JPS6148426A - Preparation of binderless crystalline aluminosilicate - Google Patents

Abstract

PURPOSE:To make unnecessary the presence of sodium in the stage of hydrothermal synthesis of a compression molded body by the titled process using the compression molded body comprising a mixture of raw material powder and aluminosilicate gel as binder and to obtain the titled salt having effective secondary pore by specifying the compsn. of said molded body. CONSTITUTION:In prepn. substantially of crystalline aluminosilicate from a compression molded body prepd. by kneading raw material powder with aluminosilicate gel, the compsn. of the molded body itself is arranged to be within a crystallizable range, and the proportion by weight of the aq. soln. to the molded body in the stage of hydrothermal synthesis is held at <=10. The binderless zeolite comprising said salt has >=about 0.3ml/g total pore volume (measured by the Hg compression method) and about 75-75,000Angstrom macropore radius, and >=about 25% of the pore volume is occupied by pores being + or -20% to the mean pore size. The X ray diffraction diagram is substantially equal to the diagram of TSZ crystalline aluminosilicate.

Description

DETAILED DESCRIPTION OF THE INVENTION A1.Object of the invention (industrial application field) The present invention relates to a crystalline aluminosilicate. More specifically, the present invention relates to a method for producing a binder-less zeo-light catalyst that does not substantially contain a binder.

(Prior art) Crystalline aluminosilicate is generally known as crystalline zeolite, and its crystal structure, both naturally occurring and synthetic, has four @ atoms formed centering on silicon (Si) at the apex. It is an aluminosilicate hydrate having a structure based on a three-dimensional skeleton of coordinated SiO4 tetrahedra and AlO4 tetrahedrons in which silicon is substituted with aluminum (,l).

SiO4 tetrahedron and AlO4 tetrahedron are 4.5.6.8.
4-membered ring, 5-membered ring, 6-membered ring formed by connecting 10 or 12 members
membered ring, 8-membered ring, 10-membered ring or 12-membered ring, and these 4.
5.6.8. It is known that the basic unit is a double ring in which 10- and 12-membered rings are overlapped, and that these are connected to determine the skeletal structure of crystalline aluminosilicate.

A specific cavity exists inside the skeleton structure determined by these connection methods, and the entrance of the cavity structure is determined by 6.8.1
0. and an opening consisting of a 12-membered ring. The formed pores have a uniform pore diameter, and only molecules below a certain size are adsorbed, and large molecules are not adsorbed because they are not allowed to enter the cavities. are known as "molecular sieves" because of their action, and are used as adsorbents, catalysts for chemical reactions, or catalyst supports in various chemical processes.

In recent years, methods that combine the above molecular sieve action and catalytic action have been intensively researched in various fields of chemical reactions. This is what is called a molecular shape selective reaction catalyst, and S, M.

As Cs1csery classifies from the functional aspect, (
1) Only specific reactants can approach the active site, (2) Only reactants with a specific shape can leave the reaction site after reacting at the active site, (3)
In a two-molecular reaction, individual molecules can freely move in and out of the reaction field, but there are three types of molecules that cannot react because the transition state is too large (“
Zeolite Chemistry andCa
ACS Monograph1
7L ACS, Washington D, C019
1976, p. 680).

This classification was made considering only the catalytic reactions inside the cavities of the crystalline aluminosilicate.

In other words, catalytic reactions on the outer surface of the crystal or on active sites near the outer surface are different from the above-mentioned catalytic action, and since all reactions occur freely, including reactions with small activation energy, the selectivity of the reaction is reduced. .

Therefore, in order to suppress such non-selective reactions on or near the outer surface of the crystal, there is a method of burying the active points by coating the outer surface of the crystal with a compound, or a method of burying the active points by coating the outer surface of the crystal with a compound, or using another method of solid acidity or alkalinity. A method of controlling the solid acidity of the active site has been considered, and the addition of silicon compounds, phosphorus compounds, magnesium compounds, etc. has been proposed.

On the other hand, there is also a method of controlling the ratio of the number of active sites with molecular shape selectivity within the crystal to the number of active sites without shape selectivity on or near the outer surface of the crystal by controlling the size of the crystal. For example, when a crystal is made larger, the proportion of active sites within the crystal increases relatively, and shape selectivity increases. However, according to this method, the approach and/or contact of the reactants with the active site is relatively restricted, resulting in a lower overall reaction activity. On the other hand, if the crystal is made smaller, the proportion of active sites on or near the outer surface of the crystal increases, resulting in a decrease in shape selectivity. The reaction activity increases as the reaction activity increases.

The charge of the Al0a-containing tetrahedron of crystalline aluminosilicate is balanced by retaining sodium cations within the crystal. It is a well-known theory that these cations are ion-exchanged by various methods to become a hydrogen type or a metal ion exchange type, and function as a solid acid catalyst.

In natural crystalline aluminosilicates, the cations are metals from group 1 of the Periodic Table of the Elements or group Ⅲ of the same table, especially sodium, potassium, calcium, magnesium and strontium. Also in synthetic crystalline aluminosilicates, The metal cations mentioned above are used, but in addition to metal cations, organic nitrogen cations have recently been proposed, such as quaternary alkylammonium ions, such as tetraalkylammonium ions. For the synthesis of crystalline aluminosilicate with a high silica/alumina ratio, it has been considered essential to use the above-mentioned nitrogen-containing organic compounds as an alkali source.

However, when using nitrogen-containing organic compounds,
In addition to the disadvantage of high raw material costs, in order to use the produced synthetic aluminosilicate as a catalyst, it is necessary to remove the nitrogen-containing organic compounds present in the synthetic product by calcining it at high temperature. This has the disadvantage of complicating the manufacturing process.

Furthermore, in the conventional manufacturing method using an amine-based organic compound such as a tetraalkylammonium compound or a primary amine of 02 to CIO as described above, the synthesis process, drying, and calcination.

During the process, various risks arise due to the potential toxicity of the organic compound or the decomposition of the organic compound, posing problems in terms of operational safety.

j Although the use of oxygen-containing organic compounds and sulfur-containing organic compounds has also been proposed, these cases do not solve the problems encountered when using nitrogen-containing organic compounds.

As a method to solve these problems, a method for producing crystalline aluminosilicate from an aqueous reaction mixture consisting essentially only of inorganic reaction materials has recently been disclosed (Japanese Patent Application Laid-Open No.
No. 8-45111).

It is expressed as a molar ratio of oxides, 0.8 to 1.5M2
/ no ・Al2O3・10~100Si02・ZH
20 (where M is a metal cation, n is the valence of the metal cation, and 2 is from 0 to 40).
The present invention relates to a crystalline aluminosilicate having a chemical composition of , and a powder X-ray diffraction pattern exhibiting at least the lattice spacing, ie, d-distance, shown in Table 1.

11.2 ±0.2 3゜ 10.1 ±0.2 3゜ 7.5 ±0.15 W.

6.03±0.1 M.

4, 26±0.07 M.

3, 86±o, os v, s.

3,82±o,os　　　　　　s.

3,76±o,os　　　　　s.

3, 72±o, os s.

3,64±0.05 3゜X as above
The aluminosilicate with a crystalline structure characterized by a line diffraction pattern was named TSZ.

In the relative intensities in Table 1, rV, S, and J are the strongest;
” is strong, “M,” is neutral, “W,” is weak, rV, W, J
indicates that it is very weak.

Moreover, analysis of the results of particularly highly accurate 2θ (θ is Bragg angle) measurement by powder X-ray diffraction analysis, which is different from the conventional method, revealed that the crystalline aluminosilicate (TSZ) according to the invention has crystallographic properties. It was concluded that the crystalline structure is monoclinic.

On the other hand, when zeolite catalysts are used industrially, for example in fixed beds of gaseous and liquid feedstocks or in fluidized bed operations such as catalytic cracking, particles with a certain size and shape, For example, it is supplied in the form of pellet-type particles or small spherical particles. In this case, the gas phase reaction is generally carried out at a large space velocity, and in the liquid phase reaction of heavy oil, diffusion from the catalyst surface is limited, so almost only the outer surface of the catalyst particles is used (in the US Since this diffusion limit is shown to be approximately 1/120 of an inch in Patent No. 3,966,644), it is desirable to maximize the area of the catalytically active zeolite catalyst surface. This problem can be improved by reducing the diameter of spherical catalyst particles, but on the other hand, the strength of the catalyst particles decreases and destruction of the catalyst particles occurs, so this method cannot improve the catalyst performance. has a limit. This can also be improved by reducing the particle size of the zeolite crystal powder, but on the other hand, shaped catalyst particles made only of zeolite crystal powder have the disadvantage that they cannot maintain sufficient strength to withstand industrial use. . Therefore, conventionally, when zeolite catalysts were used industrially, powdered zeolite was molded into, for example, pellets using a suitable binder.

However, according to this method, not only is a decrease in productivity unavoidable, such as a decrease in the space velocity of the reactants due to a decrease in the utilization rate of the zeolite used, but also As a result of the movement of the alkali or alkaline earth metals contained in the zeolite into the zeolite, it has the disadvantage that the zeolite is easily poisoned.
This method of producing pellet-type catalysts involves compressing and molding zeolite and an amorphous binder, so the amorphous binder gets into the so-called secondary pores that exist between the zeolite crystals. Although the physical strength increased, neither the amount nor the distribution of secondary pores could be controlled.

(Problems to be Solved by the Invention) Secondary pores mainly occur between particles when amorphous powder or crystalline powder is molded, so they reduce the strength of the pellet. 1. If the pores can be utilized, not only can the reactants easily move from crystal to crystal, but the catalytic activity of the pellet can be improved by substantially increasing the area of the crystal surface with catalytic activity. be able to.

The inventors of the present invention and others
We solved these problems and provided a binderless crystalline aluminosilicate with a unique shape that has excellent catalytic activity and a method for producing the same. did.

In this method, the presence of a sodium salt in the hydrothermal reaction aqueous solution is essential. However, for example N
aC1 has the effect of promoting crystallization as a mineralizing agent, but if the concentration exceeds a certain level or depending on hydrothermal conditions, it may corrode gold mud such as stainless steel. Also, NaOH
Although it is essential for the crystallization of zeolite, if it exists in an aqueous solution, it tends to crystallize from the surface layer of the molded product, and during crystallization, it can cause powdering of the pellet 7) and a decrease in strength. Improvements in these areas were desired.

Therefore, the first object of the present invention is to produce crystals consisting of substantially uniform crystal grains without requiring the addition of sulfur and lithium salts in an aqueous solution when a molded pellet is hydrothermally treated. It is an object of the present invention to provide a method for producing a binderless crystalline aluminosilicate consisting of a polyester aluminosilicate.

The second object of the present invention is to create a substantially crystalline alumino material that takes advantage of secondary pores and has practical strength.

An object of the present invention is to provide a method for producing a uniform binderless crystalline aluminosilicate composed of a silicate.

Structure of the Invention (Means for Solving the Problems) That is, the present invention produces substantially crystalline aluminosilicate from a molded product obtained by kneading raw material powder and aluminosilicate gel as a binder and press-molding the mixture. In the method for producing a binder-less crystalline aluminosilicate consisting only of salt, the molded body itself has a composition within a crystallizable range, and the weight ratio of the aqueous solution and the molded body during hydrothermal synthesis is 10.
A method for producing a binderless crystalline aluminosilicate, which is characterized by the following steps.

(Disclosure of the Invention) The binderless crystalline aluminosilicate (hereinafter referred to as binderless zeolite) consisting essentially of crystalline aluminosilicate according to the present invention also includes the aforementioned binderless zeolite. However, the binderless zeolite of the present invention has a total pore volume of 0.3 ml/g or more as measured by mercury intrusion method, a macropore radius of 75 to 75,000 pores, and a pore volume of 0.3 ml/g or more. 25% or more of the radius is included in the range of ±20% of the average pore radius, and the X-ray diffraction pattern is substantially that of TSZ crystalline aluminosilicate as shown in the table.

The outline of the manufacturing process of the binderless zeolite according to the present invention is as follows (1) Process of manufacturing raw material powder 2) Process of manufacturing aluminosilicate gel for binder 2) Process of kneading and molding raw material powder and binder It includes the steps of drying or firing the molded product, (1) hydrothermal treatment of the molded product, and so on.

The raw material powder used in the present invention means a pre-synthesized crystalline aluminosilicate. As such a pre-synthesized crystalline aluminosilicate used as a raw material powder, TSZ aluminosilicate and so-called ZSM-5 can be used.

The pre-synthesized crystalline aluminosilicate used here is
It is sufficient to use the unfired as-synthesized aluminosilicate, and it does not need to be in a completely crystalline form; it is simply pre-crystallized and has an X-ray diffraction pattern close to that of an amorphous aluminosilicate. However, when TSZ crystalline aluminosilicate is used, it is preferable to produce a binderless zeolite rich in TSZ crystalline aluminosilicate. When using zeolite, especially sodium 1
Preference is given to using it in salt form.

Regarding the composition of the above raw material powder, S i 02 /A
The j2203 ratio and Na2O/5i02 ratio are the TS described later.
It is preferable that the crystal is in the chemical formation region Z, and that the crystals have a small particle size from the viewpoint of the activity and strength of the binderless zeolite catalyst to be produced.

The TSZ crystalline aluminosilicate according to the invention is characterized by an X-ray diffraction pattern obtained by conventional powder X-ray diffraction. That is, 2θ=14°7° (d=6.0
The diffraction line of 3 people) is a single line (Slnglat), and 2θ = 23' (d-3, 86 people) and 2θ =
This structure differs greatly from the crystalline structure of the conventionally proposed crystalline zeolite in that the two diffraction lines at 23.3° (d-3, 82 people) are clearly separated. Such a specific X-ray diffraction pattern shows that the lattice spacing of the synthetic silicate does not undergo any significant changes even when the substituted cations, especially changes to the hydrogen ion type, changes in the 5i02/Aβ203 ratio, etc. .

Next, a method for producing crystalline aluminosilicate as a raw material powder used in the present invention will be explained.

The crystalline aluminosilicate that can be used in the present invention is generally prepared by using a silicon source, an aluminum source in a certain range of ratios, and adding an appropriate alkali source and water in a certain range of ratios. iJ! Di! ! L, can be prepared by heating and maintaining the aqueous reaction mixture at the crystallization temperature until crystals form. Such manufacturing conditions are, for example, about 10 hours to 1 o
This is achieved by maintaining it for several days.

TSZ crystalline aluminosilicate is a silica source, an alumina source,
containing an alkali source, water and a neutral salt of an alkali metal,
It is prepared from an aqueous reaction mixture consisting essentially of inorganic reactants, the composition of which, expressed in molar ratios of oxides, is as follows:

5i02/Aj! 203 10~13ONa20
/5i02 o, 01=0.5(Na2o+M2
/nO)/5iO2 0.03-0.3 H20/ (Na20+Mz/nO) 150-800 , preferably a metal cation selected from lithium, sodium, barium, calcium and strontium, where n is the valence of the metal cation and X- is the ion of the salt of the precipitation aid and/or mineralizer. It is. M2/nO and Na
2O are free M, )/nO and Na2O, respectively, and are generally in the form of classified acid salts, such as aluminates, silicates, etc., which are effective in hydroxide and zeolite synthesis. Moreover, the above-mentioned "free Na2O" can be opened by adding aluminum sulfate, sulfuric acid, hydrochloric acid, nitric acid, or the like.

In addition, TSZ crystalline aluminosilicate can be produced by changing the 5i02/Af203 molar ratio and the Na2O/5i02 molar ratio among the composition ratios of the aqueous reaction mixture mentioned above. Change.

That is, 5i02/Aj! of the aqueous reaction mixture! By changing the Na2O/5i02 molar ratio according to the 203 molar ratio, Na
When the 5i02/Al2O3 molar ratio is changed on the condition that the 2O/5i203 molar ratio is made the same, crystalline aluminosilicate having approximately the same crystal grain size is produced.

Furthermore, by varying the Na2O/5i203 molar ratio within the range of 1 to 15, it is possible to produce a crystalline aluminosilicate having a desired crystal grain size within the range of about 0.1 .mu.m to about 10 .mu.m.

In the present invention, a binderless zeolite can be produced by kneading a crystalline aluminosilicate synthesized in advance as described above and a binder and placing a molded product under crystallization conditions.

The mixing ratio of the pre-synthesized crystalline aluminosilicate and the binder is preferably 30 to 70% by weight of the former and 70 to 30% by weight of the aluminosilicate gel as the binder. In this case, even if the binder itself for producing the molded body does not have a crystallizable composition, it is possible to partially crystallize the binder by placing it under appropriate conditions; It is preferable that the binder itself has a composition that can be crystallized from the beginning of its formation, since the conditions for producing the binderless zeolite can be kept mild as a whole.

The aluminosilicate gel used in the present invention can be obtained by filtering the aqueous reaction mixture, which is a precursor of the TSZ crystalline aluminosilicate, for a certain period of time, and then crystallizing the aluminosilicate gel or molded product. After washing until the composition is within a range that does not cause excessive crystallization, drain thoroughly and reduce the moisture content (dry standard) to approximately 6.
It is preferable to adjust the amount from 5% by weight to about 95% by weight so that the addition of water is not particularly required at the time of crosstalk.

In the present invention, the TS2 crystalline aluminosilicate etc. produced as described above and the aluminosilicate gel are mixed at a composition ratio of El which allows the molded body to be at least crystallized.
After conditioning, kneading, and molding, the ratio of water to the molded product is set to a value that allows crystallization without a mineralizing agent, and by hydrothermal treatment, the aluminosilicate gel, which was initially amorphous, or powder Although it is amorphous in the line diffraction diagram, it is possible to crystallize pre-synthesized crystalline aluminosilicate.
In this manner, the binderless zeolite catalyst of the present invention consisting essentially of crystalline aluminosilicate can be produced.

As mentioned above, the composition of the molded body is expressed by the molar ratio of oxides, Na2O/Aj! 203 1.2-4. O3i 0
2/Af203 10”l OQNa20/S
i02 is preferably 0.02 to 0.15, especially Na2O/Aj! 203 1.5~3.03i0
2/A! 203 20~8ONa 20/S
iozo, 03~0. It is preferable to set it to 12.

FIG. 1 illustrates the above preferred range.

The amount of alkali in the molded body is an important factor for producing the binderless zeolite in the present invention. That is,
If the amount of alkali is small, crystallization may take a long time,
It may remain amorphous. In addition, alkaline deficiency can be added externally to cause crystallization, but in this case, crystallization tends to occur from the surface of the molded product, and crystallization of the molded product does not proceed uniformly, causing powdering. This is not preferable because it may lead to a decrease in the strength of the molded product.

On the other hand, if the amount of alkali is too large, the time required for crystallization will be shortened, but it may grow into large crystal particles, weakening the strength of the molded product, or causing the formation of other crystal phases. This is not desirable.

Furthermore, an important factor for producing the binderless zeolite in the present invention is the ratio (weight ratio) between the solution and the molded body during hydrothermal treatment.

As the hydrothermal reaction progresses, the composition of the molded body or binder becomes close to that of zeolite, and Na2O/5i
203 molar ratio approaches 1.

Therefore, the excess Na comes out into the solution as the hydrothermal reaction progresses.

Therefore, when the composition of the molded body is constant, if the amount of solution is small, the alkaline concentration of the solution will be high, and if the amount of solution is large, the alkaline concentration of the solution will be relatively low.

Therefore, the composition of the molded body should be within the above range, and H20
By setting the weight ratio of the /molded body to 10 or less, preferably in the range of 1 to 9, binderless zeolite can be easily synthesized without adding a mineralizing agent, especially a sodium salt, during hydrothermal treatment. I can do it.

Generally, the strength of a molded product varies depending on the size of the constituent particles, the packed structure, the coordination number of the particles, the shape of the particles, etc., and further varies depending on the volume and diameter of the pores formed. In particular, shaped zeolite catalysts are aggregates of crystal particles with various shapes, and their pore structure is a so-called binary pore structure, in which the crystal particles themselves have different characteristics. oa'! ``Kui 831
°°” 扛6? Near t'Ra? configured.

However, such crystal grains usually have little bonding strength, and are molded using some kind of binding agent or binder to give the pellet strength.

In this case, the particle size of the binder is generally smaller than the crystal particle size of the zeolite due to its intended use. Therefore, secondary pores are composed not only of pores between crystal particles but also pores between crystal particles and binder particles.

From the above, the binderless zeolite of the present invention, which is substantially composed of crystalline aluminosilicate, exhibits a sharp distribution of macropores between crystal grains in the thousands.
It is understood that having a strength that can withstand practical use cannot be easily predicted from the prior art.

In the present invention, the shape of the solid used in the hydrothermal reaction is not particularly limited, but from the viewpoint of ease of molding or usage efficiency when used as a catalyst, it is particularly pellet-shaped and irregular-shaped (Polyl).

b a 1 ), hollow cylindrical type (hollow tu
be), and the size is preferably about 1.5W in outer diameter from the viewpoint of handling.

The hydrothermal reaction of the present invention can be carried out by the method disclosed in Japanese Patent Application No. 58-45111.

As a result of the hydrothermal treatment performed in the present invention, the binder crystallizes, and the X-ray diffraction pattern of TSZ crystalline aluminosilicate, which directly represents the characteristics when synthesized without using organic cations, shows the distribution of secondary pores. is extremely sharp. Although a method for measuring the radius of the secondary pores to be controlled in the present invention is not necessarily established, the average radius can be estimated by the so-called mercury intrusion method. In the present invention, 1/ of the total pore volume obtained by this mercury intrusion method is
The average pore radius is defined as the radius that shows the cumulative value of 8 pores in No. This is important from the viewpoint of catalytic activity, as it also affects the diffusion rate.

The binderless zeolite obtained by the present invention is
It has good overall crystallinity and is a relatively uniform quadrant of crystal grains. For example, when TSZ crystalline aluminosilicate is used as the starting zeolite, the TSZ crystalline aluminosilicate formed by crystallization of the binder T of salt and starting materials
It is possible to obtain a zeolite structure that is so integrated that it cannot be distinguished from SZ crystalline aluminosilicate in a micrograph.

(Effects of the Invention) In the present invention, aluminosilicate gel 70 to 30% is used as a binder in which the amount of alkali is adjusted in advance to 30 to 70% by weight of crystalline aluminosilicate synthesized in advance.
Since the composition is kneaded with % by weight, the composition is adjusted to a range that allows the molded body to crystallize on its own and does not turn into powder due to excessive crystallization. After kneading and molding, it is dried or as needed. By firing, strong pellets can be obtained. Then, by simply adjusting the water/pellet weight ratio to 10 or less, preferably in the range of 1 to 9, and placing it in an autoclave together with water for hydrothermal treatment, the crystallization of the entire pellet can proceed uniformly. It is possible to produce binderless zeolite that maintains strength and has good crystallinity.

(Example) Example 1 (Manufacture of raw material powder) 25.0 g of sodium aluminate (Aj!203; 35.1% by weight, Na2O; 29.
1% by weight), and added this to 547°6g of water glass (
Na20; 9.3 Zffi amount%, 5i02; 28
．． 9% by weight Japanese Industrial Standard No. 3 water glass, hereinafter simply 3
(abbreviated as water glass) and 271.4 g of pure water were added to a water glass solution to form a homogeneous solution (liquid A).

Next, 157.8 g of concentrated hydrochloric acid (35%) and 351.0 g of pure water
g to prepare an aqueous hydrochloric acid solution (solution B).

Furthermore, sodium chloride, mu solution (sodium chloride 97.2
g, pure water 607. 4 g), and while stirring, add A.
Solution and Solution B were added to obtain an aqueous reaction mixture.

Approximately half of the aqueous reaction mixture was placed in a SUS autoclave, heated, and maintained at 185°C under autogenous pressure for 48 hours. Stirring was performed at 300 rpm.

The crystallized solid product was separated by filtration and after washing with water, 11
It was dried at 0°C for 16 hours.

Production of binder> Aluminum sulfate (A#203; 15.4]3i%)
65.9g, 15% sulfuric acid 33.8g, pure water 420g aluminum sulfate aqueous solution, and water glass (No. 3 water glass) 6
06g, pure water 306g water glass aqueous solution, sodium chloride aqueous solution (thorium chloride 35g 1 pure water 1200g)
and mixed with stirring. The aluminosilicate gel produced was filtered and washed with about 71 g of pure water. Thereafter, water was drained, and the moisture content was measured to be 86.4% by weight (dry basis).

Production of pellets 75 g of raw material powder, 551 g of aluminosilicate gel and 0.73 g of sodium hydroxide obtained by the above operations.
The mixture was kneaded while drying with a Ni-Goo until it reached a moldable moisture content, and molded into a pellet with an outer diameter of about 1.5 ms using an extruder.

After drying the pellets at about 110°C for 16 hours, a portion was separated and chemically analyzed, and the result was 5i02; 85.0% by weight.
, AJ203; 5.62% by weight, Na2O; 4.72
Weight f%, and scorching heat range ff1 (900°C); 3.96% by weight. Expressed in terms of oxide composition ratio, it is 1.38Na20-AIt203.25.7Si02.

Crystallization of pellets After further calcining the pellets at 600°C for about 3 hours,
．． 5 g was taken out and put into a stainless steel autoclave in Step 1 together with 613 g of pure water, and crystallized at 181° C. for 64 hours. Stirring was performed at a rotation speed of 15 Qrpm.

After the temperature was lowered, the pellet was taken out from the autoclave, washed, dried, and subjected to powder X-ray diffraction analysis to obtain a highly pure diffraction bagun of substantially TSZ.

Moreover, the electron micrograph also showed that most of the material was crystalline, and it was clear that the aluminosilicate gel had crystallized.

Furthermore, when the pore distribution was measured by mercury intrusion method, the total pore volume was 0.497 cc/g, which was ±20% of the average pore radius.
% range was found to contain 31% of the total pore volume.

The breaking strength of this pellet after drying is 1.8Kg/3m
m, it showed a strength sufficient for practical use.

Example 2 24.6 g of aluminum sulfate (A
l:zo3; 15. 4iff1%) was dissolved, and 20.4 g of concentrated sulfuric acid (95%) was further added to prepare an aluminum sulfate solution (liquid A).

Water glass (Na20; 9.36m12%, 5jO2; 2
Add 153 g of pure water to 303 g (9.4% by weight) and mix the water glass aqueous solution with it! 1! ! I did it (8 waves).

Furthermore, sodium chloride aqueous f4 solution (90g of sodium chloride
, 600 g of pure water) and add liquid A and B while stirring.
liquid was added to obtain an aqueous reaction mixture.

After the addition was completed, the mixture was stirred for about 30 minutes, then placed in an autoclave, heated, and maintained at 180° C. for 18 hours under autogenous pressure. The generated solid was filtered, washed with water, and
It was dried at ℃ for 16 hours.

(Manufacture of binder) 49.2 g of aluminum sulfate, 40.8 g of 95% sulfuric acid,
An aluminum sulfate aqueous solution containing 420 g of pure water was gradually added to a water glass aqueous solution containing 606 g of No. 3 water glass and 1506 g of pure water. The produced aluminosilicate gel was filtered, washed with approximately 81% pure water, drained, and the water content was measured to be 86.2% by weight.

Production of pellets> 5 og of the raw material powder obtained by the above operations and 370 g of aluminosilicate gel were kneaded while drying with a Ni-Goo until the moisture content reached a moldable level, and then an extrusion molding machine was used to make pellets with an outer diameter of approximately 1.
．． It was molded into a 5 mm pellet.

After drying the pellets at room temperature for a day and night, the pellets were dried at 110'C for about 1
It was dried for 6 hours. When a portion was taken and chemically analyzed,
5i02; 78.4% by weight, Aβ2'03
; 3.65iRfi%, Na2O; 5.51% by weight, and loss on ignition (900°C) i12.3% by weight.

Expressed in terms of oxide composition ratio, this is 2.48Na20-A
j! 203.36.4Si02.

(Crystallization of pellets After further calcining the pellets at 600°C for about 3 hours, 50 g
The sample was collected and placed in a lβ autoclave with 300 g of pure water, and crystallized at 180° C. for 40 hours. Stirring was performed at a rotation speed of 1100 rpm.

After the temperature was lowered, the pellets were taken out from the autoclave, washed, dried, and subjected to powder X-ray diffraction analysis to obtain a highly pure diffraction pattern of substantially TSZ.

Furthermore, electron micrographs showed that most of the material was crystalline. The fracture strength of this pellet after drying is 1. 5Kg/3m
The comparative example material powder and binder, which were layers, were manufactured in the same manner as in Example 2, except that the amounts of aluminum sulfate added were 19.7 g, 39°, and -4 g, respectively.

Chemical analysis revealed that the composition of the pellet was 5IO2;
3.4% by weight, AJ203; 3.84% by weight, Na
20; 11. 7fold f% and MM! (900
℃) was 11.0% by weight. This is expressed in terms of the composition ratio of oxides: 5.01Na20・Aj! 203-32, 5 S i 02 Theal.

After further calcining the pellets at 600℃ for about 3 hours, 50g
The sample was collected and placed in 12 autoclaves together with 300 g of pure water, and crystallized at 180° C. for 40 hours. Stirring was at 1100 rpm.

After cooling down, the pellets were taken out of the autoclave, but
At this time, it was quite powdery. After washing, drying and powder X-ray diffraction analysis showed a diffraction peak of a mixture of TSZ and mordenite.

The breaking strength of the pellet was as low as 0.7 Kg/3 mm.

[Brief explanation of drawings]

FIG. 1 shows a preferable range of the composition of a molded body for synthesizing a binderless zeolite according to the present invention, and the inner range shows a particularly preferable range. The numbers in the figure represent the molar ratio of N a 20 / A it 2 o, 3.

Claims (1)

[Scope of Claims] 1) Binderless crystalline aluminosilicate consisting essentially of crystalline aluminosilicate from a molded product obtained by kneading raw material powder and aluminosilicate gel as a binder and molding under pressure. 1. A method for producing a binderless crystalline aluminosilicate, characterized in that the molded body has a composition within a range in which it can itself be crystallized. 2) The composition ratio of the pressure-molded molded body is expressed as the molar ratio of oxides, M_2/nO/Al_2O_3:1.2-4.0SiO
_2/Al_2O_3; 10-100M_2/nO/S
iO_2: 0.02 to 0.15 (however, M is at least one metal cation selected from the group of metals in Group I and Group II of the Periodic Table of the Elements, and n is the metal cation A method for producing a binder-less crystalline aluminosilicate, characterized in that the valence is ). 3) The composition ratio of the molded body is expressed as the molar ratio of oxide, M_2
/nO/Al_2O_3; 1.5-3.0SiO_2/
The method for producing a binderless crystalline aluminosilicate according to claim 2, characterized in that Al_2O_3: 20-80 M_2/nO/SiO_2: 0.03-0.12.