JPS623014A - Crystalline aluminosilicate and production thereof - Google Patents

Abstract

PURPOSE:To produce crystalline aluminosilicate suitable for a selective contact reaction of hydrocarbon, having high catalytic activity, by using an aqueous reaction mixture consisting of inorganic materials such as an Si compound, an Al compound, an alkali metallic compound, water, etc., as raw materials. CONSTITUTION:Sodium silicate, etc., as a silica source is blended with sodium aluminate, etc., as an alumina source, water and an alkali metallic compound such as NaCl, KCl, etc., as a mineralizer in the following ratio. SiO2/Al2O3; 10-130, M2/nO/SiO2; 0.03-0.5 (M is metallic cation of group I or group II of periodic table, n is its valence) and H2O/M2/nO; 100-1,000, X<-> is anion of salt of mineralizer). The blend is heated at about 120-230 deg.C for 10-20hr to produce crystalline aluminosilicate of cation exchange type shown by molar ratio of oxide like the formula (1).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a crystalline aluminosilicate and a method for producing the same, and particularly relates to a novel crystalline aluminosilicate having molecular shape selectivity and catalytic ability and a method for producing the same. . More specifically, the present invention provides a crystalline aluminosilicate having a unique crystal structure and a high SiO2/Alz03 ratio suitable for selective catalytic reactions of hydrocarbons.

Crystalline aluminosilicate is generally known as crystalline zeolite, and its crystal structure, both naturally occurring and synthetic, is SiO+, which is formed around silicon (Si) and has four oxygen atoms coordinated at the apex. Tetrahedron and this silicon (Si)
It is an aluminosilicate hydrate having a structure based on a three-dimensional skeleton of ARO4 tetrahedron. The SiO+ tetrahedron and the A I 04 tetrahedron are 4, 5, 6, 6, 8, or 12-membered rings formed by connecting 4, 5, 6, 8, or 12 members, and these A double ring in which 4.5.6.8 and 12-membered rings are overlapped serves as a basic unit, and these are connected to determine the skeletal structure of the crystalline aluminosilicate. There are specific cavities in the skeletal structure determined by these connection methods,
The entrance of the cavity structure forms an aperture consisting of a 6, 8, 10 and 12 membered ring. The formed cavities have uniform pore diameters, and molecules of a certain size or less are adsorbed, but large molecules are not allowed to enter the cavities. Such crystalline aluminosilicates are known as "molecular sieves" due to their behavior, and the properties mentioned above can be used as adsorbents for various chemical processes and as catalysts and catalyst supports for chemical reactions. It's being used.

The electric charge of the aluminum-containing tetrahedron of the crystalline aluminosilicate as described above is maintained in balance by containing cations in the crystal. In natural crystalline aluminosilicates, the cations are the metals of the engineering group of the Periodic Table of the Elements or of 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. It has been considered that the use of organic nitrogen-containing compounds as described above as an alkali source is essential for the synthesis of crystalline aluminosilicate with a high silica/alumina ratio.

However, when using organic nitrogen-containing 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 organic nitrogen compounds present in the compound by calcination at high temperatures.

This had the disadvantage of complicating the manufacturing process.

Furthermore, as mentioned above, in conventional production methods using amine-based organic compounds such as tetraalkylammonium compounds or primary amines such as cz CIO,
During the synthesis process, drying and calcination process of organic substances, the latent toxicity of the organic substance or the decomposition of the organic substance may pose a physiological risk, which poses a problem in terms of work safety.

As a result of various research and experiments, the present inventors have discovered a crystalline aluminosilicate with a novel crystal structure that has remarkable shape selectivity and catalytic ability of 1 wJ, and also exhibits excellent performance as an adsorbent, and a We have now discovered a process which allows production from essentially inorganic reactive materials.

Therefore, the main object of the present invention is to provide a crystalline aluminosilicate having a unique crystal structure and a high degree of catalytic activity with a high SiOz/AuzOx molar ratio, and a crystalline aluminosilicate having a unique crystal structure and a high degree of catalytic activity with a high SiOz/AuzOx molar ratio. It is an object of the present invention to provide a method for producing a compound and water from an aqueous reaction mixture consisting essentially only of inorganic reaction materials.

Another object of the present invention is to provide a crystalline aluminosilicate having an extremely excellent selective decomposition activity for chain hydrocarbons and a unique crystal structure characterized by an X-ray diffraction pattern.

Still another object of the present invention is to synthesize aluminosilicate M2MO
Auz 03- S i Ol -H2O (Kokote, M
is a metal cation with n valence. ), which does not require the heat treatment step of the composite required in the prior art, thus making the manufacturing process easy and simple and making it possible to reduce manufacturing costs. The goal is to provide the following.

The present invention was completed based on the above-mentioned findings,
The above objectives can be effectively achieved.

That is, the present invention provides 0,8-1,5M,72O"Ax,o3" expressed in molar ratio of oxides.
has the chemical composition The present invention relates to a crystalline aluminosilicate having a powder X-ray diffraction pattern exhibiting the lattice spacings, ie, d-distances, shown in Table 1.

1-1-1 dog lattice plane spacing relative strength worker's knee
Engineering Z Uni] 11.2 ±0.2
S.

10.1 ±0.2 5.

7.5 ±0.15 W・6.0
3 ±0.1M.

4.26 ±0.07 M.

3.8fi ±o, 05V,
S.

3.82 ±o, os
,s.

3.76 ±0.05
S.

3.72 ±0.05
5.

3.64 ±0.05
3.

Aluminosilicate having a crystal structure characterized by an X-ray diffraction pattern as described above is hitherto unknown.
Hereinafter referred to as TSZ.

These values are the results measured by conventional methods. The irradiation was a copper doublet and a scintillation counter equipped with a strip chart recorder was used. The peak height and its position were read from the chart as a function of 20 (θ is Black's angle). From these, the relative intensities and lattice spacings (d), expressed in angstroms, corresponding to the recorded lines were measured.

In the relative strengths in Table 1, V and S are the strongest, S.

is strong, M is medium strong, W is weak, and V and W are very weak.0 The crystalline aluminosilicate (TSZ) according to the present invention is
It is characterized by an X-ray diffraction pattern obtained by a conventional method of powder X-ray diffraction. That is, 2θ=14.7° (d=6
．． The diffraction line of 03 people) is a single line (Single), and both the diffraction lines of 2θ = 23' (d = 3', 86 people) and 2θ = 23.3° (d = 3.82^) The clear separation is the biggest feature that can be distinguished from the crystal structure of the crystalline zeolite that has been proposed so far.

In addition, we performed powder X-ray diffraction analysis in addition to the conventional method to measure 2θ (θ is Black's angle) with particularly high accuracy, and analyzed the results. It was found that it belongs to the monoclinic system. For example, 1,02N, which is the product of Example 7 described below.
az OΦAflz 01・2B, 2 S ioz・
TSZ with a composition of 12.2 Hz O has a=20.
159 (±0.004) people, b=19°882 (
±Q, OQ8) people, c = 13, 405 (±
0. OQ5) large, α=90.51° (±0.03°
) shows the lattice constant of the monoclinic system. The measured values and calculated values of the lattice spacing of this typical TSZ and the Miller index are listed in Table 2.

Such a specific X-ray diffraction pattern shows the 2
Changes in i-conversion cations, especially changes to hydrogen ion type, Si
The lattice spacing is not significantly affected by changes in the Oi/A9.2Oi ratio.

The preferred composition of TSZ in as-synthesized form is 0.8-1.3 M2f? expressed in molar ratio of oxides. eA sentence: LO5-25-80
SiOY0-40H20 (where M is at least one metal cation, and n is the valence of the metal cation). According to the present invention, at least a portion of the metal cations present during synthesis are replaced by ion exchange or the like. Ion exchange is part of the Periodic Table of Elements I
This can be carried out using metal ions of Group I to Group II of the same table, hydrogen ions such as acids, or ammonium ions. By exchanging with hydrogen, ammonium, noble metals, rare earth metals, etc., catalytic activity, especially activity as a catalyst for hydrocarbon conversion, can be imparted. SiOz/A2203 molar ratio is 25-8
In the range of 0, even if TSZ is converted to a hydrogen ion type, there is no change in the mesoclinal type, and the crystal structure is not affected.

According to the present invention, crystalline aluminosilicate, namely TSZ, can be produced by the following method. That is, T.S.Z.
contains a silica source, an alumina source, an alkali source and water, consists essentially of inorganic reactive materials, and has the following composition expressed in the following molar ratio: 5LOz/A 20310-130M 21nO/S i Oz O2O3-
0,5Hz O/Myn O100-12O00X
-/S i Oz O2Ol-20(
Here, M is a metal cation selected from Group 1 of the Periodic Table of Elements and Group N of the same table, n is the valence of the metal cation, and X- is the salt of the mineralizing agent. It is an anion. ) by preparing and maintaining at autogenous pressure a temperature in the range of about 20° C. to about 230° C. for about 10 hours to about 20 hours.

The preferred composition of the aqueous reaction mixture, expressed in molar ratios, is as follows.

S i Oz /All, z 03 2O-1
2ON az O/ S i Oz 0.
03-0.3 (N az O+M27IIO) / S
t O202O3-0゜3 H2O/(Na2O+M2InO) 150-800
X-/S i Oz 0.05-
15 Additionally, the optimal range of composition for the aqueous reaction mixture, expressed in molar ratios of oxides, is as follows:

S i Oz /AJlz 0330-115N az
O/S i O2O2O5-0,3(N az O
+MMIO) / S i Ozo, 05-0.3 H2O/CN az O+M2A10) 200-
700X-/ S t Oz 0.1
-10 or more, where M is a metal selected from Groups 1 and 2 of the Periodic Table of the Elements, in particular lithium, barium, calcium and strontium. The M2/rIO and Na2O are free M27+10 and Na2O, generally in the form of ultrafine acid salts such as aluminates, silicates, which are effective in hydroxide and zeolite synthesis. Also, the above “Yu@N
a z OJ can be adjusted by addition of aluminum sulfate, sulfuric acid, hydrochloric acid, nitric acid, etc. 6 In adjusting the aqueous reaction mixture, the source of the oxide reactant of the above composition used is the one used in the production of synthetic zeolite. Commonly used silica sources, for example, include sodium silicate, silica gel, silicic acid, aqueous colloidal silica gel, dissolved silica, powdered silica, and amorphous silica. As the alumina source, activated alumina, γ-alumina, alumina trihydrate, sodium aluminate, and various aluminum salts such as aluminum chloride, nitrate, and sulfate can be used. The metal oxide represented by M2InO is added to the reaction mixture in the form of a water-soluble salt or in the form of a hydroxide with a 1.0 thorium ion source. LizQ as a source of lithium cations is added in the form of NaO, sodium hydroxide, sodium aluminate or sodium silicate;
It is added in the form of LtCu04). An aqueous reaction mixture is prepared by mixing the silica source, alumina source, alkaline source, and water. In particular, suitable silica sources are sodium silicate, water glass, colloidal silica, etc., and alumina sources are sodium aluminate, aluminum sulfate, etc. In preparing the crystalline aluminosilicate TSZ according to the present invention, an aqueous reaction is performed. The water content of the mixture is important, and as mentioned above, the reaction mixture is
(N a z + My O) i expressed in terms of molar ratio.

It is necessary to have a water content of 0 or more, preferably in the range of 200 to 700. By setting the water content within the above range, mixing and stirring of the reaction reagent gel becomes easy.

After mixing the reactants as described above, the reaction mixture is maintained at autogenous pressure in the range of about 120"0 to about 230"C+ for about 10 hours to about 20 hours.

By adding a mineralizing agent to the aqueous reaction mixture during crystallization, the crystallinity of the crystallized product can be further improved, and the formation of amorphous aluminosilicate can be suppressed. Mineralizers include NaCl, Naz CO3
,,Naz304,NazSe04. KCj
L, KBr, KF, BaC1z or E a B r
Neutral salts of alkali metals or alkaline earth metals such as Z can be used. A preferred mineralizer is NaCjl. In this case, the amount added is, when the anion of the salt as a mineralizing agent is x- (the n-valent anion is a monovalent equivalent), the preferable X-/S f O2 molar ratio is: It ranges from about 0.01 to about 20. Further, preferred loadings range from about O.OS to about 15, with optimal loadings ranging from about 0.05 to about 1O.

The produced crystalline aluminosilicate is separated from the solution by filtration, then washed with water and dried. After drying, the product is dehydrated by calcining in air or an inert gas atmosphere at a temperature of about 200° C. or higher. The dehydrated product is useful as a catalyst or catalyst support for chemical reactions. Further according to the invention, the cations in the product are at least partially removed or replaced by heat treatment and/or ion exchange. In this case, those subjected to cation exchange are particularly useful as catalysts for hydrocarbon conversion. Substitution ions can be selected depending on the desired reaction, but include rIa, IIIa, and IVa of the periodic table of elements.
, Ib, IIb, mb, ■b, and group ■ metals are preferable, and can be replaced with hydrogen ions by acid treatment or substitution with N H4+ and heat treatment, hydrocarbon decomposition, isomerization Preferred substituent ions for conversion reactions such as conversion and alkylation are hydrogen ions and Group I metal ions.

Cation exchange can be carried out by contacting the crystallized product with the desired exchange cation or salt of cations. In this case, various metal salts can be used, in particular chlorides, nitrates, sulfates, acetates and the like are preferred.

The hydrogen ion exchange type crystalline aluminosilicate according to the present invention obtained by replacing TSZ with hydrogen ions is further brought into contact with an acid to extract alumina.1. SiO
2/Alz 03 MoJL/ratio can be increased to 100 or more. As a result, the acids used in the acid extraction treatment, which can further improve acid strength and decomposition activity, include various mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid, as well as organic acids such as acetic acid and formic acid. Acids are preferred. A particularly preferred acid is hydrochloric acid. The concentration of the acid used ranges from 1 to 12 normal. The temperature of the acid extraction treatment step is from room temperature to about 95°C, preferably as high as possible.For example, if the acid extraction treatment is carried out at 90°C for 4 hours using 3N concentration hydrochloric acid, the starting material Si
02/A1103 molar ratio can be 100 or more.

According to the present invention, it is preferable to improve the catalytic activity of TSZ by introducing an active metal component through ion exchange or introducing hydrogen ions through acid treatment as described above. Mixing is performed. When TSZ contains an active ingredient, the temperature is approximately 80°C to approximately 500°C, and the temperature is approximately 5°C to approximately 50°C.
K g/cm', preferably about 10 to about 30 Kg/cm'
The raw materials for reforming are brought into contact under the reaction conditions of a pressure of about 0.5 to about 5, OV/H/V, preferably about 1,0 to about 3, and a liquid hourly space velocity of OV/H/V. Can be modified.

In addition, when containing transition metals such as CO1Ni or noble metal components such as platinum and palladium, TSZ
It can be used as a catalyst for catalytic dewaxing of gas oil fractions and lubricating oil fractions. Catalytic dewaxing is performed at approximately 50°C to approximately 450°C,
Preferably, at a temperature of about 00°C to about 400°C, about 5K
g/c rn' ~ approx. 50K g/cm'
, preferably a pressure of about 10 Kg/crn' to about 30 Kg/Crn', a pressure of about 0-25 V/H/V to about 3
V/H/V, preferably about 1.0V/) I/V to about 2
, OV/H/V reaction conditions can be employed.

Furthermore, TSZ is capable of isomerizing normal paraffins, dehydrogenating,
It also exhibits catalytic activity in conversion reactions of organic compounds such as conversion of alcohols to hydrocarbons, alkylation of aromatic rings with alcohols, and disproportionation between aromatic compounds.

The cation exchange type crystalline aluminosilicate based on T S Z according to the present invention has a specific chemical composition and a lattice spacing shown by a powder X-ray diffraction pattern, as described above, and has an organic Conversion reactions of raw materials, especially.

It has a remarkable effect in hydrocarbon decomposition reactions.

Hereinafter, the crystalline aluminosilicate of the present invention will be explained with reference to Examples.

Example 1 4g of aluminum sulfate was dissolved in 170g of pure water,
Further, 5.7 g of concentrated sulfuric acid (95 wt%) and 18 g of sodium chloride were converted to prepare an aluminum sulfate solution. This aluminum sulfate solution was mixed with 25 g of water and 63 g of water glass (Na2O; 9.5 wt%, Si02;
28.6wL%) (Japanese Industrial Standards No. 3 water glass) with stirring, and expressed as oxide molar ratio 3.9Na2OIIAuz03 *50Si02 h2
An aqueous reaction mixture was obtained with a composition of 184H2O. In this case, C1-/5iOZ of sodium chloride as a mineralizing agent
It was 5i021.02. The aqueous reaction mixture was charged into a SUS autoclave and heated to 1.
Heating was maintained at 80°C for 20 hours. The crystallized solid product was separated by filtration, washed with water, and then dried at 110°C. When a sample of this solid product was subjected to chemical analysis, it was found that Na2O;
2.6wt%, AMz03; 4.23wt%, SiO2
A chemical composition of 84.8 wt% and 8.4 wt% of H2O was obtained.

This was expressed as the molar ratio of oxides as follows.

1.01N a2O* A i2o,e 34. I
5i02-11.2 H2O This product was subjected to X-ray analysis and the results shown in Table 3 were obtained.

Table 3 Lattice spacing Relative intensity Lattice spacing Relative intensity 1
t18 74! ,,73
469.76 14
&49 59.05
1 3.45
10Z46 5 Otsu36
77.08 2
! ,,519&72 6
526 36.37 11
S, 05 136.01
13 3.00 1
35.72 7 2゜98
145.58 10
2.94 85.16
2 5.03 6 4.913 7 4.62 5 4,. 27 15 4.09 5 4.01 6 3.86 100 3.82 67 576 38 This X-ray analysis was performed by a conventional method of powder X-ray diffraction. The irradiation beam was a single α doublet of copper, and the X-ray tube voltage and tube current were 40 kV and 70 mA, respectively. 6 Diffraction angle 2θ and diffraction line intensity were measured using a goniometer and a strip chart pen recording device. A scintillation counter equipped with a counter was used. At this time, the operation speed is 2
At 0 rotation, 26/min was adopted, and the time constant of the rate meter was 1 second.

A portion of the product was calcined at 540° C. for about 3 hours and then degassed under vacuum at 300° C. for about 3 hours. The zeolite adsorbed 7.0% by weight of water at 12 mmHg and 25°C, 1.0 and 5% by weight of n-hexane at 20 mmHg and 25°C, and 4.5% by weight of cyclohexane at 20 mmHg and 25°C.

(Evaluation of Activity) In order to clarify the catalytic action of TSZ, the activity was compared with that of a crystalline aluminosilicate having a conventionally known powder xila diffraction pattern.

5% for ion exchange of sodium ions in TSZ
Ion exchange operation was performed at 80° C. for 1.5 hours using a NH4CM solution. Do this process 4 times and finish 16
H-type TSZ was prepared by firing at 00°C for 3 hours. Next, H-type TSZ powder was mixed with a separately manufactured alumina binder at a ratio of 7:3 (weight ratio after firing), water was added, and kneaded. Thereafter, extrusion molding was performed to obtain pellets with a diameter of 1.5 mm.

Using the above TSZ catalyst, an n-hexane decomposition reaction was carried out as follows.

A glass reactor was filled with 3.2 mM of the catalyst ground into a 16/30 mesh, and 3.2 mM of silica chips, which were also ground into a 16/30 mesh, were filled above the catalyst bed to improve the diffusion and heating of the reactants. The catalyst bed was maintained at 300°C.

N-hexane was placed in a saturator kept at 10° C. and nitrogen was flowed as a carrier gas so that the concentration of n-hexane in the nitrogen gas was 10%.

After a certain period of time after introducing n-hexane/nitrogen into the reactor system, the remaining amount of n-hexane is measured using gas chromatography and compared with the amount of n-hexane in the feed to determine the conversion rate. ) was sought.

After that, air was introduced into the reactor system and the catalyst bed temperature was raised to 50°.
At C, the carbonaceous material adhering to the catalyst was combusted, the catalyst was returned to a fresh state, and the experiment was conducted by changing the space velocity again.

In this way, the conversion rate of n-hexane was determined at 300°C and 275°C, and the following results were obtained (Table 4).

Similarly, the n-hexane decomposition activity of a catalyst obtained by converting a crystalline aluminosilicate having a known powder X-ray diffraction pattern into a hydrogen exchange type was also evaluated, and the results are also shown in the same table. These results revealed that the TSZ according to the present invention has significant hydrocarbon decomposition activity.

Table 4 n-hexane decomposition activity k(In -L-) -x Reaction temperature (°C) 300 300 275 30
0 500(1), □1 2.35 t56 α7
91〇 − 20tlN O, 98t21 α? 9 α50s
o t7s α96 t1? α8
5 [151451,75Q,97 t16[17
9 [15060t73 α97 120 Q, 85
0.49 (Book 1) N-Hexane 1001 Decomposition Comparative Example 1 In 405 g of pure water, 9.8 g of aluminum sulfate was dissolved, 11.2 g of concentrated sulfuric acid (95 wt%), 34.3 g
of tetrapropylammonium bromide (TPABr
) and 37.8 g of sodium chloride to prepare an aluminum sulfate solution. This aluminum sulfate solution was mixed with 76.5 g of water and 154.2 g of water glass (Na, 2O
; 9.13wt%, 5iOz; 2g, 8wt%) (Japanese Industrial Standards No. 3 water glass), mixed with stirring, expressed as the molar ratio of oxide, 4.4 (TPA)zo -52ONa2O-Amataz03
An aqueous reaction mixture was obtained having the composition: .50SiO2.2180H2O.

In this case, 0fL-/5iOz5iOz was 0.9. The aqueous reaction mixture was poured into a SUS autoclape, heated, and maintained at 160° C. for 20 hours at autogenous pressure. The crystallized solid product was separated by filtration, washed with water and dried at $110°C. A sample of this solid product was subjected to chemical analysis (TPA): 10.9 wt%, Na2O: 1°3
8wt%, Al2O3; 3.83wt%, 5tO2;
A chemical composition of 78.8 wt%, H2O; 5.0 wt% was obtained.

When this was expressed as the molar ratio of oxides, it was as follows.

0.75 (TPA)2O・0.63Naz011Ai
203 #35.05iO2*7.4H2O After calcining a portion of this product at 540°C for about 3 hours, X-ray analysis was performed in the same manner as described in Example 1, and the results shown in Figure 1 were obtained. Ta. In addition, Fig. 3 shows the magnification of the product at 5o.
A secondary electron beam image (SEM) magnified by oo is shown.

Example 2-4 Dissolve 2.5 g of aluminum sulfate in 70 g of pure water,
Next, 5.4 g of concentrated sulfuric acid (95 wt%) was added to prepare an aluminum sulfate solution (liquid A).
25g of pure water and 63g of water glass (N a Z O;
9, 5 wt%, 5fO2; 28.6 wt%) was prepared (liquid B).

Furthermore, an aqueous sodium chloride solution was prepared by dissolving 21 g of sodium chloride in 100 g of pure water.

8. Add the above solutions A and B to an aqueous sodium chloride solution simultaneously with stirring, and express the molar ratio of the oxides.
8Na2O"AJ1z03 e80siO2・348
An aqueous reaction mixture was obtained with a composition of 5H2O. In this case, the concentration of sodium chloride as a mineralizing agent was 1.2 mol relative to SiO2.

The above aqueous reaction mixture was placed in a SUS autoclave, heated, and maintained at 170°C under autogenous pressure for 20 hours to crystallize, to obtain a solid product.

The obtained solid product was separated by filtration and washed with water.

It was dried at 110°C. A sample of this solid product was subjected to chemical analysis to determine its chemical composition, and it was found that Na 20 ;
, 80 wt%, Aiz03.3.05wt%, S
The results were obtained: iOz: 89.9 wt%, H2O: 5.3 wt%. This was expressed as the molar ratio of oxides as follows.

0.87N&z O* A1103 m50. I 5
iOz $9.82O This product was subjected to X-ray analysis in the same manner as described in Example 1, and the results shown in Table 5 were obtained (Example 2).

The above solutions A and B were each prepared, and solutions A and B were simultaneously added to an aqueous ammonium carbonate solution in which 16 g of ammonium carbonate (containing 45% by weight as cOz) was dissolved in 100 g of pure water with stirring. Expressed as a molar ratio of 8.8Na2O・AM2O3"80SiO211
An aqueous reaction mixture was obtained having a composition of 3485HO.

In this case, the concentration of ammonium carbonate, which is the mineralizing agent, is SiO
2, it was 0.54 mol. The aqueous reaction mixture is
The mixture was placed in a US autoclave, heated, and kept at 170°C under autogenous pressure for 20 hours to crystallize, yielding a solid product. The obtained solid product was separated by filtration and after washing with water,
Dry at °C.

When a sample of this solid product was subjected to chemical analysis, it was found that Na
zO; 1.92wt%, AJlz01; 3
, 10wt%, Sioz; 89.0wt%, H2
A chemical composition of 0°6.0 wt% was obtained. This was expressed as the molar ratio of oxides as follows.

1.02Naz 0IIA sentence Z 031148, 9S
iO2 fist 10.9H2O This product was subjected to X-ray analysis in the same manner as described in Example 1, and the results shown in Table 5 were obtained (Example 3).

Next, each of the above solutions A and B was prepared, and at the same time, 6 g
of sodium sulfate was added to an aqueous sodium sulfate solution dissolved in 100 g of pure water with stirring, and the molar ratio of oxides was expressed as 8.8Na2O*Alz 03 ・8O8ioz
- An aqueous reaction mixture was obtained with a composition of 3458H2O. In this case, 1 degree of thorium sulfate, which is a mineralizing agent, is 5
The amount was 0.28 mol per iOz. The aqueous reaction mixture was placed in a SUS autoclave, heated to an elevated temperature, and maintained at 170°C under autogenous pressure for 20 hours. The solid product was separated by filtration, washed with water, and dried at 110"C'. A sample of this solid product was subjected to chemical analysis. Na2O; 2.15 Wt%; AJlz o3;
3.16Wt%, Sioz; 88.
8wt%, H2O.

I wanted to obtain a chemical composition of 5.9 wt%.When expressed in terms of the molar ratio of oxides, it was as follows.

1.12Nazo*AJlzo1 m47.8SiOz
-lo, 6H2O This product was subjected to X-ray analysis in the same manner as described in Example 1, and the results shown in Table 5 were obtained (Example 4).

Table 5 aA I/”o(1) d(2) I/r, (*
) d(l xtr; ts>4.09 3
409 5 ζ09 44
．． 01 5 4. CN 4 4
02 6i49 9 i4?
8 549 7A45 11
A45 1G 145 10
556 5 536 4 536
4531 10 531 1o
51 115 26 5 5.26
5 526 515 14
A05 1s! Lo5 142
．． 99 16 λ9? 15 500 1!12,? 7 16 2. ? 7
+4 2.97 t4λ93
6 2.94 5 2.94
6 Comparative Example 2 The same conditions and operations as in Example 2 were adopted except that no mineralizing agent was used. As a result, as solid products, Na2O; 2.43 wt%, Au, 03; 3.17 wt.
%, 5UO2; 88.1wt%, H2O.

A chemical composition of 6.3 wt% was obtained. The molar ratio of oxides was as follows.

1. 26Naz o-Aiz 03 m 47.2
5iO21111,3H2O This solid product was subjected to X-ray analysis in the same manner as described in Example 1, and was found to be amorphous alumina silica.

Example 5-6 Salt jk prepared by dissolving thorium in 160 g of pure water
-) -k 11um
5. 6Naz O11Auz 03 Threat 47S
An aqueous reaction mixture was obtained having the composition of ioz lI 5314H2O. In this case, the concentration of sodium chloride was 9.40 as CN, -/5iOz5A02. A solid product was obtained by heating and maintaining the aqueous reaction mixture at 180° C. at autogenous pressure as in Example 1. After washing it with water and drying it at 110°C, it was found that NaZO; 3,02 wt%, AJlz0
3.4.44wt%, SiOz; 83.8wt%
, H2O.

The chemical composition was 8.7 wt%. The molar ratio of oxides was as follows.

1.12Naz O-A sentence z 03 ・32, 1si
This product was subjected to X-ray analysis in a manner similar to that described in Example 1, giving the results shown in Table 6 (Example 5).

Next, add the above liquid A and 30 g of colloidal silica at the same time.
Adding 1.6 g of sodium chloride to a sodium chloride aqueous solution prepared by dissolving it in 160 g of pure water while stirring,
Expressed as oxide molar ratio, 5.6Naz O*Al;H
An aqueous reaction mixture was obtained having a composition of 03m 475 ioz" 5314H2O. In this case, the sodium chloride was at a concentration of 0.27 as Cl-/5iOZ5A02. The aqueous reaction mixture was subjected to the same crystallization conditions as above. A solid product was obtained by heating and maintaining the product at 110 °C.
; 3, 47 Wt%, AR203; 4.18wt
%, SiOz; 86.6wt%, H2O゜6.9
The chemical composition was wt%. When this was expressed as the molar ratio of oxides, it was as follows.

1.23Na2O"Aiz03"30.4SiO211
10,9H2O This product was subjected to X-ray analysis in the same manner as described in Example 1, and the results shown in Table 6 were obtained (Example 6)
.

Note 1) Sodium aluminate (AjLz O3; 43
．． 5 wt%, Naz O; 30.1 wt%) Note 2) Colloidal silica (Sioz; 20, Owt
%, NazO; 0, 35
W t %) Table 6 Example 5 ″A Example 6 +1.18 54 N, 1
9 499, 76 19
9.77 + 79,
04 1 9. O61
7,4667,465 72O827091 4725&72 41L57
9 18
86.01 j 4
&Oj I 4A71
11! L72
Na58 13 5
．． 59 12! L16
2 515 2SO56
52O45 498749? 74.62
7 4.62
7ζ57 10 t57
? ζ27 12
hair 27 12573
48 573 4546
5 56 3.65
29muro 0 5
161 4S49
7 549 9th 05
12 506 1
5,500 15,500
152.9B +5
2.98 142.94
6 195
5 Comparative Example 3 The same crystallization conditions and operations as in Example 5 were adopted except that sodium chloride was not used as a mineralizing agent, and the result of chemical analysis of the obtained solid product was Na2O; 3.3
3wt%, Aj2. z03; 4.19wt%, S io
z: 85.3 wt%, H2O: 7.18 wt%. This is expressed as the molar ratio of oxides as follows.

1.37Naz 0eAlz 03・34.6SiO2
・9.71H2O When this product was subjected to X-ray analysis, it was found that amorphous silica.
It was alumina.

From the above results, it is clear that TSZ obtained by the production method of the present invention
was found to have a unique crystal structure.

Example 7 5.2g of aluminum sulfate was dissolved in 70g of pure water,
Further, 4.5 g of concentrated sulfuric acid (95 wt%) was added to this to prepare an aluminum sulfate solution (liquid A). Next, add 25g of pure water and 63g of Shiraki Industrial Standard No. 3 water glass (
Na2O; 9.5wt%, Sioz; 28.6w
t%) was prepared (liquid B), and an aqueous sodium chloride solution was prepared by dissolving 18 g of sodium chloride in 100 g of pure water. The above solutions A and B were simultaneously added to an aqueous sodium chloride solution with stirring, and expressed as the molar ratio of oxides, 3.8Na20*Aiz 03 * 38S fez
- An aqueous reaction mixture with a composition of 1685H2O was obtained. In this case, the concentration of sodium chloride, which is a mineralizing agent, is
The amount was 12 O2 mol based on O2.

The above aqueous reaction mixture was charged into a SUS autoclave, heated, and kept at 170°C under autogenous pressure for 20 hours to crystallize, to obtain a solid product.

The solid product obtained was separated by filtration and after washing with water, 110
Dry at °C. A sample of this solid product was subjected to chemical analysis to determine its chemical composition; Na2O; 3.23 wt%;
A sentence z03; 5.21wt%, Sioz: 80.
3wt%! (20; 11.2 wt% was obtained. This was expressed as the molar ratio of oxides as follows. 8 1 , 02 Naz No. O Alz 03
-26,23iOz-12,2H2° This product was subjected to X-ray analysis in the same manner as described in Example 1, and the results shown in Table 7 and FIG. 2 were obtained.

Further, FIG. 4 shows a secondary electron beam image (SEM) of this product at a magnification of 5000 times. Comparing this with FIG. 3, the characteristics of monoclinic crystals are clearly visible.

Example 8 2.5 g of aluminum sulfate was dissolved in 130 g of pure water, and 9 g of concentrated sulfuric acid (95 wt%) and 21 g of sodium chloride were added to prepare an aluminum sulfate solution. This aluminum sulfate solution was mixed with 35 g of pure water and 90 g of
g Shiraki Industrial Standard No. 3 water glass (Naz O; 9.5
wt%, SiO2; 2B, 6wt%) with stirring, and the molar ratio of the oxides is expressed as 10.
5Na2O・Aiz03” 114SiO21329
An aqueous reaction mixture with a composition of 1H2O was obtained. In this case, the Ci-/5iOz molar ratio of sodium chloride as a mineralizer was 0.84. The aqueous reaction mixture was placed in a SUS autoclave, heated, and heated to 18
Heating was maintained at 0°C for 20 hours.

The crystallized solid product was separated by filtration and washed with water.
Dry at °C. When a sample of this solid product was subjected to chemical analysis, it was found that Naz O; 1.11 wt%, AJlz
O3; 2.04wt%, SiO2; 93.8wt%,
A chemical composition of 3.0 wt% H2O was obtained. This was expressed as the molar ratio of oxides as follows.

0. 89Naz O11Auz 03 m
78. 1SiO1z-8,4H2O When this product was subjected to X-ray analysis, the results shown in Table 7 were obtained.

Table 7 Example 7 Example 8 1L18 55 1t15
792J Ri 5
2.94 7 Example 9 The novel crystalline aluminosilicate (TSZ) obtained in Example 1
) and reprinted synthetic zeolite (Zeolon manufactured by Two-Tone)
In order to compare the activity of X0OH), an alcohol conversion reaction was carried out using a glass reactor.

0.35g TSZ zeolite (about L, 0ce)
A glass reactor was filled, and the catalyst bed was maintained at 500°C for 2 hours in a nitrogen stream, and the temperature was lowered to 300°C in a nitrogen stream. The temperature of the actor was maintained at 300° C., and then nitrogen was introduced as a carrier gas into a saturator in which the partial pressure of methanol was maintained at 0.163 atm, and methanol was passed through the catalyst bed.

The reaction conditions at this time are shown below.

Temperature: 1300°C Gas rate: 321 Sea/Hr Weight space velocity (SV): 2, 321+1/) I/W Methanol: 0, 81 g/Hr Methanol partial pressure: 0.163 atm.

The decomposition products were analyzed by gas chromatography and the results shown in Table 8 were obtained.

From the above results, the zeolite obtained by the present invention) TSZ
was found to have remarkable catalytic ability in alcohol conversion reactions and to have high selectivity to olefins, which are useful raw materials in the chemical industry. It has also been proven that I am good at keeping active.

Example 10 A crystalline aluminosilicate sample (identified as TSZ) prepared by the same method as that shown in Example 1 was subjected to the same ion exchange operation as in Example 1 to obtain ammonium (NH4).
Type TSZ powder was prepared.

Next, the N H4 type TSZ powder was mixed with a separately prepared alumina binder at a ratio of 7=3 (weight ratio after baking).
After adding water and mixing, extrusion molding was performed to obtain a pellet with a diameter of 1.5 mm. Then, it was baked at a dry vk of 600° C. for 3 hours. Furthermore, this pellet was added to 1N1 (NOx
) z solution at 80°C for 1 hour,
After washing with water and drying, baking at 600℃ for 3 hours, 0.6
Hy! containing 4% by weight of Ni! 11 TSZ catalyst was obtained.

A light oil fraction having the following properties was dewaxed by contacting it with the above catalyst under the reaction conditions shown in Table 9 in the presence of hydrogen. The results are shown in Table 9.

The results of Comparative Example 4 are also shown in the same table.

Specific gravity (15/4℃) 0.8753 Sulfur (wt%) 1.56 Nitrogen (wt%)
0.03 carbon/hydrogen (weight ratio) 6
．． 69 Pour point ("0) 15 Distillation test (ASTM D-2887) ("C) Initial boiling point
161 5% 273 10% 302 30% 345 50% 370 70% 392 90% 422 95% 435 87% 444 Comparative Example 4 Product prepared under the same conditions as Comparative Example 1 at 540°C for about 3 hours. After calcination, substantially the same powder X as in FIG.
A Ni-containing H-type zeolite catalyst was prepared in the same manner as described in Example 10 using a sample confirmed to have a line diffraction pattern. The Ni content of the catalyst was 0.67 wt.

A catalytic dewaxing experiment was conducted using this catalyst and the same gas oil feedstock as in Example 10. The experimental results and reaction conditions obtained are shown in Table 9.

Table 9 Reaction conditions Example 10 Comparative example 4 Temperature (℃') 310 370 3153
70 Liquid space velocity (V/) I/V) 2 2
2 2 Pressure (Kg/cm'G) 42 4
2 42 42 Processing gas velocity 450 45
0 450450 (Venue-Hz/Venue-raw material oil) Product oil (product oil fraction with boiling point of 221°C or higher) Yield
78 83 72 81 (wt% vs. feedstock oil) Pour point ('0) -15-40-15-4
0 Comparative Example 5 39.8g (7) 0.7g NaOH and 0 in hot water
．． 79 g of NaAJloz (29, 1 wt% NaZ
O235,7wt%A 3.35.2wt%H2O
) was dissolved in 3.7 g of water with 20.8 g of aqueous colloidal silica sol (40 wt% 5 iOz, 0.4% N
a2O) with stirring so that the total oxide molar composition is 5.0Naz O * AJlz 03 * 50S io
A reaction mixture of z@100H2O was prepared.

The reaction mixture was taken into an autoclave and maintained at approximately 200° C. and autogenous pressure for 72 hours.

The solid product was separated by filtration, washed with water and dried at 110°C. When a sample of this product was subjected to powder X-ray diffraction analysis, the X-ray diffraction pattern shown in Figure 5 was obtained, indicating that a portion of crystalline aluminosilicate was contained in the amorphous material. confirmed.

A portion of this product was dried and a Ni-containing H-type catalyst was prepared in the same manner as described in Example 10. Using the catalyst thus obtained, the gas oil fraction described in Example 10 was catalytically dewaxed, and the results shown in Table 10 were obtained.

Table 10 15 conditions Comparative example 5 temperature ('O
) 325 370 Liquid space velocity (V
/ H/V) 2 2 Pressure (Kg
/c rrIJG) 42 42 Processing gas velocity 450 450 (see-82/
- Raw material oil) Produced oil (produced oil fraction with a boiling point of 221°C or higher) Yield (wt%)
(to feedstock oil) 88 53 pour point ("C)
-2,5-20 These results show that the TSZ according to the present invention produces lower pour point gas oil in higher yields than zeolites prepared by methods that do not use organic cations or mineralizing agents such as tetrapropylammonium bromide. It turns out that it can be manufactured.

Example 11 This example describes the production of lubricant base oil by catalytic dewaxing.

Boiling point range of 232℃ (6
The lubricant base oil fraction of ILOOoF was subjected to phenol solvent extraction and propane solvent dewaxing, and had the following properties as a dewaxed feedstock.

Specific gravity (15/4℃) 0.88!35 sulfur negative (
Weight%) 0.98 Nitrogen (weight ppm)
35 Carbon/Hydrogen (weight ratio) 8.48 Pour point c”
c)-t.

Viscosity (100℃, cSt) 11.81 Viscosity (40
°C, c S t ) 106.4 Viscosity index
96 Boiling point range ('C('F)) Initial boiling point 334
(833) 97% 572 (+082) Using the same Ni-containing H-type TSZ catalyst as in Example 10, the boiling point range was 260°C (500'F) to about 454°C (850'F).
The lubricant base oil fraction of 'F) was subjected to catalytic dewaxing for 18 days under the following reaction conditions.

Reaction conditions Temperature (°C) 280-310 Liquid hourly space velocity (V/H/V) 1.1 Pressure (Kg/crn'G) 42 Processing gas (Ben-H1!/Dan-Feedstock oil) 450 Next, the above feedstock oil Table 11 shows the reaction conditions and dewaxing results under which the sample was subjected to catalytic dewaxing.

Comparative Example 6 Using the same Ni-containing H-type zeolite catalyst used in Comparative Example 4, the boiling point range was 280°C (500°F) to about 454°C (850'F) cl! 1m base oil fraction 18
Example 11 after being subjected to catalytic dewaxing for several days under the following reaction conditions:
A raw material oil identical to that described in 1 was subjected to catalytic dewaxing.

Reaction conditions temperature ('C) 280-32
0 Liquid space velocity (V/H/V) 1.1 Pressure (K
g/crry'G) 42 Processing gas velocity 450 (Text-H2/Father-Feedstock oil) Table 11 Troubled L ``1 Button Knee'' Kana--Number of days of oil running 011 157 +57 Temperature (''C) 310 320
335 320 335 355 Liquid space velocity (
V/H/V) 1.1 1.1 1.1
1. +1. + 1.1 pressure (Kg/cm
'G) 42 42 42
42 42 42 Processing gas velocity (text-H2/i-stock oil) 450 450 450 450 450
450 Raw Bodo (2) Yield (wt% vs. raw oil) 82β 752 7U
85.4 84j9 82. ! Pour point (”0)
-30-40-4027,5-25
-30 viscosity 1g (100℃, est) +2
,15 12β5 13. OB 12,14 1
157 12.23 Viscosity (40℃, C9k)
1270 1461 140.4+2! , 3 1
2L5 125.9 Viscosity Index
88 77 83,5 88 85.5 85(
1) Lubrication with the crude oil described in Example 11 (actual button [1 number (2) point 371'C (700°F) or higher]
1 distillate comparison example? Using the same catalyst as the Ni-containing H-type zeolite catalyst used in Comparative Example 5, a lubricant base oil fraction with a clear point range of about 260°C (500'F) to about 454°C (850'F) was heated for 18 days.
Reaction temperature from 300°C to 340°C, 1, IV/H/V (
7) Liquid hourly space velocity, 42 Kg/cm'G (7) Reaction pressure and 4501-H2/fL - Same feedstock as described in Example 11 after catalytic dewaxing under the reaction conditions of the feedstock. was subjected to catalytic dewaxing. The reaction conditions for catalytic dewaxing and the dewaxing results are shown in Table 12.

Table 12: Number of oil passing days: 0゛) Temperature (“0”) 340 38
0 400 Liquid space velocity (V/H/V)
1. l 1.1 1.1 Pressure (Kg/cryfG)
42 42 42 processing, f speed (
it-Hl/l-stock oil) 450 450 4
50 production extraction yield (wt% vs. age of raw material) 81.4 812
80.5 pour point (”0) −1
2,5-20-20 viscosity (100°C, cst)
1173 11.97 +2ρ4 viscosity (40
°C, cst) 109.0 +15
．． 9 11al viscosity index 8
5 91 92 (1), (2) Same as Table 11.

The results shown in Tables 11 and 12 show that the catalyst of the present invention allows a lubricant base oil fraction with a lower pour point to be obtained at a lower reaction temperature than with the catalysts of Comparative Examples 6 and 7. is clear.

[Brief explanation of drawings]

FIG. 1 is an X-ray diffraction pattern of a crystalline aluminosilicate synthesized by the method described in Comparative Example 1. Figure 2 shows a synthetic crystalline aluminosilicate (T) according to the present invention.
This is an X-ray diffraction pattern of SZ). Figure m3 is an electron micrograph of crystalline aluminosilicate synthesized by the method of Comparative Example 1. FIG. 4 shows the synthetic crystalline aluminosilicate (T) according to the present invention.
This is an electron micrograph of SZ). FIG. 5 is an X-ray diffraction pattern of a crystalline aluminosilicate synthesized by the method described in Comparative Example 5.

Claims (1)

[Claims] 1) Expressed by molar ratio of oxides: 0.8-1.5M_2_/_nO・Al_2O_3・1
having a chemical composition of 0-100SiO_2.0-40H_2O (where M is a metal cation and n is the valence of the metal cation), and at least the lattice planes shown in Table 1. A cation-exchanged crystalline aluminosilicate comprising a synthetic crystalline aluminosilicate containing hydrogen, ammonium or a rare earth metal and having a powder X-ray diffraction pattern indicative of spacing. ￥Table 1￥ Lattice Plane Spacing Relative Intensity ￥d(Å)￥￥(I/Io)￥ 11.2 ±0.2 S. 10.1 ±0.2 S. 7.5 ±0.15 W. 6.03 ±0.1 M. 4.26 ±0.07 M. 3.86 ±0.05V. S. 3.82 ±0.05 S. 3.76 ±0.05S. 3.72 ±0.05 S. 3.64 ±0.05 S. 2) 0.8-1.3M_2_/_n・Al_2O_3・25 expressed in molar ratio of oxide
-80SiO_2・ZH_2O (where M is at least one metal cation,
n is the valence of the metal cation, Z is 0-20
It is. ) and a powder X-ray diffraction pattern exhibiting at least the lattice spacing shown in Table 1. 3) In the chemical composition, M is an element in group I and II of the periodic table.
3. A crystalline aluminosilicate according to claim 1 or 2, which is at least one selected from the group of metal cations of the group A. 4) The crystalline aluminosilicate according to claim 3, wherein the metal cation of Groups I and II of the Periodic Table of Elements is at least one selected from the group of alkali metal ions and alkaline earth metal ions. salt. 5) The crystalline aluminosilicate according to claim 4, wherein the alkali metal ion and the alkaline earth metal ion are at least one selected from the group of sodium cations, lithium cations, and calcium cations. 6) The crystalline aluminosilicate according to claim 4, wherein the alkali metal ion is a mixture containing sodium cations and lithium cations. 7) The molar ratio of oxides is 0.8-1. 3Na_2O・Al_2O_3・25-8
Claim 1 having a chemical composition of 0SiO_2.0-20H_2O and having a powder X-ray diffraction pattern showing the lattice spacing shown in the table below.
Crystalline aluminosilicate as described in Section. Surface lattice spacing Relative intensity ￥d(Å)￥￥(I/Io)￥ 11.2 ±0.2 S. 10.1} ±0.2S. 9.9} ±0.2 M. 9.7 ±0.2 W. 7.5 ±0.15 W. 7.1 ±0.15 W. 8.4 ±0.1 M. 6.03 ±0.1 M. 5.58 ±0.1 M. 5.03 ±0.1 W. 4.62 ±0.07 W. 4.26 ±0.07 M. 3.86 ±0.05V. S. 3.82 ±0.05 S. 3.76 ±0.05S. 3.72 ±0.05 S. 3.64 ±0.05 S. 8) Expressed by molar ratio of oxides: 0.8-1.5 M_2_/_n・Al_2O_3・1
having a chemical composition of 0-100SiO_2.0-40H_2O (where M is a metal cation and n is the valence of the metal cation), and at least the lattice planes shown in Table 1. A method for producing a hydrogen ion-exchanged crystalline aluminosilicate comprising contacting a synthetic crystalline aluminosilicate with an acid having a powder X-ray diffraction pattern indicative of spacing. 9) Consisting essentially of inorganic reactive materials, having the following composition expressed by the following molar ratios: SiO_2/Al_2O_3 10-130 M_2_/_nO/SiO_2 0.03-0.5 H_2O/M_2_/_nO 100-1, 000 X^-/SiO_2 0.01-20 (where M is at least one metal cation,
n is the valence of the metal cation and X^- is the anion of the salt as a mineralizing agent. ), the reaction mixture is heated and maintained at a crystallization temperature until crystals form, and a crystalline aluminosilicate having a powder X-ray diffraction pattern exhibiting a lattice spacing at least as shown in Table 1 is prepared. A manufacturing method according to claim 8 for manufacturing salt. 10) The aqueous reaction mixture consists essentially of inorganic reactants and has the following composition expressed by the following molar ratios: SiO_2/Al_2O_3 20-120 M_2_/_nO/SiO_2 0.03-0.3 H_2O/M_2_/_nO 150-800 X^-/SiO_2 0.05-15 (where M is at least one metal cation,
n is its valence and X^- is the anion of the salt as a mineralizing agent. ) A method for producing a crystalline aluminosilicon salt according to claim 9. 11) The aqueous reaction mixture consists essentially of inorganic reactant materials and has the following composition expressed by the following molar ratios: SiO_2/Al_2O_3 30-115 M_2_/_nO/SiO_2 0.05-0.3 H_2O/M_2_/_nO 200-700 X^-/SiO_2 0.1-10 (where M is at least one metal cation,
n is the valence of the metal cation and X is the anion of the salt as mineralizing agent. ) The method for producing a crystalline aluminosilicate according to claim 10. 12) Claims 9, 10 or 11, wherein M in the aqueous reaction mixture is at least one selected from the group of metal cations of Group I and Group II of the Periodic Table of Elements. A method for producing a crystalline alumina silicate as described in Section 1. 13) The metal cation of Group I and Group II of the Periodic Table of the Elements is at least one selected from the group of alkali metal cations and alkaline earth metal cations, according to claim 12. Method for producing crystalline aluminosilicate. 14) The crystalline aluminosilicate according to claim 13, wherein the alkali metal cation and the alkaline earth metal cation are at least one selected from the group of sodium cation, lithium cation and calcium cation. Manufacturing method. 15) The method for producing a crystalline aluminosilicate according to claim 13, wherein the alkali metal cation is a mixture containing a sodium cation and a lithium cation. 16) Production of crystalline aluminosilicate according to claim 9, 10 or 11, in which the aqueous reaction mixture is kept at autogenous pressure and a temperature in the range of 120°C to 230°C is adopted as the crystallization temperature. Law. 17) After heating the aqueous reaction mixture to the crystallization temperature of 10
17. The method for producing a crystalline aluminosilicate according to claim 16, wherein heating is maintained for a period of time to 20 hours. 18) Claim 9, 10 or 18) wherein the mineralizing agent is at least one selected from the group of neutral salts of alkali metals and alkaline earth metals or at least one neutral salt of ammonium. 12. A method for producing a crystalline aluminosilicate according to item 11. 19) The crystalline aluminosilicate according to claim 18, wherein the neutral salt of alkali metal and alkaline earth metal is at least one selected from the group of sodium chloride, sodium sulfate, sodium carbonate and barium chloride. Manufacturing method. 20) The total oxide molar composition of the aqueous reaction mixture is 4Na
_2O・Al_2O_3・50SiO_2・2000H
_2O, contains 1.0 mol of NaCl as a mineralizer based on SiO_2, and crystallization conditions are about 170°C and about 2
12. The method for producing a crystalline aluminosilicate according to claim 11, which takes 0 hours. 21) Expressed by the molar ratio of oxides, 0.8-1.5M_2_/_n・Al_2O_3・10
-100SiO_2.0-40H_2O (where M is a metal cation and n is the valence of the metal cation) and has a lattice spacing at least as shown in Table 1. Synthetic crystalline aluminosilicate with a powder X-ray diffraction pattern showing NH_4^+
A method for producing a hydrogen ion exchange type crystalline aluminosilicate from a precursor substituted with 22) Expressed by the molar ratio of oxides, 0.8-1.5M_2_/_n・Al_2O_3・10
-100SiO_2.0-40H_2O (where M is a metal cation and n is the valence of the metal cation) and has a lattice spacing at least as shown in Table 1. A hydrogen ion exchange type crystalline aluminosilicate obtained by contacting a synthetic crystalline aluminosilicate having a powder A method for producing a crystalline aluminosilicate comprising increasing the silica/alumina ratio of the crystalline aluminosilicate.