JPH09315814A - Production of zeolite having large particle diameter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a producing method of a zeolite useful for a catalyst, a catalyst carrier, an adsorbent, an adsorption separating agent or the like and having a diameter >=10 times that of a zeolite obtained by a usual method and a producing method particularly of a zeolite of a faujasite type, an A type, a mordenite type or the like having large particle diameter. SOLUTION: The zeolite is produced by preparing a water based mixture for zeolite synthesis having the composition, xM2 O.Al2 O3 .ySiO2 .zH2 O expressed by the molar ratio of oxides, heating the water based mixture at a temp. enough to crystallize the zeolite and crystallizing while vaporizing the water in the water based mixture at a water vaporizing rate of 50-500mol/day when expressed by the molar ratio (z) of water.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst, a catalyst carrier,
Useful as an adsorbent, adsorption separator, ion exchanger, etc.,
The present invention relates to a method for producing zeolite in which single particles (non-aggregated particles) have a large particle size.

[0002]

BACKGROUND OF THE INVENTION Zeolites are catalysts, catalyst carriers, adsorbents,
It is used as an adsorption separator, a detergent, etc., and the size of the zeolite particles used is one of the important properties.

For example, in the performance of the catalyst, when the particle size is small, the external surface area of the zeolite particles increases, and depending on the type of reaction, the activity of the external surface increases or decreases the overall activity, or the selectivity is high. May increase or decrease. It is also well known that zeolite having a large particle size is preferable for a catalyst that requires thermal stability.

Pellets processed by mixing zeolites,
It is also known that when used as fluid particles or the like, the particle size of zeolite has a great influence on the strength and wear resistance thereof.

As a detergent builder, the particle size is about 1 μm from the viewpoint of enhancing the ion exchange property and preventing adhesion to clothes.
It is also known that a zeolite having a small size of m or less and good dispersibility is preferable.

There are many kinds of synthetic zeolites, and the average particle size thereof is usually in the range of about 0.5 μm to 50 μm. However, the range of zeolite particle size also differs depending on the type. For A type zeolite, 0.5 μm to 5 μm,
1 μm to 5 μm for faujasite-type and mordenite-type zeolite, 0.5 for pentasil-type zeolite
The range of the normally obtained particle size is from μm to 50 μm.

In addition to the type of zeolite, a general factor in the production that affects the zeolite particle size is SiO.
₂ / Al ₂ O ₃ molar ratio, concentration of alkali, aging time of hydrogel, crystallization time, silica raw material, size and amount of seed crystal, etc. are known as “Zeolite Vol, 12 N”.
O, page 18 1995 ". Specifically, the particle size decreases with increasing SiO ₂ / Al ₂ O ₃ molar ratio, decreases with increasing alkali concentration, decreases with increasing hydrogel aging time, and decreases with seed crystal size. It is described that when the amount of seed crystals is large, it becomes small. Further, it is described that the order of pouring, temperature, mechanical stirring degree, etc. at the time of preparation of the aqueous mixture affect the particle size, but these do not have a universal direction.

However, the range of the particle size that can be changed by these general methods is 2 to 4 times or 1/2 to 1/4, and the range of the normal particle size should be greatly reduced or increased. I can't.

Japanese Patent Publication No. 4-514 concerning the applicant's application
No. 86 gazette uses a special silica-alumina sol as a raw material as a silica source and an alumina source, and it is 4 to 20 μm.
Although a method for producing a faujasite-type zeolite having a large particle size of m has been described, no attention has been paid to the evaporation of water and its rate during production.

Further, as a special method, "H. Leche
rt Zeolites Vol, 13 NO, 3 1
993 ”describes that a silica-alumina hydrogel is filled in a Teflon container, and an external heater is moved extremely slowly (0.5 mm / day) to the lower part from the upper part outside the container to heat it, and it takes 40 days or more. It is described that giant zeolite particles having a maximum particle size of about 0.5 mm are produced. However, in this method, since the gel is viscous and convection does not occur, the heat from the external heater is difficult to transfer inward (horizontal direction), and it is difficult to heat the inside of a large container. Method.

[0011]

The object of the present invention is to provide a catalyst,
To provide a method for producing a zeolite which is useful as a catalyst carrier, an adsorbent, an adsorption separator, etc., and has a particle size about 10 times or more larger than that of a zeolite obtained by a usual method, particularly a faujasite type, an A type, Another object is to provide a method for producing zeolite having a large particle size such as mordenite type.

[0012]

Means for Solving the Problems As a result of various investigations on manufacturing factors affecting the particle size of zeolite, the present inventors believe that it is important to control the amount of zeolite nucleation. Came to. However, it is generally considered that the crystallization of zeolite first generates nuclei and grows as particles, and in the method of preparing an aqueous mixture under supersaturation conditions in which the molar ratio of water is small and heating the mixture to crystallize it. , It is difficult to artificially control the generation of nuclei, and it is difficult to intentionally increase or decrease the size of particles. In the method of adding a separately prepared seed crystal for crystallization, the particle size can be increased to some extent by reducing the amount of the seed crystal added, but even if the seed crystal is further reduced, the crystallization time is increased. It may be long, may not form the desired type of zeolite, or may not form at all.

Usually, the molar ratio of water in the aqueous zeolite synthesis mixture is in the range of 100 to 500, but in the present invention, the molar ratio of water is set to 1,000 to 10,000, that is, the aqueous zeolite synthesis mixture having a low concentration is used. A mixture is prepared and the water evaporation rate from the aqueous mixture is 50 to 5 expressed as the molar ratio of water.
At a rate of 00 mol / day, the molar ratio of water is approximately 50 to 250.
Crystallization is performed while evaporating water until the maximum particle size is 5 μm to 100 μm and the weight average particle size is 3 μm to 50 μm.

That is, the present invention is expressed by the molar ratio of oxides.

[Chemical formula 2] xM ₂ O · Al ₂ O ₃ · ySiO ₂ · zH ₂ O (M is an alkali metal cation, 0.5y ≦ x ≦ 1.4
y, 5 ≦ y ≦ 25, 1,000 ≦ z ≦ 10,000), and an aqueous mixture for zeolite synthesis is prepared,
The aqueous mixture is heated at a temperature sufficient to crystallize the zeolite to evaporate the water content of the aqueous mixture at a water evaporation rate of 50-500 moles / day, expressed using the value of the water molar ratio z. The present invention relates to a method for producing zeolite, which is characterized by causing crystallization.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The preferred mode of the present invention is to first express the molar ratio of oxides.

[Chemical formula 3] xM ₂ O · Al ₂ O ₃ · ySiO ₂ · zH ₂ O (M is an alkali metal cation, 0.5y ≦ x ≦ 1.4
y, 5 ≦ y ≦ 25, 1,000 ≦ z ≦ 10,000) to prepare an aqueous mixture for zeolite synthesis.

As the silica source, a silica-containing material having reactivity and solubility with alkali can be used. Preferred are sodium silicate, silica sol, silica alumina sol, alkoxysilane and the like. Further, as the alumina source, an alumina-containing material having reactivity and solubility with alkali can be used, but sodium aluminate, silica alumina sol, aluminum alkoxide and the like are preferable.

The number of moles y of SiO ₂ is in the range of 5 to 25, although the range varies depending on the type of zeolite. When it is less than 5, the effect of the present invention that the hydrogel remains in the aqueous mixture and the gel precipitates at the bottom of the synthesis container during heat aging and the particle size becomes large cannot be obtained. On the other hand, when it is higher than 25, the purity of the obtained zeolite is low, and in extreme cases, it becomes amorphous, which is not preferable.

Although an alkali metal compound is used as the alkali source, it varies depending on the type of zeolite to be produced. For example, in the case of faujasite type zeolite, an alkali metal compound is used, and sodium hydroxide is particularly preferable. It should be noted that although a part or all of the alkali metal can be a basic nitrogen-containing organic compound, it should be noted that many of them are evaporated when water is evaporated. M ₂
The mole number x of O is 0.5y ≦ x ≦ 1.4y. Preferably, 0.6y ≦ x ≦ 1.2y. When x is less than 0.5y (that is, less than 1/2 of the number of moles of silica), the particle size of the zeolite is small, and when x exceeds 1.4y and is high, crystals are not formed or even if they are formed. The yield is extremely low, which is not preferable.

In addition to the above, a halide such as NaCl, a sulfate such as Na ₂ SO _{4 or} the like may be directly added as a mineralizer or may be produced in an aqueous mixture.

The number of moles of H ₂ O is 1,000 to 10,000.
It is 0, preferably 1,050 to 8,000. 1,0
If it is less than 00, there is no effect of increasing the particle diameter, and
When it is higher than 00, crystalline zeolite is not formed and it becomes amorphous, which is not preferable.

In the case of producing faujasite type zeolite, the composition of the aqueous mixture is such that the number of moles y of SiO ₂ is 6
˜20, the number of moles x of M ₂ O is 0.8y ≦ x ≦ 1.2y,
The number of moles of H ₂ O is preferably 1,050 to 8,000. In addition, when producing A-type zeolite, S
The mole number y of iO ₂ is 5 to 10, and the mole number x of M ₂ O is 1.0.
y ≦ x ≦ 1.4y, the number of moles of H ₂ O is 1,050 to 8,
It is preferably 000. Further, in the case of producing a mordenite type zeolite, the number of moles y of SiO ₂ is 10
25, the number of moles x of M ₂ O is 0.5y ≦ x ≦ 1.0y,
The number of moles of H ₂ O is preferably 1,050 to 8,000.

An aqueous mixture containing a silica source, an alumina source and an alkali source is prepared. In this case, it is preferable that a gel does not form in the aqueous mixture or even if it does, it does not remain, and the temperature is raised to at least the crystallization temperature. It is preferable that the gel disappears at the point of time and a transparent sol is formed. Aging at room temperature for 1 to 48 hours is also effective for forming a transparent sol.

The crystallization temperature is preferably 80 ° C. or higher and lower than the boiling point. If the temperature is lower than 80 ° C, the crystallization time will be prolonged and the particle size will not be further increased.
It does not rise above the range, but it is important not to bring it to a boiling state. When it is boiled, it is difficult to obtain pure faujasite-type or A-type zeolite. When vaporizing water vapor at a predetermined rate in a range not boiling by using a pressure cooker (autoclave), it is possible to carry out at a high temperature of 105 ° C or higher, but there is no effect of further increasing the particle size and the purity is high. It is not preferable because it becomes difficult to obtain zeolite and the manufacturing equipment becomes expensive.

Crystallization is then carried out while evaporating water, and the water evaporation rate at this time is in the range of 50 to 500 mol / day expressed by the value of the number of moles of water, z. If it is less than 50, the particle size does not increase further and the crystallization time becomes long, which is not preferable. When it is higher than 500, there is no great difference from the case where the compound is crystallized by mixing at a high concentration, and the effect of increasing the particle size is poor, which is not preferable.

The crystallization is stopped when the number of moles z of water is about 250.
It is preferable to carry out at the time when it reaches ~ 50. z is 250
If it is higher, the crystallization is not completed, and the gel phase may remain, which lowers the crystallinity, which is not preferable. Further, if z is less than 50, the zeolite may be aggregated or the crystallinity of the zeolite may be lowered, which is not preferable.

The maximum particle size of the zeolite single particles (non-aggregated particles) obtained by taking out the aqueous mixture after the molar number z of water becomes approximately 250 to 50 and filtering and washing is 5 μm or more, preferably 10 to 100 μm. Is the range. 5 μm
Those less than can be easily produced without using the method of the present invention. The weight average particle diameter of the obtained zeolite single particles (non-aggregated particles) is generally 3 μm or more, preferably 5 to 50 μm. Those having a thickness of 3 μm or less can be easily manufactured without using the method of the present invention.

Next, the obtained zeolite can be used as it is, but it is also possible to fractionate and use particles having a required size, if necessary. Further, it can be used after being subjected to ion exchange, drying, firing, steaming, etc., and can also be molded into pellets, spherical particles or the like for use.

[0028]

The present invention will be described below with reference to examples.
The present invention is not limited to this.

The samples obtained in the respective examples and comparative examples were examined for crystallinity, weight average particle size and maximum particle size. The type of zeolite and the degree of crystallinity were determined by the X-Ray diffraction method. The weight average particle diameter was measured by suspending the sample in water, adding sodium pyrophosphate as a dispersant, and further applying ultrasonic waves to sufficiently disperse the particles, and then measuring the particle size distribution (Capa-5).
00). The particle size of 5 μm or more is measured by the natural sedimentation method, and the particle size of 5 μm or less is 2000 rp
It was measured after centrifugal sedimentation at m. The maximum particle size was taken by scanning electron microscope (SEM) photographs so that at least 100 particles were photographed in one picture, and the particle size (major axis) of the top 5 particles was measured by visual observation. This was calculated by dividing this by the photographing magnification. The average particle size and the maximum particle size of the amorphous type were not measured.
Table 1 shows the compounding compositions of the following Examples and Comparative Examples, Table 2 shows the production conditions, and Table 3 shows the physical properties of the products.

Example 1 Aqueous sodium aluminate solution (2.70 as Na ₂ O)
145 g of 48 wt% sodium hydroxide aqueous solution was added to 291 g of Al ₂ O _{3 (} wt%, containing 3.5 wt% as Al ₂ O ₃ ), and while stirring this, a water glass solution (2.19 wt% as Na ₂ O and 7 as SiO ₂ ) was added. 0.014 wt%) was added, and the oxide molar ratio was 16 Na ₂ O.
An aqueous sodium aluminosilicate mixture for zeolite synthesis of Al ₂ O ₃ .20SiO ₂ .1067H ₂ O was prepared. 1 kg of this is 12 cm in inner diameter, 10 cm in height and 1 in internal volume
A Teflon container having a cylindrical shape of 1 liter and having a lid capable of adjusting the degree of opening and closing was filled, and the container was set in a dryer with a ventilation fan set to a temperature of 95 ° C. The opening degree of the upper lid was adjusted in advance so that the moisture evaporation rate was about 200 mol / day in terms of z value, and after 5 days, it was taken out from the dryer and filtered and washed. The slurry when taken out from the dryer is 149
It was reduced to g. This is a faujasite type,
The average particle diameter was 4 μm and the maximum particle diameter was 10 μm.

Comparative Example 1 1 kg of the aqueous mixture prepared in Example 1 was filled in the same Teflon container as used in Example 1, the upper lid was completely sealed and placed in a dryer with a ventilation fan set to a temperature of 95 ° C. Set After 5 days, it was taken out from the dryer, filtered, washed, and dried, and the same measurement as in Example 1 was performed. This was a faujasite type, but the yield was extremely small.

Comparative Example 2 Aqueous sodium aluminate solution (5.8w as Na ₂ O)
To 272 g of t% and 7.5 wt% of Al ₂ O ₃ ), 289 g of a 48 wt% sodium hydroxide aqueous solution was added, and while stirring this, a water glass solution (4.7 wt% as Na ₂ O, 15 wt% as SiO _2). % Content) 1.
Add 6 kg and oxide molar ratio of 16Na ₂ O.Al ₂ O ₃
An aqueous mixture of sodium aluminosilicate for zeolite synthesis of 20SiO ₂ · 473H ₂ O was prepared. 1k of this
g was filled in the same Teflon container as used in Example 1, and this was set in a dryer with a ventilation fan set to a temperature of 95 ° C. The opening degree of the upper lid was adjusted in advance so that the water evaporation rate was about 200 mol / day in terms of z value, and after 48 hours, it was taken out from the dryer and filtered and washed. The amount of slurry when taken out from the dryer was reduced to 296 g. This is a faujasite type with an average particle size of 0.2μ.
When the particle size was m or less, the maximum particle size was as small as 0.4 μm.

Comparative Example 3 1 kg of the aqueous mixture prepared in Comparative Example 2 was filled in the same Teflon container as used in Example 1, and the upper lid was completely sealed and placed in a dryer with a ventilation fan set to a temperature of 95 ° C. Set After 48 hours, it was taken out from the dryer and filtered and washed. This was of faujasite type and had an average particle diameter of 0.2 μm or less and a maximum particle diameter of 0.5 μm.

Example 2 Aqueous sodium aluminate solution (1.54 as Na ₂ O)
145 g of a sodium hydroxide aqueous solution having a concentration of 48 wt% was added to 510 g of wt% and 2.0 wt% of Al ₂ O ₃ ), and a water glass solution (1.25 wt% as Na ₂ O and 4 as SiO ₂ was added while stirring this). 3 wt% (containing 0.0 wt%) was added to obtain an oxide molar ratio of 16Na ₂ O.Al ₂ O ₃
An aqueous mixture of sodium aluminosilicate for zeolite synthesis of 20SiO ₂ · 1903H ₂ O was prepared. 1 of these
The same Teflon container used in Example 1 was filled with kg, and this was placed in a dryer with a ventilation fan set to a temperature of 95 ° C. The opening degree of the upper lid was adjusted in advance so that the moisture evaporation rate was about 200 mol / day in terms of z value, and after 10 days, it was taken out from the dryer and filtered and washed. The slurry when taken out from the dryer was reduced to 87 g. This is a faujasite type with an average particle size of 12 μm.
The maximum particle size was as large as 20 μm.

Example 3 Aqueous sodium aluminate solution (0.77 as Na ₂ O)
2 wt%, containing 1.0 wt% as Al ₂ O ₃ ) 2.04
A sodium hydroxide aqueous solution 289 having a concentration of 48 wt% per kg
g, and while stirring this, 12 kg of a water glass solution (containing 0.626 wt% as Na ₂ O and 2.0 wt% as SiO ₂ ) was added, and the oxide molar ratio was 16 Na ₂ O.
An aqueous sodium aluminosilicate mixture for zeolite synthesis of Al ₂ O ₃ .20SiO ₂ .3853H ₂ O was prepared. 1 kg of this was filled in the same Teflon container as used in Example 1, and this was set in a dryer with a ventilation fan set to a temperature of 95 ° C. The opening of the top lid is adjusted in advance so that the water evaporation rate is about 200 mol / day in terms of z value.
After 0 days, it was taken out from the dryer and washed by filtration. The slurry when taken out from the dryer was reduced to 45 g. This is a faujasite type with an average particle size of 3
The maximum particle size was 0 μm and the maximum particle size was 45 μm.

Comparative Example 4 1 kg of the aqueous mixture prepared in Example 3 was filled in the same Teflon container as used in Example 1, the upper lid was completely sealed and placed in a dryer with a ventilation fan set to a temperature of 95 ° C. Set After 20 days, it was taken out from the dryer, washed by filtration, and then dried, and the same measurement as in Example 3 was performed. This was in the form of a cloudy hydrogel and was not granulated.

Example 4 Aqueous sodium aluminate solution (0.38 as Na ₂ O)
6 wt%, containing 0.5 wt% as Al ₂ O ₃ ) 2.04
Aqueous sodium hydroxide solution 145 with a concentration of 48 wt% in kg
g, and 12 kg of a water glass solution (containing 0.313 wt% as Na ₂ O and 1.0 wt% as SiO ₂ ) was added while stirring this, and the oxide molar ratio was 16 Na ₂ O.
An aqueous sodium aluminosilicate mixture for zeolite synthesis of Al ₂ O ₃ .20SiO ₂ .7753H ₂ O was prepared. 1 kg of this was filled in the same Teflon container as used in Example 1, and this was set in a dryer with a ventilation fan set to a temperature of 95 ° C. Adjust the opening of the top lid so that the water evaporation rate is about 200 mol / day in z value.
After 0 days, it was taken out from the dryer and washed by filtration. The slurry when taken out from the dryer was reduced to 23 g. This is a faujasite type with an average particle size of 3
The maximum particle size was 8 μm and the maximum particle size was 65 μm.

Comparative Example 5 Sodium aluminate aqueous solution (0.23 as Na ₂ O)
2 wt%, containing 0.3 wt% as Al ₂ O ₃ ) 340 g
15g of sodium hydroxide aqueous solution with a concentration of 48wt% was added to the above, and a water-glass solution (containing 0.188wt% as Na ₂ O and 0.6wt% as SiO ₂ ) while stirring this
2 kg, and the oxide molar ratio is 16Na ₂ O.Al ₂ O
_An aqueous sodium aluminosilicate mixture for zeolite synthesis of 3/20 SiO ₂ 12953 H ₂ O was prepared. 1 kg of this was filled in the same Teflon container as used in Example 1, and this was set in a dryer with a ventilation fan set to a temperature of 95 ° C. The opening of the upper lid was adjusted in advance so that the moisture evaporation rate was about 200 mol / day in terms of z value, and after 80 days, it was taken out from the dryer and filtered and washed. The slurry when taken out from the dryer was reduced to 14 g. This was amorphous and the solid yield was very small.

Example 5 1 kg of the aqueous mixture prepared in Example 3 was filled in the same Teflon container as used in Example 1, which was heated at a temperature of 95 ° C.
It was set in the dryer with a ventilation fan set to. The opening of the upper lid was adjusted in advance so that the water evaporation rate was about 50 mol / day in terms of z value, and after 80 days, it was taken out from the dryer and filtered and washed. The slurry when taken out from the dryer was reduced to 45 g. This was a faujasite type having an average particle diameter of 45 μm and a maximum particle diameter of 58 μm.

Example 6 1 kg of the aqueous mixture prepared in Example 3 was filled in the same Teflon container as used in Example 1, which was heated to 95 ° C.
It was set in the dryer with a ventilation fan set to. The opening of the upper lid was adjusted in advance so that the water evaporation rate was about 100 mol / day in z value, and after 40 days, it was taken out from the dryer,
It was filtered and washed. The slurry when taken out from the dryer was reduced to 45 g. This is a faujasite type with an average particle size of 35 μm and a maximum particle size of 55 μm.
It was a big one.

Example 7 1 kg of the aqueous mixture prepared in Example 3 was filled in the same Teflon container as used in Example 1, which was heated to 95 ° C.
It was set in the dryer with a ventilation fan set to. The opening of the upper lid was adjusted in advance so that the water evaporation rate was about 400 mol / day in z value, and after 10 days, it was taken out from the dryer,
It was filtered and washed. The slurry when taken out from the dryer was reduced to 45 g. This is a faujasite type with an average particle size of 12 μm and a maximum particle size of 23 μm.
It was a big one.

Comparative Example 6 1 kg of the aqueous mixture prepared in Example 3 was filled in the same Teflon container as used in Example 1 and the temperature was 95 ° C.
It was set in the dryer with a ventilation fan set to. The opening degree of the upper lid is about 1,000 mol / m
Adjust it to be a day, remove it from the dryer after 4 days,
It was filtered and washed. The slurry when taken out from the dryer was reduced to 45 g. This was of faujasite type and had an average particle diameter of 1.5 μm and a maximum particle diameter of 4 μm.

Comparative Example 7 Aqueous sodium aluminate solution (0.77 as Na ₂ O)
2 wt%, containing 1.0 wt% as Al ₂ O ₃ ) 1.02
A sodium hydroxide aqueous solution 378 having a concentration of 48 wt% in kg
g, 6 kg of a water glass solution (containing 0.626 wt% as Na ₂ O and 2.0 wt% as SiO ₂ ) was added with stirring, and the oxide molar ratio was 30 Na ₂ O · A.
An aqueous mixture of sodium aluminosilicate for zeolite synthesis of 1 ₂ O ₃ .20SiO ₂ 3934H ₂ O was prepared. 1 kg of this was filled in the same Teflon container as used in Example 1, and this was set in a dryer with a ventilation fan set to a temperature of 95 ° C. The opening of the upper lid is adjusted beforehand so that the water evaporation rate is about 200 mol / day in z value, and
After a day, it was taken out from the dryer and filtered and washed. The slurry when taken out from the dryer was reduced to 55 g.
A small amount of spherical gmelinite type is generated in this product, and P
The molds were mixed, the average particle diameter was 2.5 μm, and the maximum particle diameter was 5 μm.

Example 8 Aqueous sodium aluminate solution (0.77 as Na ₂ O)
2 wt%, containing 1.0 wt% as Al ₂ O ₃ ) 1.02
211 wt% sodium hydroxide aqueous solution with a concentration of 48 wt%
g, and while stirring this, 6 kg of a water glass solution (containing 0.626 wt% as Na ₂ O and 2.0 wt% as SiO ₂ ) was added, and the oxide molar ratio was 20 Na ₂ O · A.
An aqueous mixture of sodium aluminosilicate for zeolite synthesis of 1 ₂ O ₃ .20SiO ₂ .3876H ₂ O was prepared. 1 kg of this was filled in the same Teflon container as used in Example 1, and this was set in a dryer with a ventilation fan set to a temperature of 95 ° C. The opening of the upper lid is adjusted beforehand so that the water evaporation rate is about 200 mol / day in z value, and
After a day, it was taken out from the dryer and filtered and washed. The slurry when taken out from the dryer was reduced to 48 g.
This is a faujasite type with an average particle size of 8μ.
m, and the maximum particle diameter was 18 μm.

Comparative Example 8 Sodium aluminate aqueous solution (0.77 as Na ₂ O)
2 wt%, containing 1.0 wt% as Al ₂ O ₃ ) 1.02
11 g of sodium hydroxide aqueous solution having a concentration of 48 wt% per kg
Was added, and 6 kg of a water glass solution (containing 0.626 wt% as Na ₂ O and 2.0 wt% as SiO ₂ ) was added with stirring, and the oxide molar ratio was 8Na ₂ O · Al ₂
An aqueous mixture of sodium aluminosilicate for zeolite synthesis of O ₃ .20SiO ₂ .3806H ₂ O was prepared. 1 kg of this was filled in the same Teflon container as used in Example 1, and this was set in a dryer with a ventilation fan set to a temperature of 95 ° C. The opening degree of the upper lid was adjusted in advance so that the moisture evaporation rate was about 200 mol / day in terms of z value, and after 20 days, it was taken out of the dryer and filtered and washed. The slurry when taken out from the dryer was reduced to 38 g. This is a faujasite type with an average particle size of 1.5μ.
m, and the maximum particle diameter was 3 μm.

Comparative Example 9 Sodium Aluminate Aqueous Solution (Na ₂ O 1.16)
94 g of 48 wt% sodium hydroxide aqueous solution was added to 680 g of wt% and Al ₂ O ₃ contained 1.5 wt%, and while stirring this, a water glass solution (0.94 wt% as Na ₂ O and 3 as SiO ₂ ) was added. 6 wt% (containing 0.0 wt%) was added to obtain an oxide molar ratio of 16Na ₂ O.Al ₂ O ₃
An aqueous sodium aluminosilicate mixture for zeolite synthesis of 30SiO ₂ · 3603H ₂ O was prepared. 1 of these
The same Teflon container used in Example 1 was filled with kg, and this was placed in a dryer with a ventilation fan set to a temperature of 95 ° C. The opening degree of the upper lid was adjusted in advance so that the moisture evaporation rate was about 200 mol / day in terms of z value, and after 20 days, it was taken out of the dryer and filtered and washed. The slurry when taken out from the dryer was reduced to 56 g. This one was amorphous.

Example 9 Aqueous sodium aluminate solution (0.96 as Na ₂ O)
5 wt%, containing 1.25 wt% as Al ₂ O ₃ ) 816
119 g of sodium hydroxide aqueous solution having a concentration of 48 wt%
Was added, and 6 kg of a water glass solution (containing 0.7825 wt% as Na ₂ O and 2.5 wt% as SiO ₂ ) was added with stirring, and the oxide molar ratio was 16 Na ₂ O · A.
An aqueous mixture of sodium aluminosilicate for zeolite synthesis of 1 ₂ O ₃ .25SiO ₂ .3709H ₂ O was prepared. 1 kg of this was filled in the same Teflon container as used in Example 1, and this was set in a dryer with a ventilation fan set to a temperature of 95 ° C. The opening of the upper lid is adjusted beforehand so that the water evaporation rate is about 200 mol / day in z value, and
After a day, it was taken out from the dryer and filtered and washed. The slurry when taken out from the dryer was reduced to 50 g.
This product is mainly spherical gmelinite type and a small amount of P type is mixed, and the average particle size is 30 μm and the maximum particle size is 4 μm.
It was 2 μm.

Example 10 Aqueous sodium aluminate solution (0.69 as Na ₂ O)
5 wt%, containing 0.9 wt% as Al ₂ O ₃ ) 1.13
A sodium hydroxide aqueous solution 165 having a concentration of 48 wt% per kg
g, 5.33 kg of a water glass solution (containing 0.563 wt% as Na ₂ O and 1.8 wt% as SiO ₂ ) was added with stirring, and the oxide molar ratio was 16 Na ₂
An aqueous sodium aluminosilicate mixture for zeolite synthesis of O.Al ₂ O ₃ .16SiO ₂ .3570H ₂ O was prepared. 1 kg of this was filled in the same Teflon container as used in Example 1, and this was set in a dryer with a ventilation fan set to a temperature of 95 ° C. The opening degree of the upper lid was adjusted in advance so that the moisture evaporation rate was about 200 mol / day in terms of z value, and after 20 days, it was taken out of the dryer and filtered and washed. The slurry when taken out from the dryer was reduced to 45 g. This was of faujasite type and had an average particle diameter of 10 μm and a maximum particle diameter of 21 μm.

Comparative Example 10 Aqueous sodium aluminate solution (0.27 as Na ₂ O)
wt%, containing 0.35 wt% as Al ₂ O ₃ ) 2.91
25 g of sodium hydroxide aqueous solution having a concentration of 48 wt% per kg
A water-glass solution (containing 0.22 wt% as Na ₂ O and 0.7 wt% as SiO ₂ ) with stirring.
3.43 kg was added to obtain an oxide molar ratio of 4Na ₂ O · A.
The _{l 2 O 3 · 4SiO 2 ·} 3505H 2 O for zeolite synthesis sodium aluminosilicate aqueous mixture was formulated. 1 kg of this was filled in the same Teflon container as used in Example 1, and this was set in a dryer with a ventilation fan set to a temperature of 95 ° C. The opening degree of the upper lid was adjusted in advance so that the moisture evaporation rate was about 200 mol / day in terms of z value, and after 20 days, it was taken out of the dryer and filtered and washed. The slurry when taken out from the dryer was reduced to 23 g. This is a faujasite type with an average particle size of 2 μm.
The maximum particle size was 4 μm.

[0050]

[Table 1] X indicates that the requirements of the present invention were not satisfied. The same applies to the following tables.

[0051]

[Table 2] * Evaporation rates are shown roughly in the text but accurate in the table.

[0052]

[Table 3] FAU is faujasite type, AM is amorphous, P.I. G indicates a mixture of P type and gmelinite type, and Tr indicates that the amount of formation is extremely small.

[0053]

According to the method of the present invention, a catalyst, a catalyst carrier,
A zeolite having a large particle size, which is useful as an adsorbent or an adsorbent / separator, can be obtained by an industrial method without using a special raw material or a special device.

Claims (1)

[Claims] 1. A ## STR1 ## expressed in terms of mole ratios of oxides _{xM 2 O · Al 2 O 3} · ySiO 2 · zH 2 O (M represents an alkali metal cation, 0.5y ≦ x ≦ 1.4
y, 5 ≦ y ≦ 25, 1,000 ≦ z ≦ 10,000), and an aqueous mixture for zeolite synthesis is prepared,
The aqueous mixture is heated at a temperature sufficient to crystallize the zeolite to evaporate the water content of the aqueous mixture at a water evaporation rate of 50-500 moles / day, expressed using the value of the water molar ratio z. A method for producing a zeolite, characterized in that the crystallization is carried out.