JPS6158812A - Manufacture of crystalline aluminosilicate zeolite - Google Patents

Abstract

PURPOSE:To make the grain size of the titled zeolite small and to increase SiO2/ Al2O3 molar ratio and its purity by containing the crystalline material of raw material mixture free from organic cations to the raw material mixture consisting of silica, alumina and organic cations or the like. CONSTITUTION:The crystalline aluminosilicate powder having X rays diffraction pattern shown in the table by crystallizing the raw material mixture free from organic cations is obtained. This powder is contained in the raw material mixture contg. silica, alumina, alkali metals, organic cations and water. Thereafter the raw material mixture is heated and crystallinzed to obtain ZSM-5 type crystalline aluminosilicate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing ZSM-5 type crystalline aluminosilicate zeolite (hereinafter abbreviated as single KZSM-5).

[Conventional technology]

ZSM-5 is produced by crystallizing a raw material mixture consisting of silica, alumina, alkali metals, tetrapropylammonium ions, and water.
r) et al. (Special Publication No. 46-100+5
4), and many synthesis methods have been proposed since then.

A method has been proposed in which seed crystals are present in a raw material mixture for crystallization. For example, there is the following method.

(1) The method disclosed in JP-A-56-37215 uses seed crystals to reduce the amount of expensive organic mineralizing agent used.

(2) The method disclosed in Japanese Patent Publication No. 57-7819 uses seed crystals instead of organic mineralizers to produce ZSM-
This is the way to get 5.

The goal of both methods is to reduce the amount of organic mineralizing agent used. In addition, the seed crystal in these methods is a crystal synthesized in the coexistence of an organic mineralizing agent, and even if such a crystal is synthesized as a seed crystal,
As detailed below, the average particle size of the final product is 1
It is extremely difficult to obtain particles smaller than microns.

On the other hand, JP-A-56-54222 and JP-A-50-
No. 5335 discloses that Z with a particle size of 1 micron or less
Methods for producing SM-5 have been disclosed, but these methods require vigorous stirring during crystallization or
This method requires keeping at a temperature of 0 to 110°C for 4 days or less, and the process is complicated.

[Problems to be solved by the present invention]

The object of the present invention is to obtain particles with an average particle size of 1 micron or less.
The object of the present invention is to provide a method by which ZSM-5 having a high i02/AJ20s molar ratio can be easily produced on an industrial scale.

By reducing the particle size, a catalyst with very high catalytic activity and long catalytic life can be obtained when used as a catalyst for catalytic conversion of hydrocarbons such as crab king and isomerization.

[Means for solving problems]

The present inventors have obtained an X-ray diffraction pattern obtained by reacting a raw material mixture consisting of silica, alumina, an alkali metal, an organic cation, and water with a raw material mixture that does not contain organic cations, and which has an X-ray diffraction pattern shown in Table 1 below. The presence of a crystalline aluminosilicate zeolite having
It has been found that M-5 can be easily obtained.

Table 1 Relative strength 113 Strong 10.0 Strong 3.73 Weak 641 Weak 3.01 Weak 3.73 Weak 3.58 Weak 3.01 Weak 4.67 Weak 4.28 Weak 3.84 Very Strong 3.74 Strong 3.66 Weak 3.47 Weak 3.37 Weak 3.52 Weak 3.06 Weak 2.99 Weak The present invention was made based on this knowledge.

The details will be explained below.

[Function] The crystalline zeolite powder present in the raw material mixture as a seed crystal of the present invention is obtained by reacting a raw material mixture that does not contain organic cations, and has a crystalline zeolite powder having an X-ray diffraction pattern shown in Table 1. It is essential that it is an aluminosilicate powder. This seed crystal has its Sin, /At,
O, the molar ratio is 15-65. However, those with a 70 molar ratio of 20 to 30 tend to have the above-mentioned X-ray diffraction pattern. The amount of the seed crystal added is desirably α01 to 5% by weight based on the raw material mixture.

This seed crystal is, for example, 51Ct as described below.

It can be manufactured using A raw material mixture is prepared consisting of white carbon as a silica source, aluminium (IJ) as an alumina source, sodium hydroxide and water as an alkali modifier. Alternatively, a raw material mixture is prepared in which an amorphous aluminosilicate homogeneous phase compound obtained by simultaneously and continuously reacting a sodium silicate aqueous solution and an aluminum-containing aqueous solution is dispersed in a sodium hydroxide aqueous solution. do. A feature of the present invention is that these raw material mixtures do not contain any (organic cations).

The raw material mixture is expressed by the molar ratio of each oxide, 5t02/A120s = 20-45Na20/5
i02 =0.05~f2.3H, O/5iO1=
12-70. The raw material mixture was stirred at room temperature until it became sufficiently homogeneous, and then heated at 120°C to 120°C while stirring in an autoclave.
Crystallization is carried out by keeping at a temperature of 200° C. for 5 hours to 5 days.

Next, solid-liquid separation is performed, thoroughly washed, and dried overnight at 110°C.

The crystalline zeolite obtained by K in this way is 5i02
/AJ203 is a crystalline zeolite with a % ratio of 20 to 30 and an X-ray diffraction pattern shown in Table 1, and serves as a seed crystal that can be used in the present invention.

One feature of the X19 diffraction pattern of the seed crystal is that there are only two peaks between the lattice spacings d=3.70λ to d=3.86λ, even though it was synthesized without using an organic mineralizer. It is something that cannot be observed.

ZSM-5, which was synthesized by adding an organic mineralizing agent, was
As disclosed in Publication No. 6-10064, d=3
．． Two to three peaks are observed between 70λ and d=3.86λ. However, the patent publication No. 56, which was synthesized using silica sol as a silica source without adding an organic mineralizer,
The X-ray diffraction pattern of the ZSM-5 similar zeolite disclosed in Publication No. 49851 is d=3.70λ~d=
Four peaks are observed between 3.86λ. That is, the seed crystal used in the present invention is obtained from Japanese Patent Publication No. 56-49851.
This is a crystalline aluminosilicate zeolite that is essentially completely different from the ZSM-5 similar zeolite disclosed in the above publication.

Table 1, which was synthesized without using an organic mineralizer,
The ZSM-5 type crystalline aluminonolicade zeolite used in the present invention, which has the X-ray diffraction pattern shown in the figure, has a crystalline size of several hundred angstroms compared to other ZSM-5 or ZSM-5-like zeolites. It is characterized by very small particle size and very small aggregates.

The ZSM-5 type crystalline aluminosilicate zeolite used as this seed crystal is sometimes obtained as an aggregate of relatively large crystal particles, but this aggregate has very weak bonds between the crystal particles and cannot be dispersed in water. Alternatively, it can be easily made into small particles by pulverizing with a pulverizer. This is also a major feature of the seed crystal of the present invention.

On the other hand, the ZSM-5 type and ZSM that have been disclosed so far
-5 Similar zeolites have large crystal particles, and if they form aggregates, the bonds between the crystal particles of the aggregates are strong, and even if they are dispersed in water or crushed with a grinder, they will not be reduced to small particles. It is extremely difficult to do so. Even if such a material is used as a seed crystal, it is natural that ZSM of less than 1 micron will be produced.
-5 cannot be manufactured.

Crystallizing a raw material mixture that does not contain organic cations
The crystalline zeolite thus obtained having the X-ray diffraction pattern shown in Table 1 is 5i02/l
'Jt Os solubility ratio is 15-35.

When the 5i02/All Os molar ratio exceeds 65, the particle size becomes very large and the shape of the particles changes from 5i0 to 65.
It is completely different from that in which the 2/Al2O8 molar ratio is 20 to 30.

That is, the seed crystal with a 5i02/A40s molar ratio of 20 to 50 used in the present invention has very small crystal particles.
And if it is aggregated, disperse it in water, or
Relatively large aggregates can be reduced to small particles by a simple method such as pulverization using a pulverizer.

The drawing shows an electron micrograph of the seed crystal used in the present invention. As shown in the photograph, the seed crystal particles are aggregates of small crystals without a clear particle outline, and can be easily crushed as described above.

Using the seed crystal according to the present invention having the above characteristics, ZS
When M-5 is synthesized, ZSM-5 having a particle size of 0.1 to 1.0 microns is obtained. Also, surprisingly, ZS
Nuclei generation of M-5 occurs countless times on the particle surface of the nuclide crystal,
This nucleus grows only to a maximum size of Q, 5 microns. Furthermore, it was found that the nuclide crystals did not grow at all. Even more surprisingly, the seed crystal and ZSM-5
The particles are separated in a subsequent washing step to obtain uniform ZSM-5 with a particle diameter of 1 micron or less.

On the other hand, ordinary ZSM-
5. Alternatively, if synthesis is performed using ZSM-5-like zeolite as a seed crystal, large seed crystals that cannot be crushed remain in the product, and furthermore, the s-crystals cause crystal growth, resulting in very large particles. A mixed product is obtained, and nucleation on the seed crystal particle surface is considerably less.

Therefore, the seed crystal according to the present invention is a normal ZSM-5
Alternatively, it has properties completely different from ZSM-5 similar zeolites. That is, the seed crystal that can be used in the present invention is a Si 02 /
A620 is only crystalline aluminosilicate powder with a molar ratio of 15-55. The nuclide crystal is present in the raw material mixture at 0.01 to 5 M-ff551.

The silica source used in the present invention is not particularly limited as long as it is commonly used in the production of crystalline zeolite (
Examples include white carbon, colloidal silica, and dissolved silica.

The alumina source is not particularly limited as long as it is commonly used in the production of crystalline zeolite, including sodium aluminate and aluminum sulfate.

Examples include potassium aluminate, aluminum nitrate, aluminum chloride, colloidal alumina, and alumina.

Furthermore, an amorphous aluminosilicate homogeneous phase compound, zeolite, etc. can also be used as a silica source and an alumina source.

As an alkali metal source, hydroxide is used.

Potassium hydroxide, sodium silicate, which serves as a silica source, sodium aluminate, which serves as an alumina source, and the like are used.

As the organic cation, ZSM-5 type or ZSM-
There is no particular restriction as long as it is commonly used for zeolites similar to No. 5, and examples thereof include tetraalkylammonium ions, alkylamines, ammonia ions, and the like.

Conditions such as ratio of raw materials, temperature, pressure for 2 hours, etc. may be those commonly used as shown below.

The ratio of silica to alumina in the raw material mixture of the present invention is Si
02/AltOs molar ratio is 10 to oo, alkali metal to silica ratio is M, O/SiOH molar ratio is 0.01 to 30, organic cation (3) to silica ratio is R20/Si The O2 molar ratio is preferably in the range of o,oooi to 10. In addition, the seed crystal is 0% of the raw material mixture.
．． 01-5 heavy view% gin.

The synthesis reaction of the present invention is carried out using the raw material mixture in an autoclave at 806C to 300C under autogenous pressure until crystalline zeolite is produced. The time required for crystallization is 1 hour to 100 days, depending on the heating temperature.

After the crystallization is completed, a crystal powder is obtained by thoroughly washing with water and drying according to a known method. The crystal particles obtained here are ZSM-5 type crystalline zeolite having a substantially uniform particle size distribution with an average particle size of 1 micron or less.

[Effect 1 of the invention As is clear from the above explanation, according to the present invention, sto, / AJ, O with an average particle size of 1 micron or less
High purity ZSM-5 with a high s molar ratio can be easily obtained.

ZSM-5 obtained by the present invention is subjected to ion exchange with appropriate cations as necessary, and calcined as necessary, and then sieved with one molecule of adsorbent.

It can also be used as a catalyst.

〔Example〕

<Manufacture of seed crystal> Seed crystal A Pure water asoy, solid sodium hydroxide 6,ny, sodium aluminate aqueous solution (Nano:
18.6vrtX, kl, o,: 20. O
wt%.

R20: 61.4 + wt
i02: 87.7wtX+ Alt203: 0.
5wt%) 170F was added with stirring. After crystallizing this raw material mixture in an autoclave at 160°C for 72 hours, the reaction product was separated into solid and liquid, thoroughly washed with water, and then dried at 110°C. Next, it was ground in a mortar. The X-ray diffraction pattern of the obtained product was as shown in Table 2. The results of chemical analysis are 1, 1 N820S Al
2O, @ 21. It was 5in2.

Table 2 Relative intensity within lattice spacing 11.3 5010.
0 413.73
93.41
83.01
123.75
93.58 103.
01 94.57
B4.28
83.84
1003.74
573.66 25
3.47 103.3
7 113.52
123.06
122.99
19. Crystal B An overflow type reaction tank (actual volume: 3.51!'I) in a stirred state contains a sodium silicate aqueous solution (Si02: 2
5wtX, 1.5 l of Na2O: 8.2wtX)
/br, and aqueous aluminum sulfate solution with sulfuric acid added (AJ203: 4.3 wtX, SO,: 35, 5
wtX) was simultaneously and continuously fed at a feed rate of 0.51/hr to cause a reaction.

The apparent residence time of the reaction slurry was 50 minutes.

The reaction temperature was 30-32° C. The pH of the overflowing slurry was 3.3-3.6. Separate the discharged slurry into solid and liquid,
After sufficient water washing, 1, 1 Na2O・Al2O3m 23. I 5i02
An amorphous aluminosilicate homogeneous phase compound having a composition of 140H20 was obtained.

The thus prepared amorphous aluminosilicate homogeneous phase compound 266I was added to an aqueous solution of solid sodium hydroxide Z1J in 426 g of pure water with stirring.

This raw material mixture was heated to 155°C at 272°C in an autoclave.
After time crystallization, the reaction product is separated into solid and liquid,
After washing thoroughly with water, it was dried at 110°C. Next, it was ground in a mortar. The X-ray diffraction pattern of the obtained product was almost the same as in Table 2. The result of chemical analysis is t Q Na20 mA403 s 22.45i02
Met.

Seed crystal C pure water 413. p, solid sodium hydroxide a, oII, sodium aluminate (AJt Os: 32.98 w
tX, Nano: 53.13wtX) 3.6
, li' to make a homogeneous aqueous solution, and then colloidal silica sol (manufactured by Catalysts Kasei Kogyo Co., Ltd., trade name: Cataloi).
d S-30L+ 5i02: 50wt%)2
70II was added with stirring. This raw material mixture was heated to 180°C in an autoclave.

After 21 hours of crystallization, the reaction product was separated into solid and liquid, thoroughly washed with water, and then dried at 110°C. Next, it was ground in a mortar.

The result of X-ray diffraction of the obtained product is d=3.70X-
d=! The results were substantially the same as in Table 2 except that four peaks were observed during L86X. The results of chemical analysis were: 1, ONx, O・A1203J425i02.

To 487I of seed crystal pure water, 10.6g of solid sodium hydroxide, 217g of tetrapropylammonium bromide. V, sodium aluminate aqueous solution (Na20: 1 B, 6 wtX
# Al2O3: 20. Owt'X.

)i20:6L4wt%)2.8.9 was added to make a uniform aqueous solution, and then white carbon (manufactured by Nippon Silikani Gyo Co., Ltd., trade name Nip Seal VN-5, 5i02: 87.7
wtX1M20. =0.5wt9C) 7 & 11 were added with stirring. This raw material mixture was heated to 160°C in an autoclave.

After 48 hours of crystallization, the reaction product was separated into solid and liquid, thoroughly washed with water, and then dried at 110°C. Next, it was ground in a mortar.

The X-ray diffraction pattern of the obtained product was almost the same as in Table 2. The result of chemical analysis is t 5 Na2OIIAJ
It was 203-1035i02.

Seed crystal E Pure water 580I, solid sodium hydroxide 3.9p, tetrapropylammonium bromide 28.7L sodium aluminate aqueous solution (Na20: 1B, 6wt9, A401: 20.OwtX.

H, 0: 614 wt
7.7 wtX* Al2O3: 0.5 wtX)9
2.2 fl were added with stirring. The raw mixture was heated in an autoclave at 160°C.

After 48 hours of crystallization, the reaction product was separated into solid and liquid, thoroughly washed with water, and then dried at 110°C. Next, it was ground in a mortar.

The X-ray diffraction pattern of the obtained product was almost the same as in Table 2. The results of chemical analysis are 1. i Na2Oll
It was Al2O3@275i02.

Example 1 Pure water 487f! into a container, add 1 part of solid sodium hydroxide
0.6L Tetrapropylammonium bromide 23.7L
Sodium aluminate aqueous solution (Na20:18, 6w
t%+AI, 0,20. Owt'gi, H2O:
6L4wt%) 2.8I was added to make a homogeneous aqueous solution, and then white carbon (Japan Silikani Industry Exhibition, trade name Nip'/-k VN-3,5i02: 87.7
wtX, AJ203: 0.5wtX) 7
6-11 was added with stirring. After adding 3!9 of crystalline aluminosilicate powder (seed crystal A) to this raw material mixture, it was placed in a No. 11 autoclave at a circumferential speed of 0.5 r.
The mixture was crystallized by heating at 180° C. for 14 hours while stirring at rL/sec. Next, the reaction product was separated into solid and liquid, thoroughly washed with water, and then dried at 110°C. Table 6 shows the results of X-ray diffraction of the obtained product. The results of chemical analysis were: 1, I Nano aM, o, #895i02. The average particle size of this product was 0.8 microns.

Table 3 Relative intensity within lattice spacing 1 t2 4210.
0 29Z50
83.70
53.37
93.03 103.73
73.57
8s, oo
'64.62
74.37 f34.
26 114.00
B3.85
1003.72
443.65 2
73.41 103.32
103.05
10 Example 2 The procedure of Example 1 was repeated except that the amounts of crystalline aluminosilicate powder (seed crystal A) were changed to is, o, and y. The results of X-ray diffraction were almost the same as in Table 3. Also,
The result of chemical analysis is 0.91 Nano' AJ203 ・575i02
Met. The average particle size of this product was 0.7 microns.

Example 3 Seed crystal B was used instead of seed crystal A as crystalline aluminosilicate powder. Example 1 except that OI was added.
This was done in accordance with. The results of xa diffraction were almost the same as in Table 3. In addition, the results of chemical analysis are as follows: 1, I Na, Oa l'J, O, ++ 915in
.

Met. The average particle size of this product was 0.8 microns.

Comparative Example 1 The procedure of Example 1 was followed except that the crystalline aluminosilicate powder was not added to the raw material mixture. The results of X-ray diffraction of this product were almost the same as in Table 3. The average particle size of this product was 2.6 microns.

Comparative Example 2 The procedure of Example 1 was followed except that 18.0.9% of seed crystal C was added instead of the seed crystal as a crystalline aluminosilicate powder. The average particle size of this product is 3
,0 microns.

Comparative Example 6 The same procedure as in Example 1 was conducted except that 18.051 g of seed crystal A was added instead of seed crystal A as the crystalline aluminium non-licade powder. The average particle size of this product is 1
．． It was 8 microns.

Comparison fl14 As a crystalline aluminide powder, seed crystal E was used instead of seed crystal 18. The procedure of Example 1 was followed except that CM9 was added. The average particle size of this product is 2
．． It was 2 microns.

[Brief explanation of drawings]

The drawing is an electron micrograph of an example of a seed crystal used in the present invention.

Claims (1)

[Claims] (1) A raw material mixture containing silica, alumina, an alkali metal, an organic cation, and water is heated and crystallized to form ZSM-
In the method for producing type 5 crystalline aluminosilicate, during crystallization, the X-ray diffraction pattern shown in the table below, obtained by crystallizing a raw material mixture that does not contain organic cations, is used. 1. A method for producing a ZSM-5 type crystalline aluminosilicate zeolite, characterized in that a crystalline aluminosilicate zeolite having a crystalline aluminosilicate powder having the following properties is present. Lattice spacing (Å) Relative strength 11.3 Strong 10.0 Strong 6.73 Weak 6.41 Weak 6.01 Weak 5.73 Weak 5.58 Weak 5.01 Weak 4.37 Weak 4.28 Weak 3. 84 Very strong 3.74 Strong 3.66 Weak 3.47 Weak 3.37 Weak 3.32 Weak 3.06 Weak 2.99 Weak (2) Crystalline aluminosilicate powder with the X-ray diffraction pattern shown in the table The method according to claim 1, wherein 0.01 to 5% by weight of the raw material mixture is present. (3) The method according to claims 1 and 2, wherein the crystalline aluminosilicate powder having the X-ray diffraction pattern shown in the table has a SiO_2/Al_2O_3 molar ratio of 20 to 30.