of 300-600 m < ² > / g, The inorganic porous body as described in any one of Claims 1-6 characterized by the above-mentioned.   The inorganic porous body according to any one of claims 1 to 7, which has at least one diffraction peak in a range of 33 to 50 mm in X-ray diffraction. It is a manufacturing method of the inorganic porous body according to claim 1,
By introducing a quaternary ammonium ion between layers of layered silicic acid consisting of magadiite or kenyanite by ion exchange to widen the layer spacing, further introducing a metal oxide between the layers, and then firing the layered silicic acid A method for producing an inorganic porous material, wherein quaternary ammonium ions are removed and the layer of layered silicic acid is crosslinked with a metal oxide.   The method for producing an inorganic porous body according to claim 9, wherein the metal oxide is silica.   The method for producing an inorganic porous body according to claim 10, wherein the silica is a hydrolysis product of tetraalkoxysilane.   The method for producing an inorganic porous material according to claim 11, wherein the quaternary ammonium ion is a long-chain dialkyldimethylammonium ion or a long-chain alkylaryldimethylammonium ion.   The method for producing an inorganic porous body according to claim 12, wherein the long-chain alkyl group of the quaternary ammonium ion has 8 to 24 carbon atoms.

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