JPH0940417A - Production of crystalline microporous substance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To inexpensively obtain a crystalline microporous substance useful as an adsorbent, catalyst, etc., by mixing a specific crystallization control agent with a soln. of a silicon dioxide component, then batching off precipitated particulates and heating these particulates to crystallize. SOLUTION: An alkaline inorg. material liquid mixture is produced by mixing the crystallization control agent selected from the ammonium ions (e.g.; tetra-n- butylammonium ion) expressed by formula R4 N<+> (R is H, <=10C alkyl, aryl), the phosphonium ion (e.g.; tetra-n-butylphosphonium ion) of the formula R4 P<+> and amines (e.g.; pyrrolidine) and a silicon dioxide component (e.g.; water glass). The particulates precipitated in the inorg. material liquid mixture are separated from the liquid mixture by a method of sepn. solid from the liquid. The solid component formed by the sepn. of the solid from the liquid is then heated to crystallize and to obtain the crystalline microporous substance. The crystalline microporous substance is obtainable as well by mixing an aluminum salt with the silicon dioxide component, batching off the precipitated particulates and heating the particulates to crystallize.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a crystalline microporous body, for example, an adsorbent, a catalyst and a material for separation, that is, a chlorofluorocarbon refrigerant and an insulating medium for high voltage power equipment. As a desiccant such as sulfur fluoride gas and air for vehicle air brakes, an adsorption remover for nitrogen compounds in wastewater and radioactive substances in radioactive wastewater, and as a catalyst supporting various metals by supporting various metals, The present invention relates to a method for producing a crystalline microporous body mainly used in the field of petrochemical industry.

[0002]

2. Description of the Related Art As crystalline microporous materials, there are many natural products such as mordenite and ferrierite, and also as artificial crystalline microporous materials, zeolite-A, zeolite-X, ZSM-5. (Japanese Patent Publication No. 46-
No. 10064) and ZSM-11 (Japanese Patent Publication No.
Various types are known. In the case of producing the artificial crystalline microporous body as described above, after performing a mixing step of forming an inorganic material mixture liquid containing a silicon dioxide component, an aluminum oxide component, and an organic ammonium salt. It was manufactured by a so-called "hydrothermal synthesis method" in which a crystallization step of crystallizing a crystalline microporous body in the above-mentioned inorganic material mixed liquid by high-pressure heating is performed.

That is, in the hydrothermal synthesis method, it was considered that the crystallization step of preparing the above-mentioned inorganic material mixed solution and then heating and crystallizing it should be carried out in a dispersed state in the liquid. In order to obtain the high temperature and high pressure necessary for crystallization, the inorganic material mixed liquid had to be stored in a high pressure heating container (autoclave) in a liquid state and heated.

[0004]

According to the above-mentioned conventional hydrothermal synthesis method, the high-pressure heating container is expensive, and the inorganic material mixture liquid contains an alkali metal oxide or alkaline earth metal oxide component. , It is strongly alkaline because it contains oxides and hydroxides, and in order to prevent corrosion due to alkali, the high-pressure heating container was treated with stainless steel or a fluororesin coating. This included factors that increased the manufacturing cost in terms of manufacturing equipment, such as the need to use materials. In addition, in order to handle the above strongly alkaline mixed liquid, it is necessary to take sufficient measures regarding safety for workers engaged in the work, and as a result, it must be said that it is a very expensive synthesis method. I didn't get it.

Further, according to the hydrothermal synthesis method, in the crystallization step, it is usually carried out at a high temperature condition of 70 to 200 ° C., and sometimes higher, for several days, sometimes 10 days or more for a long time. Since the mixed solution had to be heated, there was also the problem that violent reaction conditions were necessary.
This was also reflected in the manufacturing cost.

Furthermore, although the crystalline microporous body obtained by the hydrothermal synthesis method is in the form of fine particles and may need to be molded in some cases, the crystalline microporous body in the form of fine particles generally has the following properties. Since it does not have a cohesive force, it must be sintered at an extremely high temperature or must be molded with a binder interposed. Therefore, the surface layer of the crystal is melted by the sintering at a high temperature and the porous structure is formed. Are blocked, or the proportion of the crystalline microporous body in the molded product is smaller, the ratio of the porous structure per unit weight of the molded product is reduced, the porous structure The derived physical properties such as adsorption activity and catalytic activity tended to be low.

Therefore, in view of the above situation, an object of the present invention is to provide a method for producing a crystalline microporous body which can be synthesized at a low cost under more mild conditions, and further, an inexpensive crystalline microporous body. Alternatively, it is to provide a crystalline microporous body molded product, and to provide a crystalline microporous body that exhibits high performance in various fields of use.

[0008]

Means for Solving the Problems To achieve this object, the characteristic means of the method for producing a crystalline microporous body of the present invention is that an ammonium ion (R ₄ N ⁺ : R is hydrogen, alkyl having 10 or less carbon atoms) is used. Group or at least one selected from an aryl group), a phosphonium ion (R ₄ P ⁺ : R is at least one selected from hydrogen, an alkyl group having 10 or less carbon atoms or an aryl group), and an amine. Crystallization modifier and silicon dioxide (S
a mixing step of forming an alkaline inorganic material mixed solution containing an iO ₂ ) component, and after the mixing step, fine particles precipitated in the inorganic material mixed solution are separated from the inorganic material mixed solution. The liquid separation step is performed, and the solid component separated by solid-liquid separation is heated to be crystallized. The crystallization modifier is tetra-n-butylammonium ion ((n-C ₄ H _{9) 4} N ^+), tetra n-
Propylammonium ion _{((n-C 3 H 7} ) 4 N +), tetraethylammonium ion _{((C 2 H 5) 4} N +), tetramethylammonium ion ^{_{((CH 3) 4 N +}} ), n- propyl trimethyl ammonium ion _{((n-C 3 H 7} ) (CH
₃ ) ₃ N ⁺ ), benzyltrimethylammonium ion ((C
_{7 H 7) (CH 3)} 3 N +), tetra-n- butyl phosphonium ion _{((n-C 4 H 9} ) 4 P +), benzyl triphenyl phosphonium ion _{((C 7 H 7) (} C 6 H 5 ) ₃ P ⁺ ), 1,4-dimethyl-1,4-diazobicyclo (2,2,2) octane, pyrrolidine, n-propylamine (n-C ₃ H ₇ NH
₂ ) and methylquinuclidine are preferably used. Also,
The crystallization step, after enclosing the solid component that has been solid-liquid separated in a closed container, is performed by heating the closed container,
Alternatively, it may be carried out by supplying water vapor to the solid component separated by solid-liquid separation, and after the solid component separated by solid-liquid separation may be molded, a crystallization step may be carried out. Is.

[Operation / Effect] When the silicon dioxide (SiO ₂ ) component and the crystallization modifier are allowed to coexist under alkaline conditions (mixing step), in the inorganic material mixture liquid coexisting with the crystallization modifier, Inorganic materials are aggregated around the crystallization modifier to form fine particles of the composite, and thus the composite can be isolated as a solid component by a solid-liquid separation process. The present invention is based on the new finding that the solid component of the isolated composite body undergoes a phase change by heat treatment to be crystallized into a porous crystal body. That is, by heating the solid component to crystallize it (crystallization step), the solid component is crystallized in a state in which the inorganic material surrounds various crystal modifiers as cores. After all, a crystalline microporous body having a porous structure with uniform pore diameters can be formed from the crystals by a simple operation of heating the solid-state composite.

As the crystallization modifier, ammonium ions (R ₄ N ⁺ : R is hydrogen, at least one selected from alkyl groups having 10 or less carbon atoms or aryl groups), phosphonium ions (R ₄ P ⁺ : R may be at least one selected from hydrogen, at least one selected from an alkyl group having 10 or less carbon atoms or an aryl group) and amines, and particularly tetra n-butylammonium ion ((n-C ₄ H _{9) 4} N ^+), tetra n-
Propylammonium ion _{((n-C 3 H 7} ) 4 N +), tetraethylammonium ion _{((C 2 H 5) 4} N +), tetramethylammonium ion ^{_{((CH 3) 4 N +}} ), n- propyl trimethyl ammonium ion _{((n-C 3 H 7} ) (CH
₃ ) ₃ N ⁺ ), benzyltrimethylammonium ion ((C
_{7 H 7) (CH 3)} 3 N +), tetra-n- butyl phosphonium ion _{((n-C 4 H 9} ) 4 P +), benzyl triphenyl phosphonium ion _{((C 7 H 7) (} C 6 H 5 ) ₃ P ⁺ ), 1,4-dimethyl-1,4-diazobicyclo (2,2,2) octane, pyrrolidine, n-propylamine (n-C ₃ H ₇ NH
₂ ) and methylquinuclidine are preferable as long as they contain at least one selected from the group consisting of various ammonium salts,
It is believed that phosphonium salts and amines can be used. The tetrapropylammonium salt gives a crystalline microporous body having an MFI structure, and the tetrabutylammonium salt gives a crystalline microporous body having a MEL structure. If an organic ammonium salt is selected, crystalline microporous materials having various pore sizes can be obtained.

When an aluminum salt is made to coexist in a mixed solution containing a silicon dioxide (SiO ₂ ) component to make it alkaline (mixing step), the inorganic material mixed solution in which the aluminum salt is made to coexist contains aluminum. It is easy to form a complex. Also for this composite, when the solid-liquid separation step of performing solid-liquid separation from the inorganic material mixed solution and the crystallization step of heating crystallization are performed, the skeleton of the porous body undergoes a phase change to be crystallized to form a porous crystalline body. Since it can be seen that the crystalline microporous body can be obtained in the same manner as described above, the crystalline microporous body can be formed by a simple operation of only heating the solid state one. So, for example,
ZSM-5 structure zeolite, which has been very expensive in the past, can now be provided at low cost.

Further, since the solid component of the composite tends to have a cohesive force, it can be preformed by a simple operation such as pressurizing. Therefore, after molding the composite, The crystallization step has an advantage that even a molded product having a complicated shape can be easily obtained.

The crystallization step is performed by enclosing the solid-liquid separated complex in a closed container and then heating the closed container, or by vaporizing the solid-liquid separated complex with water vapor. It may be supplied, and according to such a heating method, it is not necessary to heat to a high temperature under high pressure, the handling is easy, and the manufacturing cost is easily set low.

Therefore, since crystallization can be carried out by a simple process of heating the solid component, there is no need to carry out hydrothermal synthesis using a high-pressure heating container, and it can be handled in a solid state and water in a mixed liquid state. It is easier to handle than performing thermal synthesis, and there is less need to enhance measures such as alkali corrosion resistance even as a heating container, making it possible to reduce manufacturing costs in terms of equipment and manufacturing costs in terms of safety management. Can be set cheaply, and the crystallization conditions for heating are milder than before (for example, 130 ° C. in the examples described later).
It is possible to manufacture it at low cost even under the reaction condition for 8 hours), and the economical efficiency is improved. In addition, since crystalline microporous materials can be synthesized with simple equipment such as glass containers, even for small-scale research and development, small quantities, large quantities,
It is considered to be useful for manufacturing various crystalline microporous materials.

Further, since a crystalline microporous body having a high cohesive force can be obtained by simple preforming even a molded article having a complicated shape, conventionally, the crystalline microporous body is preformed using a binder. In comparison with the product obtained by firing, it is possible to increase the performance of the molded product derived from the porous structure, such as the ratio of the porous structure per unit weight can be increased, and the performance as a molded product is conventionally improved. It has become possible to use it in various fields that were not used because of its low price.

Furthermore, when only the solid component of the composite is molded and then crystallized, the molded product has better dimensional stability than the molded product formed by high temperature sintering, and the molded product From a manufacturing standpoint, it can be said to be useful for lowering manufacturing costs such as improved yield.

Further, by using the solid component of the composite as a binder, for example, natural zeolite or a plurality of types of crystalline microporous bodies can be molded to produce a product having a crystalline microporous body as a whole. it can.

It is also possible to introduce aluminum element into the crystal structure by exposing the crystalline microporous body to aluminum chloride vapor or introducing aluminum ions when forming a composite. The porous body can be used as a catalyst for the production of ethylbenzene or paraxylene.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments will be shown below, but the present invention is not limited thereto. In addition, as the raw material set, the following composition was used (all of the percentages are% by weight). ○ No. 3 water glass: analytical value SiO ₂ : 29.17%, N
a ₂ O: 9.82% (Toda silicate No. 3 manufactured by Nippon Chemical Industry Co., Ltd.) ○ Silica powder (high-purity silica powder manufactured by Tama Chemical Industry Co., Ltd.) ○ Tetrapropylammonium bromide ((n -C ₃ H _{7) 4} NO
H) :( Tokyo Chemical Industry Co., Ltd.) ○ tetrabutylammonium bromide _{((n-C 3 H 7} ) 4 NB
r) :( Tokyo Chemical Industry Co., Ltd.) ○ tetrapropylammonium hydroxide _{((n-C 3 H 9} ) 4 N
OH) aqueous solution: 20 to 25% (manufactured by Tokyo Chemical Industry Co., Ltd.) ○ Benzyltrimethylammonium hydroxide ((C ₇ H ₇ ) (C
H _{3) 3} NOH) water solution: 40% (Tokyo Kasei Kogyo Co., Ltd.) ○ aluminum tri -sec- butoxide: (Al (O-
(CH (CH ₃ ) (C ₂ H ₅ )) ₃ ) (manufactured by Tokyo Chemical Industry Co., Ltd.) ○ Sodium aluminate (NaAlO ₂ ): (manufactured by Wako Pure Chemical Industries, Ltd.) ○ Tetraethyl orthosilicate ( Tokyo Chemical Industry Co., Ltd.
Company Ltd. "TEOS") ○ tetrabutylammonium hydroxide _{((n-C 4 H 9} ) 4 NO
H) Aqueous solution: 40% ("TBA" manufactured by Tokyo Chemical Industry Co., Ltd.)
OH ") ○ Copper acetylacetonate (Cu (CH ₃ COCHCOC
H _{3) 2):} ((Ltd.) Dojin Chemical Laboratory)

[Example 1] 1 g of 100 g of No. 3 water glass
Deionized water was added to dilute the 200 g, this tetrapropylammonium bromide _{((n-C 3 H 7} ) 4 NOH) 13g a by adding well撹袢to give a soft gel-like inorganic material mixture liquid ( Mixing step). If you add about 18g of concentrated hydrochloric acid,
This gel became a stiffer gel. The pH of the supernatant of this gel was found to be about 8. The solid gel was thoroughly washed with deionized water, filtered under reduced pressure, collected, and air-dried at room temperature to obtain a white powder (solid-liquid separation step). This powder is believed to have a complex with water glass and tetrapropylammonium ion _{((n-C 3 H 7} ) 4 N +). The powder of the composite thus produced was put into a test tube made of hard glass, the test tube was sealed in air, and the test tube was placed in a thermostatic chamber at 150 ° C for 2 hours.
A heat treatment of leaving for 4 hours was performed (crystallization process). Then, it was left to cool to room temperature and a reaction product was obtained from the test tube. When the reaction product was examined by measuring the powder X-ray diffraction spectrum, it was found to be a crystalline microporous body composed of silicalite-1 having an MFI structure.

Example 2 1 to 100 g of No. 3 water glass
Deionized water was added to dilute the 200 g, this tetrapropylammonium bromide _{((n-C 3 H 7} ) 4 NBr) and aluminum chloride 13g and 2.3g were well撹袢added,
A soft gel-like inorganic material mixed solution was obtained (mixing step). When about 16 g of concentrated hydrochloric acid is added, this gel becomes
It became a stiffer gel. The pH of the supernatant of this gel
Was about 8. The solid gel was thoroughly washed with deionized water, filtered under reduced pressure, collected, and air-dried at room temperature to obtain a white powder (solid-liquid separation step). The powder, water glass, tetrapropylammonium ion _{((n-C 3 H 7} ) 4 N +), is considered to have become a complex of aluminum oxide. Put the powder of the composite thus produced in a hard glass test tube,
The test tube was sealed in air. This was heat-treated by leaving it in a constant temperature bath at 150 ° C. for 24 hours, and then allowed to cool to room temperature to obtain a reaction product from the test tube (crystallization step). When this reaction product was examined by measuring a powder X-ray diffraction spectrum, it was found to be a crystalline microporous body composed of ZSM-5 having an MFI structure.

[Example 3] 100 g of No. 3 water glass was added to 1
Deionized water was added to dilute the 200 g, this tetrabutylammonium bromide _{((n-C 4 H 9} ) 4 NBr) was well撹袢added 16g, to obtain a soft gel-like inorganic material mixture liquid ( Mixing step). When about 12 g of concentrated hydrochloric acid was further added, this gel became a stiffer gel. When the pH of the supernatant of this gel was examined, it was about 8. The solid gel was thoroughly washed with deionized water, filtered under reduced pressure, collected, and naturally dried at room temperature to obtain a white powder (solid-liquid separation step). This powder is believed to have a complex with water glass and tetra-butyl ammonium ion _{((n-C 4 H 9} ) 4 N +). The powder of the composite thus produced was placed in a hard glass test tube, and the test tube was sealed in air. This was heat-treated by leaving it in a constant temperature bath at 130 ° C. for 40 hours, and then allowed to cool to room temperature to obtain a reaction product from the test tube (crystallization step).
When this reaction product was examined by measurement of powder X-ray diffraction spectrum, silicalite-2 having a MEL structure was obtained.
It was found to be a crystalline microporous body consisting of.

Example 4 About 1 g of the powder of the composite material produced in Example 1 was placed on a small glass filter, and this glass filter was coated with fluorine resin on the inner surface together with about 7 g of deionized water. Put the composite powder in a pressure-resistant container and keep it from touching water directly.
Heat treatment was performed for 8 hours with 30 ° C. steam to obtain a reaction product (crystallization step). When this reaction product was examined by measurement of powder X-ray diffraction spectrum, MFI
It was found to be a crystalline microporous body composed of silicalite-1 having a structure.

Example 5 The powder of the composite body produced in Example 1 was uniaxially compressed at 500 MPa using a hydraulic press to obtain a molded product. The molded product was placed in a test tube of hard glass, sealed in air, and heat-treated by allowing it to stand in a constant temperature bath at 130 ° C. for 20 hours, and then allowed to cool to room temperature to obtain a reaction product. (Crystallization step). The reaction product was taken out and examined, but no deformation could be confirmed.
When this reaction product was examined by measurement of powder X-ray diffraction spectrum, it was found to be a crystalline microporous body composed of silicalite-1 having an MFI structure, as in Example 1.

Example 6 About 1 g of the composite powder produced in Example 1 was placed on a small glass filter and subjected to heat treatment at 130 ° C. for 20 hours under atmospheric pressure to obtain a reaction product. Obtained (crystallization step). When this reaction product was examined by measurement of powder X-ray diffraction spectrum, it was found to be a crystalline microporous body composed of silicalite-1 having an MFI structure, as in Example 1.

Example 7 60 g of silica powder was added to 90
g of tetrapropylammonium hydroxide ((n-C _ThreeH₉)_Four
(NOH) Aqueous solution left for 2 weeks at room temperature to dissolve uniformly
Then, an inorganic material mixed solution was obtained (mixing step). This inorganic
White precipitate occurs when a large amount of methanol is added to the mixed material solution.
Occurred. The white precipitate was collected by vacuum filtration,
And air dried at room temperature to obtain white powder (solid-liquid separation
Process). This powder consists of silica and tetrapropylammonium
Um-ion ((n-C_ThreeH₇)_FourN⁺) Is a complex with
It is considered to be. The powder of the composite of hard glass
It was placed in a test tube and sealed in air. To this, 150 ℃
Heat treatment for 20 hours in a constant temperature bath until room temperature
After allowing to cool, a reaction product was obtained (crystallization step). This reaction
The product was examined by measuring powder X-ray diffraction spectra
The result is silicalite-1 having an MFI structure.
It was found to be a crystalline microporous body.

[Example 8] 100 g of No. 3 water glass was added to 1
A solution prepared by adding 00 g of deionized water and diluting it, and 40 g of sodium aluminate (NaAlO ₂ ) 60 g of deionized water
Was mixed with the solution dissolved in, and the mixture was stirred well to obtain a gel-like inorganic material mixed solution (mixing step). The pH of the supernatant of this inorganic material mixed solution was about 10. The solid gel was thoroughly washed with deionized water, filtered under reduced pressure, collected, and air-dried at room temperature to obtain a white powder (solid-liquid separation step). This powder is considered to be a composite of water glass and aluminum oxide.
The SiO ₂ / Al ₂ O ₃ molar ratio of the thus-produced composite powder was 5.3 by fluorescent X-ray analysis. The composite powder was placed in a hard glass test tube and sealed in air. This was subjected to a heat treatment of leaving it in a constant temperature bath at 130 ° C. for 24 hours, and allowed to cool to room temperature to obtain a reaction product (crystallization step). When this reaction product was examined by measurement of powder X-ray diffraction spectrum,
It was found to be a crystalline microporous body composed of Na-P1 having a GIS structure.

Example 9 The powder of the composite produced in Example 8 was placed in a test tube of hard glass and sealed in air. This was subjected to a heat treatment of leaving it in a constant temperature bath of 150 ° C. for 45 hours, and allowed to cool to room temperature to obtain a reaction product (crystallization step). When this reaction product was examined by measurement of powder X-ray diffraction spectrum, it was found to be a crystalline microporous body composed of an anal sim having an ANA structure.

[0029] and tetraethylorthosilicate EXAMPLE 10 62.5 g, tetrabutylammonium hydroxide _{19.5g ((n-C 4 H} 9) 4 NOH) aqueous solution, 68.
When mixed with 3 g of deionized water and heated at 80 ° C. for 1 hour, a gel-like inorganic material mixed solution was obtained (mixing step) (This phenomenon is caused by hydrolysis of tetraethyl orthosilicate, It is believed that this is due to condensation with elimination.). The inorganic material mixture solution was filtered under reduced pressure to obtain a solid component, thoroughly washed with acetone, and then naturally dried to obtain a powder (solid-liquid separation step). The powder and amorphous silicon dioxide is considered that have become complex with tetrabutylammonium ion _{((n-C 4 H 9} ) 4 N +). The composite powder was placed in a hard glass test tube and sealed in air. To this, 150
A heat treatment was performed by leaving it in a constant temperature bath at ℃ for 71 hours, and the reaction product was obtained by cooling to room temperature (crystallization step). When the reaction product was examined by measuring the powder X-ray diffraction spectrum, it was found to be a crystalline microporous body composed of silicalite-2 having a MEL structure.

[0030] and tetraethylorthosilicate Example 11 83.3 g, tetrapropylammonium hydroxide _{36.2g ((n-C 3 H} 9) 4 NOH) aqueous solution, 1g
When mixed with the copper acetylacetonate in Example 1 and heated at 80 ° C. for 1 hour, a gel-like inorganic material mixed solution was obtained (mixing step). The inorganic material mixture solution was filtered under reduced pressure, thoroughly washed with acetone, and then naturally dried to obtain a green powder (solid-liquid separation step). The powder comprises a copper acetylacetonate is believed that is a composite of an amorphous silicon dioxide and tetra-propyl ammonium ion _{((n-C 3 H 9} ) 4 N +). The powder of the composite,
It was put in a test tube made of hard glass and sealed in air. This was subjected to a heat treatment of leaving it in a constant temperature bath at 150 ° C. for 24 hours, and allowed to cool to room temperature to obtain a reaction product (crystallization step). When this reaction product was examined by measurement of powder X-ray diffraction spectrum, it was found to be a crystalline microporous body composed of silicalite-1 having an MFI structure,
It is considered that the crystalline microporous body contains copper acetylacetonate and can be used as a catalyst for denitration and the like.

Example 12 83.3 g of tetraethyl orthosilicate, 16.7 g of benzyltrimethylammonium hydroxide ((C ₇ H ₇ ) (CH ₃ ) ₃ NOH) aqueous solution, and 4.9 g of aluminum tri- sec-butoxide
(And _{Al (O- (CH (CH 3} ) (C 2 H 5)) 3), ethanol were mixed 20g, was heated for one hour at 80 ° C., gel-like inorganic material mixture liquid was obtained ( Mixing step) The inorganic material mixture solution was filtered under reduced pressure, thoroughly washed, and then naturally dried to obtain a white powder (solid-liquid separation step).
When the line spectrum was measured, it was found that Si / Al
Elemental ratio of 95: see that a 5, and the aluminum oxide amorphous silicon dioxide, become complex with benzyltrimethylammonium ion _{((C 7 H 7) (} CH 3) 3 N +) It is considered that The composite powder was placed in a hard glass test tube and sealed in air. This was subjected to a heat treatment of leaving it in a constant temperature bath at 150 ° C. for 530 hours, and allowed to cool to room temperature to obtain a reaction product (crystallization step). When this reaction product was examined by measurement of powder X-ray diffraction spectrum, it was found to be a crystalline microporous body composed of mordenite having a MOR structure.

Example 13 A solution of 84 g of tetraethyl orthosilicate and 5 g of aluminum tri-sec-butoxide dissolved in 40 g of ethanol and a solution of 1.7 g of sodium hydroxide (NaOH) dissolved in 20 g of deionized water. And were mixed and stirred well to obtain a gel-like inorganic material mixed solution (mixing step). The solid gel was thoroughly washed with deionized water, filtered under reduced pressure, collected, and air-dried at room temperature to obtain a white powder (solid-liquid separation step). This powder is considered to be a composite of amorphous silicon dioxide and aluminum oxide.
The SiO ₂ / Al ₂ O ₃ molar ratio of the composite powder produced in this manner was 40 by fluorescent X-ray analysis. The composite powder was placed in a hard glass test tube and sealed in air. This was subjected to a heat treatment of leaving it in a constant temperature bath of 150 ° C. for 500 hours, and allowed to cool to room temperature to obtain a reaction product (crystallization step). When this reaction product was examined by measurement of powder X-ray diffraction spectrum,
It was found to be a crystalline microporous body having a ZSM-5 type structure. The X-ray diffraction spectrum of the crystalline microporous material thus obtained is shown in FIG.
(A) is an X-ray diffraction spectrum of the complex before the crystallization step, and FIG. 1 (b) is a crystalline microporous body after the heat treatment for 500 hours after the previous crystallization step. It is an X-ray diffraction spectrum. According to FIG. 1, the crystalline microporous body gradually shows a spectrum extremely close to the spectrum obtained from the ZSM-5 type structure (see FIG. 2) with the heat treatment, and crystallization progresses. You can read that.

[Brief description of drawings]

1 is the X of the microporous body obtained in Example 13. FIG.
Line diffraction spectrum

FIG. 2 X-ray diffraction spectrum of ZSM-5

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Fujio Mizukami, 1-1 East, Tsukuba City, Ibaraki Prefecture Institute of Industrial Science and Technology, Institute of Materials Engineering (72) Inventor, Kaido Kiyozumi, 1-1, East, Tsukuba City, Ibaraki Prefecture Institute of Materials Engineering

Claims (6)

[Claims] 1. An ammonium ion (R ₄ N ⁺ : R is hydrogen, at least one selected from an alkyl group or an aryl group having 10 or less carbon atoms), and a phosphonium ion (R
₄ P ⁺ : R is at least one crystallization regulator selected from hydrogen, at least one selected from an alkyl group having 10 or less carbon atoms or an aryl group), amines, and a silicon dioxide (SiO ₂ ) component. Performing a mixing step of forming an alkaline inorganic material mixed solution comprising, after the mixing step, performing a solid-liquid separation step of separating the fine particles precipitated in the inorganic material mixed solution from the inorganic material mixed solution, A method for producing a crystalline microporous body, which comprises performing a crystallization step of heating and crystallizing a solid component separated by solid-liquid separation. Wherein said crystallization modifier, tetra n- butylammonium ion _{((n-C 4 H 9} ) 4 N
^+), Tetra-n- propylammonium ion _{((n-C 3 H 7} ) 4
N ^+), tetraethylammonium ion _{((C 2 H 5) 4} N +), tetramethylammonium ion ^{_{((CH 3) 4 N +}} ), n- propyl trimethyl ammonium ion ((n-C ₃
H ₇ ) (CH ₃ ) ₃ N ⁺ ), benzyltrimethylammonium ion ((C ₇ H ₇ ) (CH
₃ ) ₃ N ⁺ ), tetra-n-butylphosphonium ion ((n-C ₄ H ₉ ) ₄ P
⁺ ), Benzyltriphenylphosphonium ion ((C ₇ H ₇ ) (C
₆ H ₅ ) ₃ P ⁺ ), 1,4-dimethyl-1,4-diazobicyclo (2,2,2
2) octane, pyrrolidine, n- propylamine _{(n-C 3 H 7 NH} 2), methyl quinuclidine, The method according to claim 1 which contains at least one crystalline microporous material. 3. A mixing step of forming an alkaline inorganic material mixed solution containing a silicon dioxide (SiO ₂ ) component and an aluminum salt is performed, and after the mixing step, it is precipitated in the inorganic material mixed solution. A method for producing a crystalline microporous body, comprising performing a solid-liquid separation step of separating fine particles from the inorganic material mixed solution, and performing a crystallization step of heating and crystallizing the solid component separated by the solid-liquid separation. 4. The crystalline micropores according to claim 1, wherein the solid component separated by solid-liquid separation is sealed in a closed container, and then the closed container is heated to perform the crystallization step. Body manufacturing method. 5. The method for producing a crystalline microporous body according to claim 1, wherein the crystallization step is performed by supplying water vapor to the solid component obtained by the solid-liquid separation. 6. The method for producing a crystalline microporous body according to claim 1, wherein the crystallization step is performed after molding the solid component separated by solid-liquid separation.