JPH01115880A - Production of inorganic laminar porous form - Google Patents

Abstract

PURPOSE:To obtain the titled porous form of high open-cell content with large interlaminar space, suitable for catalysts, molecular sieves etc., by interlaminarly introducing a specific metallic oxide precursor into a laminar compound being in a swelled state followed by drying and calcination to interlaminarly produce a metallic oxide as the pillar material. CONSTITUTION:First, a swellable laminar compound 1 (e.g. sodium salt of montmorillonite) is dispersed in a solvent 4 (e.g. water) to intrude side solvent 4 into the spaces between the layers 1a, 1a to effect swelling of the compound 1. Thence, a metallic oxide precursor selected from respective nitrates, chlorides, acetates, sulfates and alkoxides of Y, Ba, Sr and Cu is added to the resultant dispersion to effect cation exchange with the cations existing interlaminarly within the laminar compound 1 to introduce said precursor into the spaces between the layers. The resulting laminar compound 1 is dried and calcined to produce a metallic oxide 2 as the pillar material within said spaces between the layers 1a, 1a, thus obtaining the objective porous form.

Description

[Detailed description of the invention] 〔Technical field〕 The present invention relates to a method for producing an inorganic layered porous body.

[Background technology]

A method for producing an inorganic layered porous body in which a metal oxide is produced as a pillar material between layers of layered compounds in a swollen state is known. Inorganic layered porous materials have excellent heat insulation properties, so
Used for insulation, etc. One of the methods for manufacturing the above-mentioned inorganic layered porous material uses a metal hydroxide as a precursor of the metal oxide (see Japanese Patent Application Laid-Open No. 54-5884, Japanese Patent Application Laid-Open No. 54-16386, etc.) ) However, the inorganic layered porous material produced by this method has a small interlayer spacing and is therefore unsuitable for applications such as catalysts and molecular sieves.

On the other hand, there is a method for producing an intercalation compound in which the interlayers of a smectite mineral are swollen with a dispersion medium of a water-soluble polymer compound, and a cationic oxide or polymeric silica is inserted and reacted with this (Japanese Patent Application Laid-Open No. 60-131878, JP 60-137812, JP 60-137812, JP 60-137812, JP 60-137812.
137813, JP 60-155526, JP 60-166217, etc.) However, in this manufacturing method, when the firing temperature is lower than 500°C, the water-soluble polymer is completely burned off. carbon remains between the layers. In order to completely remove this carbon, it is necessary to perform firing at a temperature of 500°C or higher, but this destroys the structure of the smectite mineral itself, which is the main structure, and the layer expanded by water-soluble polymers. Unable to maintain distance. Therefore, this manufacturing method is unsuitable for manufacturing inorganic layered porous bodies used for applications such as catalysts.

[Purpose of the invention]

The present invention was made in view of the above circumstances, and is an inorganic layered porous material that has a large interlayer spacing and does not contain carbon between the layers, and can be effectively used for catalysts, adsorbents, etc. The purpose is to provide a manufacturing method.

[Disclosure of the Invention] In order to achieve this object, the inventors have proposed using a material that has a large molecular weight and does not cause problems during firing as the pillar material inserted between the layers of the layered compound in a swollen state. In order to obtain an inorganic layered porous body by producing a metal oxide as a pillar material between layers of a layered compound in a swollen state, yttrium is used as a precursor of the metal oxide. ,barium,
The gist of the present invention is a method for producing an inorganic layered porous material using at least one selected from the group consisting of nitrates, chlorides, acetates, sulfates, and alkoxides of strontium and copper.

The present invention will be explained in detail below.

As shown in FIG. 1, which schematically shows the structure, the inorganic layered porous body A obtained using the present invention has a metal oxide 2 between the layers 1a and 1a of the inorganic layered compound 1 shown in FIG. is inserted as a pillar material, and the interlayer distance 3 is 10 to 30
held by a person. As the inorganic layered compound 1, Na
-Montmorillonite, Ca-montmorillonite, acid clay, 3-octahedral synthetic smectite, synthetic mica (Na-fluorine silicon mica), Na-teniolite, Li-teniolite, Na-hectorite, Li-hectorite, etc. , and is not limited to these as long as it is a swellable layered compound. In addition, when using a low-swellable inorganic layered compound such as Ca-montmorillonite or acid clay, it is necessary to apply shearing force by kneading or the like to cause swelling.

As a precursor to become the metal oxide 2 which is the pillar material,
Yttrium, barium, strontium or copper nitrate, chloride, acetate, sulfate or general 2M''% (O
It is possible to use an alkoxide represented by R) x (M: each of the above metals; R: an alkyl group such as a methyl group, ethyl group, propyl group, butyl group; 8 is a valence number). In addition,
These precursors may be used alone or in combination.

Next, the method for manufacturing the inorganic layered porous material A according to the present invention will be explained in detail with reference to schematic diagrams.

The swellable clay mineral is made of a collection of swellable inorganic layered compounds 1, as shown in FIG. First, the inorganic layered compound 1, which is the main material of the inorganic layered porous material A, is dispersed in a solvent, and as shown in FIG. 3, the solvent 4 is allowed to penetrate between the layers 1a and 1a to cause swelling. Generally, water can be used as the solvent 4, but other polar solvents such as methanol, DMFSDMSO, etc. can be used alone or in combination.

Next, the inorganic layered compound 1 in a swollen state is dispersed,
An aqueous solution of the metal salt or metal alkoxide is added to this solution. In addition, when using an alkoxide, it is added after hydrolysis. In this aqueous solution, the metal exists in the form of a complex ion, and undergoes cation exchange with the cation present between the layers of the inorganic layered compound 1.

In this way, as shown in FIG. 4, a layered compound having pillars 2 between layers 1a and 1a is obtained.

Finally, this layered compound is dried at 60 to 70°C and then fired at 200 to 600°C to form an inorganic layered porous body A. Note that the firing can be omitted, but it is preferable to perform the firing because the structure of the inorganic layered porous body can be made more stable.

Next, examples of this invention will be described.

(Example 1) A 10 wt% aqueous solution of yttrium nitrate (reagent manufactured by Hanui Kagaku ■) was prepared, and to this was added Na-montmorillonite (Nipia F manufactured by Kunimine Industries ■) that had been swollen with water in advance.
The reaction was carried out at about 70°C. Next, water is removed from this reaction product by centrifugation, and the obtained solid is oriented with a spatula to obtain a plate-shaped body. After drying this plate-shaped body with hot air at a temperature of 60 to 70°C, It was fired at 500° C. for 2 hours to obtain a plate-shaped molded porous body sample having a thickness of 3 fl and made of inorganic layered porous body A.

The molar ratio of yttrium, Na-montmorillonite, and water was 10:1,000.

(Example 2) A plate-shaped molded porous body sample was obtained in the same manner as in Example 1 except that copper nitrate was used instead of yttrium nitrate.

(Example 3) A plate-shaped molded porous body sample was obtained in the same manner as in Example 1 except that barium nitrate was used instead of indium nitrate.

(Example 4) A plate-shaped molded porous body sample was obtained in the same manner as in Example 1 except that strontium nitrate was used instead of yttrium nitrate.

(Example 5) A plate-shaped molded porous body sample was obtained in the same manner as in Example 1 except that copper acetate was used instead of yttrium nitrate.

(Example 6) A plate-shaped molded porous body sample was obtained in the same manner as in Example 1 except that barium chloride was used instead of indium nitrate.

(Example 7) A plate-shaped molded porous body sample was obtained in the same manner as in Example 1 except that strontium sulfate was used instead of yttrium nitrate.

(Example 8) A plate-shaped molded porous body sample was prepared in the same manner as in Example 1, except that a sufficiently mixed 10 wt % aqueous solution of indium nitrate and barium chloride was used instead of the yttrium nitrate aqueous solution. Obtained.

The molar ratio of yttrium, barium, Na-montmorillonite, and water was 5:5:1000.

(Example 9) Instead of the yttrium nitrate aqueous solution, 19 wt % aqueous solutions each of barium acetate (reagent manufactured by Hanui Chemical ■) and sulfuric acid (m < reagent manufactured by Hanui Chemical ■) were prepared, and a mixture of these was used. A plate-shaped molded porous body sample was obtained in the same manner as in Example 1 except that the sample was prepared in the same manner as in Example 1.

The molar ratio of barium, copper, Na-montmorillonite, and water was 5:5:1 near 000.

(Example 10) Instead of the indium nitrate aqueous solution, 10-t% aqueous solutions of each of yttrium nitrate, barium chloride, and copper acetate were prepared, and a mixed solution of these sufficiently mixed was used.
A plate-shaped molded porous body sample was obtained in the same manner as in Example 1.

The molar ratio of yttrium, barium, copper, Na-montmorillonite, and water was 1:2:3:1.
It was 00.

(Example 11) Instead of an aqueous yttrium nitrate solution, yttrium ethoxide was mixed with an appropriate amount of ethyl alcohol at 70°C under an IN-NH,OH catalyst. A plate-shaped molded porous material sample was obtained in the same manner as in Example 1, except that the reacted material was used.

The molar ratio of yttrium ethoxide to NH and OH was 1.

(Example 12) A plate-shaped molded porous body sample was obtained in the same manner as in Example 11 except that copper ethoxide was used instead of yttrium ethoxide.

(Example 13) A plate-shaped molded porous body sample was obtained in the same manner as in Example 11 except that barium ethoxide was used instead of indolium ethoxide.

(Example 14) A plate-shaped molded porous body sample was obtained in the same manner as in Example 11 except that strontium ethoxide was used instead of yttrium ethoxide.

(Example 15) Instead of the yttrium nitrate aqueous solution, copper ethoxide and barium ethoxide were dissolved and reacted with an appropriate amount of ethyl alcohol at 70°C under an IN-NH,OH catalyst. A plate-shaped molded porous body sample was obtained in the same manner as in Example 1.

In addition, copper ethoxide, barium ethoxide, NH4OH
% Na-montmorillonite and water were in a molar ratio of 2:3 near:1:1000.

(Example 16) Instead of the yttrium nitrate aqueous solution, yttrium ethoxide (reagent manufactured by Sumitomo Cement), barium ethoxide (reagent manufactured by Sumitomo Cement), and copper ethoxide (special reagent manufactured by Sumitomo Cement) were dissolved in the applicable ethanol. , in the same manner as in Example 1, except that a well-mixed mixture was reacted at about 70°C under an IN-NH40H catalyst.
A plate-shaped molded porous material sample was obtained.

In addition, yztrium ethoxide, barium ethoxide,
The molar ratio of copper ethoxide and aqueous ammonia is 1=2.
: It was 3' near. Also, yztrium ethoxide,
The molar ratio of barium ethoxide, copper ethoxide, Na-montmorillonite, and water is 1:2:3:1Nia00
It was 0.

(Example 17) A plate-shaped molded porous body sample was obtained in the same manner as in Example 11 except that yttrium isopropylate was used instead of yttrium ethoxide.

(Example 18) A plate-shaped molded porous body sample was obtained in the same manner as in Example 11 except that copper methylate was used instead of yttrium ethoxide.

(Example 19) Instead of the yttrium nitrate aqueous solution, barium isopropylate and strontium isopropylate were used IN
With ethyl alcohol applied under NH,OH catalyst, 70
Example 1 except that the one dissolved and reacted at ℃ was used.
A plate-shaped molded porous body sample was obtained in the same manner as above.

The molar ratio of barium isopropylate, strontium isopropylate, NH40H% Na-montmorillonite, and water is 2:3 near:1 near 0
It was 00.

(Comparative example) 0.036 g of polyethylene oxide with a degree of polymerization of 50,000
Dissolve in 9n+J of water. 31-t% colloidal silica (specially manufactured by Catalysts & Chemicals Industry Co., Ltd., S'I-350) 0.9 in 9mj of dissolved 0.4 wt% polyethylene oxide aqueous solution
Add +nZ and stir to mix. In this aqueous solution, N
1.00 g of a-montmorillonite was added, further stirred and mixed, and then left to dry in a drying bed at 50'C for 2 days to obtain porous samples. The porosity, average interlayer distance, and density of the sample were measured. The results are shown in Table 1. Note that the porosity was calculated using the following formula.

XT Where, P: Surface area of the sample Q: Surface area of the interlayer inorganic compound R: Outer surface area of the interlayer compound in the sample S: Weight of the layered compound in the sample T: Theoretical ratio when all layers of the layered compound are open Surface Area Here, the specific surface area was determined using the BET method in the nitrogen adsorption method, and the average interlayer distance was determined using the CI method in the nitrogen adsorption method. The nitrogen adsorption method was performed using Autosorb 6 manufactured by Quantachrome.

From the results in Table 1, all of the samples of Examples 1 to 19 obtained using the method for producing an inorganic layered porous body according to the present invention had
It can be seen that the porosity and interlayer distance are larger than those of the comparative sample obtained using the conventional manufacturing method.

〔Effect of the invention〕

As described above, the method for producing an inorganic layered porous material according to the present invention is capable of producing an inorganic layered porous material with a large porosity and large interlayer distance, and which has a wide range of uses such as catalysts and molecular sieves. enable.

[Brief explanation of the drawing]

FIG. 1 is a schematic side view of an inorganic layered porous material according to the present invention, FIG. 2 is a schematic side view of a layered compound, FIG. 3 is an explanatory diagram showing the swelling process, and FIG. It is an explanatory view showing a process of inserting an inorganic compound into a layered compound in a swollen state. A... Inorganic layered porous material 1... Inorganic layered compound 1.
...Layer 2...Metal oxide 3...Interlayer distance 4...
・Solvent Figure 1 Figure 2

Claims (2)

[Claims] (1) In producing an inorganic layered porous body by producing a metal oxide as a pillar material between layers of layered compounds in a swollen state, yttrium,
barium, strontium and copper nitrates, chlorides,
A method for producing an inorganic layered porous material using at least one selected from the group consisting of acetates, sulfates, and alkoxides. (2) Swellable layered compounds include Na-montmorillonite, Ca-montmorillonite, acid clay, 3-octahedral synthetic smectite, synthetic mica, Na-teniolite, Li
- A method for producing an inorganic layered porous material according to claim 1, which uses at least one selected from the group consisting of taeniolite, Na-hectorite, and Li-hectorite.