JP2000154015A - Production of intermediate of crystalline microporous body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To surely filter an intermediate for a microporous body in a short time and to dry to enable mass production by mixing a crystallization controlling agent with an alkaline inorg. material containing a silicon dioxide component, filtering the precipitated slurry-state fine particles, and spray drying the particles at a specified temp. SOLUTION: A crystallization controlling agent such as ammonium ion, phosphonium ion and amines is mixed with an alkaline inorg. material mixture liquid containing a silicon dioxide component. Then fine particles in a slurry state precipitated in the inorg. material mixture liquid are subjected to solid- liquid separation. In this process, the fine particles in the slurry state are preferably separated by continuous filtration using a rotary filter while keeping the thickness of the filtered solid component to 0.5 to 5 mm. The fine particles are supplied to a rotary disk atomizer 15 and sprayed in a drying chamber 11 through a source liquid pump 14, while dry air is introduced through a heater 13 to dry the particles at 100 to 150 deg.C. Thereby, the intermediate of crystalline microporous body can be fast obtd. in a large amt. while avoiding modification of silicon dioxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adsorbent, a catalyst or a material for separation, that is, a chlorofluorocarbon-based refrigerant, sulfur fluoride gas as an insulating medium for high-voltage power equipment, air for a vehicle air brake, and the like. It is mainly used in the petrochemical industry, etc. as a desiccant, an adsorbent for nitrogen compounds in wastewater and an adsorbent for radioactive substances in radioactive wastewater, and as a catalyst for supporting various metals and supporting various uses. The present invention relates to a method for producing an intermediate of a crystalline microporous body.

[0002]

2. Description of the Related Art A large number of crystalline microporous materials exist as natural products such as mordenite and ferrierite, and zeolite-A, zeolite-X and ZSM-5 also exist as artificial crystalline microporous materials. (Special Publication 46-
10064) and ZSM-11 (Japanese Patent Publication No. Sho 5).
Various types are known. When producing an artificial crystalline microporous body as described above, after performing a mixing step of forming an alkaline mixed solution containing a silicon dioxide component, an aluminum oxide component, and an organic ammonium salt, And a crystallization step of crystallizing the crystalline microporous body in the inorganic material mixture by high-pressure heating, that is, a so-called hydrothermal synthesis method.

However, in the above-mentioned hydrothermal synthesis method, a high-pressure heating vessel is expensive, and the inorganic material mixture contains an alkali metal oxide or alkaline earth metal oxide component as an oxide or hydroxide. Therefore, in order to prevent corrosion by alkali, the high-pressure heating vessel must be made of stainless steel or treated with a fluorine resin coating or the like. Also,
In the crystallization step, it was necessary to heat the mixture at a high temperature condition of usually 70 ° C. to 200 ° C. in some cases or more, and in some cases for a long time of 10 days or more, which required severe reaction conditions. there were. In addition, the crystalline microporous body obtained by the hydrothermal synthesis method is in the form of fine particles, and although it is necessary to mold it in some cases, generally, the fine crystalline microporous body itself has a cohesive force. Therefore, sintering at extremely high temperatures or molding with a binder interposed must be performed, so that sintering at high temperatures melts the crystal surface layer and blocks the porous structure. The ratio of the crystalline microporous material in the molded product is reduced, and the ratio of the porous structure per unit weight of the molded product is reduced, and the adsorption activity, catalytic activity, and the like derived from the porous structure are reduced. Properties tended to be low.

In order to solve the above problem, an alkaline inorganic material mixture containing a crystallization regulator and a silicon dioxide component such as kanemite fine particles is prepared, and a slurry precipitated in the inorganic material mixture is prepared. There has been proposed a method for producing a crystalline microporous body in which an intermediate of a crystalline microporous body of fine particles is separated from a mixed liquid of inorganic materials, and a solid component subjected to solid-liquid separation is heated to be crystallized (JP-A-Hei. 8-3
19112). The crystalline microporous material thus obtained is synthesized with energy saving, and the fine particles obtained as an intermediate have caking properties, which are effective physical properties in obtaining a molded product of the crystalline microporous material. have.

[0005]

However, aside from producing a crystalline microporous material on a small scale using a small-capacity glass container such as a beaker, when considering mass production of the crystalline microporous material, There is an unsuitable point as a means. That is, in the filtration step, the most general-purpose vacuum filtration is employed at the laboratory level as a filtration means for filtering slurry-like fine particles precipitated in the inorganic material mixed solution, but the vacuum filtration is performed in a large amount of slurry at once. It is difficult to filter fine particulates. Also, in the drying step, even if natural drying which is simple as a drying means is adopted,
Considering the production of a large amount of crystalline microporous material at once,
Natural drying is not suitable from the viewpoint of drying speed.
Further, as a forced drying means for forcibly drying the fine particles, for example, drying by heating or the like can be considered, but the dried fine particles are modified by a silicon dioxide component such as kanemite as compared with those obtained by natural drying. There was a case. Further, at present, there is no known efficient method for supplying filtered intermediate fine particles to an apparatus for performing forced drying.

Accordingly, an object of the present invention is to provide a method for producing a crystalline microporous intermediate suitable for mass production, that is, an alkaline inorganic material comprising a crystallization modifier and a silicon dioxide component. It is an object of the present invention to provide a method for producing an intermediate of a crystalline microporous body which can be filtered and dried accurately and in a short time at a time even if the slurry-like fine particles precipitated in a mixed solution have a large volume.

[0007]

[MEANS FOR SOLVING THE PROBLEMS] To achieve this object
Of the method for producing an intermediate of the crystalline microporous body of the present invention
The composition is ammonium ion (R_FourN⁺: R is hydrogen, carbon
Selected from alkyl groups or aryl groups of several tens or less
At least one), a phosphonium ion (R _FourP⁺: R
Is hydrogen, an alkyl group having 10 or less carbon atoms or aryl
At least one selected from groups), selected from amines
At least one crystallization modifier, and silicon dioxide (S
iO_Two) An alkaline inorganic material mixed solution containing the component
Perform a mixing step of mixing, and precipitate in the inorganic material mixed solution.
The discharged slurry-like fine particles are separated from the inorganic material mixed liquid.
Perform a solid-liquid separation step of separating, the slurry-like fine particles
A drying step of performing a filtration step of filtering and drying the fine particles.
A process for producing an intermediate of a crystalline microporous body.
When performing the drying step, a drying chamber is provided,
A supply section for supplying dry air into the drying chamber, and
And in a dry air atmosphere flowing through the drying chamber.
A spray provided with a spray device for spraying the fine particles
Using a lier, the fine particles should be 100 ° C or higher and 150 ° C or lower.
It consists in feeding to the drying chamber under the following conditions. Said
The crystallization modifier is tetra-n-butylammonium ion
((n-C_FourH₉)_FourN ⁺), Tetra-n-propylammonium
Mion ((n-C_ThreeH₇)_FourN⁺), Tetraethylammonium
Um ion ((C_TwoH_Five)_FourN⁺), Tetramethylammonium
Mion ((CH_Three)_FourN⁺), N-propyltrimethylan
Monium ion ((n-C_ThreeH₇) (CH_Three) _ThreeN⁺), Benzyl
Trimethylammonium ion ((C₇H₇) (CH_Three)
_ThreeN⁺), Tetra n-butylphosphonium ion ((n-C
_FourH₉)_FourP⁺), Benzyltriphenylphosphonium ion
((C₇H₇) (C₆H_Five)_ThreeP⁺), 1,4-dimethyl-1,
4-diazobicyclo (2,2,2) octane, pyrrolidi
N-propylamine (n-C_ThreeH₇NH_Two), Methyl
At least one cation selected from quinuclidine
It may be a crystalline crystallization regulator. Also in the filter
While feeding the solid-liquid mixture, filter on the filter.
To remove excess solid components that accumulate to a predetermined thickness or more.
Solid-liquid mixing using a removable rotary filter
While supplying the slurry-like fine particles as a material,
The thickness of the solid component filtered on the filter is 0.5 mm or less.
One that keeps the upper 5mm or less and performs the filtration step continuously
It may be.

[Action] When a silicon dioxide component such as kanemite and at least one crystallization controlling agent selected from ammonium ions, phosphonium ions and amines are allowed to coexist under alkaline conditions, the surroundings of the crystallization controlling agent are reduced. Inorganic materials aggregate. At this time, an intermediate of a crystalline microporous body, which is a fine particle of the composite, is arranged at a position where the inorganic materials are easily bonded to each other. In other words, in the formation of the intermediate, the silicon dioxide component forms a layered structure, ie, a layered silica structure, and aggregates around the crystallization modifier while maintaining the layered structure to form the intermediate. It is thought to be due to the reaction mechanism. The intermediate is isolated as a solid component by a solid-liquid separation step, and the isolated intermediate undergoes a phase change by heat treatment to be crystallized, whereby a porous crystal is obtained.

In order to perform the drying step, the present inventors have provided a drying chamber, a supply section for supplying dry air into the drying chamber, and a supply section for supplying the dry air into the dry air atmosphere flowing through the drying chamber. When the fine particles are dried by using a spray dryer provided with a spraying device for spraying the fine particles and supplying the fine particles to a drying chamber under an inlet temperature of 100 ° C. or higher and 150 ° C. or lower, a silicon dioxide component such as kanemite is obtained. Experimentally proved the fact that high-speed and large-scale drying treatment can be performed while avoiding denaturation of
The present invention has been completed based on this fact. Here, the temperature of the object to be dried when the object to be dried such as the fine particles is introduced into the drying chamber is referred to as an inlet temperature.

That is, even when the fine particles are dried using the above-mentioned spray dryer, the cohesion of the intermediate fine particles may be reduced in the drying step, which is caused by the modification of the intermediate. As a result of extensive studies, it was experimentally found that by controlling the amount of heat applied to the intermediate in the drying step, a dry powder of the intermediate having high cohesion can be produced. That is, using a spray dryer having a drying chamber, a supply unit for supplying dry air into the drying chamber, and a spray dryer provided with a spray device for spraying the fine particles into a dry air atmosphere flowing through the drying chamber, The intermediate produced by supplying the fine particles to the drying chamber at an inlet temperature of 100 ° C. or more and 150 ° C. or less has excellent caking properties, and has found that a molded product of a crystalline microporous body can be obtained. It was. In the case where the control of the calorific value is not performed, such a phenomenon is caused by denaturation at the time of drying, a change in the structure occurs, and a phase change at the time of forming the crystalline microporous body is inhibited. This is because denaturation does not occur and the phase change is not inhibited. In addition, the said inlet temperature of a spray dryer is 10
If the temperature is lower than 0 ° C., disadvantages may occur from the viewpoint of the drying speed.

Furthermore, the intermediate layered silica structure is a sheet layer formed by two-dimensionally bonding SiO ₄ tetrahedra, and the sheet layer of the layered silica structure has a hydroxyl group from silicon atom. , That is, silanol (Si-O
H) is present but the inlet temperature of the spray dryer is 1
When the temperature is set higher than 50 ° C., dehydration condensation between silanols (Si—OH) having a layered silica structure is promoted,
Where a silicon dioxide component such as kanemite tends to be modified by forming a siloxane bond (Si-O-Si), when the inlet temperature of the spray dryer is set to 150 ° C or lower, the siloxane bond (Si-O-Si) -Si)
It is considered that the tendency of denaturation of silicon dioxide components such as kanemite due to the formation of is not seen.

[0012] Here, as the silicon dioxide component, kanemite _{(NaHSi 2 O 5 · 3H 2} O) is preferably Additional sodium disilicate _{(Na 2 Si 2 O 3)} , makatite (Na ₂ Si ₄ O ₉ · 5H ₂ O), islayite (Na ₂ S)
i ₈ O ₁₇ .XH ₂ O), Magadiite (Na ₂ Si ₁₄ O)
₂₉ · XH ₂ O), etc. are representative, but is not limited thereto.

The crystallization regulator includes an ammonium ion (R ₄ N ⁺ : R is at least one selected from hydrogen, an alkyl group or an aryl group having 10 or less carbon atoms), and a phosphonium ion (R ₄ P ⁺ : R is hydrogen, at least one selected from an alkyl group or an aryl group having 10 or less carbon atoms), as long as at least one of amines, selected from, in particular, 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-propyltrimethylammonium ion ((nC 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 (nC ₃ H ₇ NH)
₂ ), methylquinuclidine, and at least one selected from methylquinuclidine are preferable, and it is considered that various ammonium salts, phosphonium salts, and amines can be used. When a tetrapropylammonium salt is used, the final product is a crystalline microporous material having an MFI structure, and when a tetrabutylammonium salt is used,
Since a crystalline microporous body having an MEL structure is obtained, an intermediate of a crystalline microporous body having various pore sizes can be obtained by selecting the organic ammonium salt according to the structure to be synthesized.

In the filtration step, while supplying the solid-liquid mixture to the filter, the solid-liquid mixture is filtered using a rotary filter capable of scraping out and removing excess solid components deposited on the filter to a thickness equal to or greater than a predetermined thickness. While supplying the slurry-like fine particles as a mixture, the thickness of the solid component filtered on the filter is maintained at 0.5 mm or more and 5 mm or less, and the filtration step is continuously performed. Even if a large amount of solid fine particles are deposited on the filter, the thickness of the fine particle layer formed on the filter can be suppressed to a predetermined range by appropriately removing the solid content on the filter, and the fine particle layer impairs the filtration efficiency. It is easy to maintain in a difficult state, and efficient filtration can be performed. Moreover,
The thickness of the cake layer, which is the thickness of the solid component on the filter, is set to 0.
Since the filtration is performed while maintaining the thickness at 5 mm or more and 5 mm or less, the cake itself of the fine particle layer can realize a configuration for filtering the fine particles, and can minimize clogging of the filter. When continuous filtration is performed, maintenance may need to be performed due to clogging of the filter, but silica fine particles such as kanemite, which cause clogging of the filter, are easily reduced due to a decrease in pH. Since it becomes soluble silica fine particles, clogging can be easily eliminated by washing with water. Furthermore, by washing with an acid, it is possible to further promote the solubility of the silica fine particles and shorten the washing time, and it is useful for easily maintaining and continuously producing the intermediate. .

As a result, even if a large amount of slurry-like fine particles precipitated in the mixture of the alkaline inorganic material containing the crystallization modifier and the silicon dioxide component, filtration and drying can be performed quickly and surely even if the amount is large. An intermediate of a crystalline microporous body could be efficiently produced.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.
In addition, as a raw material set, the one having the following composition was used (all the percentages shown are% by weight). ○ No. 3 water glass: Analytical value SiO ₂ : 29.17%, Na
₂ O: 9.82% (manufactured by Nippon Chemical Industry Co., Ltd.) ○ Tetrapropylammonium bromide ((n-C ₃ H ₇ ) ₄ NB
r) :( Tokyo Chemical Industry Co., Ltd.) ○ aluminum chloride _{(AlCl 3 · 6H 2 O)} :( Kishida Chemical Co., Ltd.)

A No. 3 water glass was prepared in a 500 mL beaker, and sodium hydroxide was dissolved therein. Then, the solution was transferred to an evaporating dish made of alumina and placed in a thermostat at 150 ° C. to evaporate the water content. The product from which the water was evaporated was put into an electric furnace together with the evaporating dish and calcined at 700 ° C. for about 5 hours, and allowed to cool to room temperature to obtain a reaction product. The reaction product is immersed in water in a beaker to obtain sodium disilicate powder which is a precipitate of fine powder. When the raw material sodium disilicate powder is put into deionized water, kanemite fine particles are generated, and part of the kanemite fine particles are dissolved in the mixing step with the crystallization modifier, and silicate ions and sodium ions are eluted, and silicate The kanemite fine particles are dispersed in the aqueous sodium solution. By filtering this, kanemite fine particles remain, but sodium silicate flows out together with the filtrate. When the remaining aqueous solution of sodium silicate-kanemite is dried, sodium silicate precipitates as amorphous, and becomes a mixture of kanemite and amorphous. The intermediate is a product in which crystallization control agent is combined with kanemite and amorphous by a chemical reaction. This intermediate is subjected to high pressure
Exposure to high temperature conditions results in a crystalline microporous body.

In place of the sodium disilicate powder as the silicon dioxide component, a commercially available layered sodium silicate powder (such as SKS-6 manufactured by Clariant Japan) can be used. In such a case, it is not necessary to use an expensive electric furnace for baking water glass to produce sodium disilicate powder, and an intermediate of a crystalline microporous body can be produced at low cost.

The spray dryer 10 is of a blow-down type in which the drying air is convected in the drying chamber 11 to dry the particles while dropping the fine particles. As shown in FIG. 1, the drying air is supplied into the drying chamber 11. The supply unit is configured to include the air filter 12 and the electric heater 13, and the spraying device is configured to include the stock solution pump 14 and the rotating disk atomizer 15. The volume of the drying chamber 11 is 800Φ × 120.
At 0H, the dried fine particles are collected in the product receiver 17 by the cyclone 16 from the bottom of the drying chamber 11. Here, the temperature of the object to be dried when the object to be dried is introduced from the spray device into the drying chamber is referred to as an inlet temperature.

As shown in FIG. 2, the rotary filter 20 has filters (filter plates) 21 and stir plates 22 alternately arranged at narrow intervals in a pressure-resistant filter chamber 23, and the stir plate 22 is constantly rotated during filtration. By doing so, excess solid components that accumulate to a predetermined thickness or more are scraped out. Filter (filter plate)
Reference numeral 21 denotes a structure in which a filter cloth is stretched on both sides of a plate provided with a filtrate discharge groove. The solid-liquid mixture in the form of an undiluted slurry is supplied under pressure from one of the filtration chambers 23, and a filter (filter plate) 2.
1 is dewatered by filtration while moving through the gap,
3 is discharged as a hard paste cake from a cake discharge valve provided on the other side of the cake. The filtrate is a filter (filter plate) 2
It is discharged outside through 1.

FIG. 3 is a diagram showing an X-ray signal pattern showing the structure of the intermediate according to the difference in the inlet temperature of the spray dryer. At an inlet temperature of 150 ° C., no kanemite denaturation was observed in the intermediate, but at an inlet temperature of 170 ° C., slight kanemite denaturation was found, and at an inlet temperature of 200 ° C., kanemite denaturation was clearly confirmed.

[Embodiment 1] 4.0 Kg of layered sodium silicate was dispersed in 90 L of deionized water, and after the generated kanemite precipitated, the supernatant was removed to make 20 L, and deionized water was added again to make 40 L. And tetrapropylammonium bromide (TPABr) as a crystallization regulator
1200 g were added. This was heated to 60 ° C. and stirred for 3 hours. Thereafter, the mixture was allowed to cool to room temperature, and the pH was lowered to 10.5 by adding 2 mol / L hydrochloric acid. Here, the reason why the alkaline inorganic material mixed liquid containing TPABr as a crystallization regulator and a silicon dioxide component is stirred at 60 ° C. is because the yield of the intermediate can be improved, It is preferable to stir the alkaline inorganic material mixed solution under a liquid condition of 60 ° C. or lower to improve the yield of the intermediate. Further, the pH of the alkaline inorganic material mixed solution containing TPABr as a crystallization modifier and a silicon dioxide component is adjusted to 10.5 in order to improve the moldability of the intermediate, and By adjusting the pH of the mixture of alkaline inorganic materials to a range of not less than 9.0 and not more than 12.5, the moldability of the intermediate can be improved, and it is particularly effective when preforming the intermediate. The slurry thus formed was filtered with a rotary filter for 2 hours while stirring, and concentrated to 20 L. Further, the step of adding 20 L of deionized water and concentrating by filtration was repeated twice, each for 3 hours. To reduce the viscosity of the obtained 20 L slurry and make it easier to feed, dilute it by adding 5 L of deionized water and send it to a spray dryer at a flow rate of 5 L / hr. Spray-drying was performed for 5 hours using an atomizer having a rotation number of 35,000 rpm. The obtained dry powder had a weight of 3.2 kg and a water content of 7%. When extrusion molding was performed using this, a molded article having a good honeycomb shape could be obtained. This molded product was heated at 150 ° C. for 24 hours in a Teflon-made closed container and examined by powder X-ray diffraction spectrum measurement. As a result, it was found to be a honeycomb-shaped crystalline microporous body made of silicalite-I.

[Embodiment 2] In the filtration step of Embodiment 1, the filtrate flow rate of the rotary filter is set to
At 0 minutes, the flow rate was 13 L / hr, but it was lowered to 5 L / hr at the end of the filtration step due to clogging of the filter cloth. Then, for washing the filter cloth, tap water was passed from the forward direction for 5 minutes while operating the rotary filter. One day later, the same filter cloth washing step was performed again. After this, filtration was performed again using the slurry of Embodiment 1, and 10
The liquid flow rate per minute recovered to 13 L / hr, and the filtration step could be performed as in the previous case.

COMPARATIVE EXAMPLE 1 A kanemite-containing slurry obtained in the same process as in the first embodiment was subjected to an inlet temperature of 200.degree.
Spray drying was performed at 00 ° C with a spray dryer. When the powder X-ray diffraction spectrum of the obtained powder was measured, a crystal pattern different from that of kanemite appeared due to denaturation by dehydration at a high temperature. After heating this powder at 150 ° C. for 24 hours in a closed container made of Teflon, the powder X-ray diffraction spectrum was measured. As a result, no crystal pattern appeared. [Comparative Example 2] 3 L of deionized water was placed in a beaker, 150 g of sodium disilicate powder was dispersed in the beaker.
L, and again, deionized water was added to make 1.5 L, and 40.0 g of TPABr was added thereto and stirred. 60 ℃
And stirred for 3 hours. After cooling to room temperature,
The pH was lowered to 10.5 by adding 2 mol / L hydrochloric acid. The obtained slurry is suction-dehydrated with a Buchner funnel,
Add deionized water to the dehydrated product, wash it, feed it again and dehydrate it,
Then, it was air dried. The obtained powder was about 100 g. In this method, the washing and dewatering step required two days, and the drying step required one week. On the other hand, in the method of Embodiment 1, the washing, dehydration and drying steps are completed in a total of 12 hours,
3.2 Kg of intermediate powder was obtained.

Another Embodiment At least one crystallization modifier selected from ammonium ions, phosphonium ions, and amines and kanemite fine particles may be mixed in the presence of aluminum ions under a liquid condition of 60 ° C. or lower. It is possible. That is, when the crystalline microporous intermediate is exposed to aluminum chloride vapor, or when a composite of a crystallization regulator and kanemite fine particles is formed, aluminum elements may be introduced into the crystal structure by introducing aluminum ions. it can. A molded product from such a crystalline microporous intermediate can be used as a catalyst for the production of ethylbenzene or para-xylene.

[Brief description of the drawings]

FIG. 1 is a schematic view of a spray dryer.

FIG. 2 is a schematic view of a rotary filter.

FIG. 3 is a diagram showing an X-ray signal pattern showing the structure of an intermediate of a crystalline microporous material.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Spray dryer 11 Drying chamber 12 Air filter 13 Electric heater 14 Stock solution pump 15 Rotating disk type atomizer 16 Cyclone 17 Product receiver 20 Rotary filter 21 Filter 22 Stirring plate 23 Filtration room

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shinichi Shimizu 5-6-1 Koyodai, Ryugasaki-shi, Ibaraki F-term in Kubota Fundamental Technology Research Institute (reference) 4G072 AA29 BB05 BB12 BB15 GG03 GG05 HH21 JJ33

Claims (3)

[Claims] 1. An ammonium ion (R ₄ N ⁺ : R is at least one selected from hydrogen, an alkyl group or an aryl group having 10 or less carbon atoms), a phosphonium ion (R
₄ P ⁺ : R is at least one selected from hydrogen, an alkyl group or an aryl group having 10 or less carbon atoms), at least one crystallization regulator selected from amines, and a silicon dioxide (SiO ₂ ) component. Performing a mixing step of mixing with the alkaline inorganic material mixed liquid, performing a solid-liquid separation step of separating slurry-like fine particles precipitated in the inorganic material mixed liquid from the inorganic material mixed liquid, and filtering the slurry-like fine particles A method for producing an intermediate of a crystalline microporous body, which performs a filtration step of performing a drying step of drying the fine particles, wherein the drying step includes performing a drying chamber (11). 11) a supply unit for supplying dry air to the inside, and a spray device for spraying the fine particles into a dry air atmosphere flowing through the drying chamber (11). Using a certain spray dryer (10), a manufacturing method of an intermediate of crystalline microporous material supplying said fine particles to the drying chamber (11) under conditions of 100 ° C. or higher 0.99 ° C. or less. 2. The method according to claim 1, wherein the crystallization controlling agent is tetra-n-butylammonium ion ((nC ₄ H ₉ ) ₄ N ⁺ ), tetra-n-butyl ammonium ion.
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 (nC ₃ H ₇ NH)
₂ ) The method for producing an intermediate of a crystalline microporous material according to claim 1, which is at least one cationic crystallization modifier selected from methylquinuclidine. 3. A rotary filter (20) capable of scraping off and removing excess solid components deposited on a predetermined thickness or more while being filtered on the filter (21) while supplying the solid-liquid mixture to the filter (21). While supplying the slurry-like fine particles as the solid-liquid mixture, the thickness of the solid component filtered on the filter (21) is set to 0.1.
The method for producing an intermediate of a crystalline microporous body according to claim 1, wherein the filtration step is continuously performed while keeping the thickness at 5 mm or more and 5 mm or less.