JPS58194737A - Crystalline silicate and preparation thereof - Google Patents

Abstract

PURPOSE:To crystalline silicate, having a specific chemical composition, and utilizable as a highly selective catalyst for conversion reactions of various organic compounds or a separating adsorbent in mixture solutions or mixed gases. CONSTITUTION:A crystalline silicate in the dehydrated form having the chemical composition expressed by the formula [R2 are one or more monovalent or bivalent cations; n is the valence of R; M2 are one or more trivalent transition metal ions and/or Al ions; (a+b+c)=1; a>=0; b>=0; c>=0; (a+b)>0; Y>=12] expressed in terms of molar ratio of the oxides. The crystalline silicate is useful as a highly active and selective catalyst for conversion reactions of various organic compounds, e.g. synthetic reactions of aromatic hydrocarbon mixtures from methanol. The silicate has uniform 5-7Angstrom pore diameter, is capable of adsorbing organic compounds but scarcely adsorbs water. Therefore, the silicate can be used as a separating adsorbent for mixture solutions or mixed gases.

Description

[Detailed description of the invention] It is related to the manufacturing method.

Molecular sheep type crystalline zeolites are well known and important commercial products. As a group of compounds, molecular sheep zeolites consist of total aluminum and SiO and A10 bonded by covalent oxygen atoms such that the ratio of silicon atoms to oxygen atoms is 1 = 2; from a rigid three-dimensional network structure of tetrahedrons. It is an aluminosilicate. A10;
Tetrahedrons are usually balanced in valence by bonding with cations, which in most naturally occurring zeolites are alkali or alkaline earth metal cations;
Synthetic zeolites or those that have undergone ion exchange treatment can be essentially any metal cation, hydrogen, ammonium, or organic cation of appropriate atomic or molecular size.

In all of these zeolite compositions, hzo2
Tetrahedrons are crystallographically significant parts of the crystal structure and apparently contribute to the acidic character of the overall structure.

Until recently, it was not possible to synthesize zeolites with S102/Al203 ratios of 12 or more.

And natural zeolite is 12 or more S i O 2
/A/2o3 ratio. However, this problem has recently been overcome and high S 10 2 /A
A series of zeolites are now available that have a high l205 ratio, high stability, extremely high acidity points, and have catalytic ability for the conversion of methanol and other oxygenated organic compounds to aromatic hydrocarbons. Ta.

This is accomplished by adding organic cations such as tetraalkylammonium during zeolite synthesis.

For example, those containing quaternary ammonium as an organic cation (Japanese Patent Publication No. 46-10064, Japanese Unexamined Patent Publication No. 51-198)
6 7 2 9 8, 67 2 9 9), No. 3
Those containing a primary amine having 2 to 10 carbon atoms (Japanese Unexamined Patent Publication No. 1977-25097), those containing a primary amine having 2 to 10 carbon atoms
0-54598), those containing alcohol (Japanese Patent Application Laid-open No. 5
2-43800), those containing alcohol and ammonia (% 151600), those containing monoethanolamine, monopropanolamine or derivatives (
Methods using JP-A-54-1 07499) and those containing organic sulfur compounds (JP-A-54-1 37500) are known.

As mentioned above, zeolites are composed of a rigid three-dimensional network structure of S104 and A10λ tetrahedra bonded by covalent oxygen atoms, and the Alo″4 tetrahedrons are usually valently bonded by bonding with ion-exchangeable cations. is balanced to .

It is well known in conventional zeolite synthesis technology that Ge can be used instead of Si and Ga can be used instead of A/.

However, according to the research of the present inventors, 12 or more 810
When synthesizing zeolite with a ratio of 2/A/2oS, Aj
When La, Go, and other transition metal compounds are used instead of , it is possible to synthesize a regular porous crystalline silicate with a certain crystal structure, and when protonated, there is almost no A/. Nevertheless, it was found that the acidic points conventionally thought to originate from the A10'' tetrahedron exist in an amount corresponding to the number of atoms of La, Ce, and other transition metals.More surprisingly, in general, A significant change in catalyst performance was found by using the crystalline silicate obtained as described above instead of an aluminosilicate called zeolite.

For example, in the reaction of converting methanol and other oxygen-containing organic compounds into aromatic hydrocarbons, a conventional zeolite called ZSM-5 from Mopil Co., Ltd.
No. 10064, Japanese Patent Application Laid-open No. 52-8005), Duren (m
．． p. There is a problem that several percent of the temperature (79°C) is produced as a by-product. However, when the crystalline silicate obtained as described above was used, an epoch-making result was obtained in that aromatic hydrocarbons higher than Clo, such as durene, were hardly produced.

As a result, the generation of carbon was suppressed and the life of the catalyst was extended.

This phenomenon is caused by the fact that when the active site is considered to be around the A/ atom, most of A/ has been replaced by t, a, ce, and other transition metals, resulting in further substituent groups in the substituted aromatic. This is presumed to be because the increasing reaction and polycondensation reaction of aromatic hydrocarbons are suppressed.

The present invention has been made based on the above findings. (1) In the dehydrated form, expressed as the molar ratio of oxides, (tOfO,4)R2/rlO・[aLIL203・
bCe2o5・CM2O3]eyS102 and (2) a source of silica, a source of lanthanum and/or cerium, a source of transition metals and/or alumina, water and,
A reaction mixture containing a nitrogen- or oxygen-containing organic compound is formed, and the mixture is heated for a time and at a temperature that results in the formation of a crystalline silicate. )%/l, ratio 1 table 0
,.

(10±0.4)R2/. os(aLa2o3*bce
2o5saM2o,)eysio2-in the above formula, R:1
The present invention relates to a method for producing a crystalline silicate having a monovalent or more monovalent chemical composition.

The source of silica can be any silica compound commonly used in zeolite synthesis, such as solid silica powder, colloidal silica,
Alternatively, silicates such as water glass are used.

The source of lanthanum, cerium or transition metal is lanthanum,
Compounds such as sulfates, nitrates, and chlorides of cerium or transition metals are used.

In addition, the trivalent transition metal ion (M) in the present invention refers to group III elements such as iron, cobalt, rhodium, ruthenium, and palladium, rare earth elements other than lanthanum and cerium,
Refers to trivalent cations of the nanoelements titanium, vanadium, chromium, diopter, tantalum, and antimony.

The source of alumina is most preferably sodium aluminate, but compounds such as chlorides, nitrates, sulfates, oxides or hydroxides can be used.

As the alkali source, hydroxides of alkali metals such as sodium, alkaline earth metals such as calcium, or compounds with aluminic acid or silicic acid are used.

As the organic compound containing nitrogen or oxygen, which is one of the raw materials for hydrothermal synthesis of crystalline silicate, the following can be used.

(1) Organic amines;
secondary amines such as dipropylamine and jetanolamine, and tertiary amines such as tripropylamine and triethanolamine.
(2) Non-organic amines, such as ethylenediamine, diglycolamine, etc., or mixtures of the above compounds and halogenated hydrocarbons (propyl bromide, etc.), other tetraprobylammonium salts, natono-quaternary ammonium salts, etc. (3) Alcohols alone or in mixtures with ammonia; monoalcohols such as ethanol, diols such as ethylene glycol, or mixtures of the above alcohols and ammonia; various types of these; The organic compounds are merely examples, and the present invention is not equally limited thereto.

In addition, monovalent or divalent cations (R) in the present invention include alkali metal ions, alkaline earth metal ions, ions of the above-mentioned organic compounds, or hydrogen ions formed by treatments such as calcination and ion exchange. Point to ion.

The crystalline silicate of the present invention is one in which part or all of A/ in the structure of conventional zeolite is replaced with La, Cte or other transition metal, and further 5102/(
It is characterized by a ratio of La203+Cθ2o3+M20.5) of I2 or more, and is produced starting from a reaction mixture with the following molar composition.

5IO2/(La205+Cθ203+M2O5)JSulu6000(preferably 10-200)OH/5102
0-160 (preferably 0.2-0.8) H20/51
o22 to 1000 (preferably 10 to 200) Organic compound/(La20y, +c620s)+11 to 100 (preferably 5 to 50) The hydrothermal synthesis temperature is preferably 80 to 300°C, preferably 13°C.
The temperature range is from 0 to 200°C, and the hydrothermal synthesis time is 0.5
-14 days, preferably 1-10 days. The pressure is not particularly limited, but it is preferable to use autogenous pressure.

The hydrothermal synthesis reaction is continued by heating the raw material mixture to the desired temperature and stirring if necessary until crystalline silicate is formed. After the crystals are formed, the reaction mixture is cooled to room temperature, passed through the mouth, washed with water, and the crystals are separated. Further, drying is usually carried out at 100° C. or higher for about 5 to 24 hours.

The crystalline silicate produced by the above-mentioned method can be molded into an appropriate size as it is or mixed with a binder etc. conventionally used for catalyst molding, using well-known techniques, and used as a catalyst. can be used.

The crystalline silicate of the present invention is a regularly porous crystalline material having a certain crystal structure and generally exhibits the X-ray diffraction pattern shown in Table 1.

Table 1 Standard techniques were used to obtain the data in Table 1 above.

The irradiation is copper Ka rays. Engineering. is the intensity of the strongest peak, I/I. is the relative intensity.

The data in Table 1 above is different from the data for ZSM-5 described in Japanese Patent Publication No. 10064/1983.

Preferably, the crystalline silicate is activated by heating in air at a temperature ranging from 400 to 700'C for 2 to 48 hours before use as a catalyst.

The alkali metals present in this crystalline silita tuft may be exchanged with one or more other cations by conventional methods to give crystalline silicates in the H form or other metal cation forms such as iron, rhodium, ruthenium, potassium, etc. . For example, as a method for ion exchange to H type, by firing the crystalline silicate produced by the method described above,
After removing the organic compound, it can be immersed in a strong acid such as hydrochloric acid to directly convert it into the H type, or it can be immersed in an aqueous solution of an ammonium compound to form the NH4 type, and then fired to form the H type.

Furthermore, the crystalline silicates can be impregnated with one or more metal compounds for catalytic purposes. Suitable metals include copper,
Included are zinc, chromium, lead, antimony, bismuth, titanium, vanadium, manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium, platinum, lanthanum, or cerium.

The impregnated silicate preferably contains 0.1 to 5.0 weight percent metal oxide. The metal compounds used are precisely those compounds which decompose on application of heat to give the corresponding oxides and which are soluble in water, such as nitrates or chlorides. Mixtures of crystalline silicates and metal oxides are thus prepared by impregnation with an aqueous solution of the compound of the desired metal and dry calcination. .

The catalyst obtained in the above manner can be used for reactions such as polymerization, alkylation, isomerization, and disproportionation of organic compounds, especially for converting aromatic compounds or lower olefins from alcohols or ethers, as shown in the examples below. It exhibits high catalytic activity for the synthesis reaction that conventional catalysts do not have.

The crystalline silicate of the present invention has extremely high catalytic activity for organic reactions using carbonium ions as intermediates. The reaction generally involves heating an organic compound or a raw material containing an organic compound at a temperature of 408C to 700C at 200C.
pressure below atm, and 0.1 h-'~1000
It may be brought into contact with the crystalline silicate-containing catalyst of the present invention at a weight hourly space velocity of h-1 (hereinafter abbreviated as WH8V).

More specifically, when the conversion involves polymerization of an olefin-containing feedstock, the temperature is 260°C to 500°C, the pressure is 5 Q atm or less, W, H, S, V.

is 0.5h to 50h. When the conversion reaction is alkylation of an aromatic compound such as benzene or toluene with an olefin or alcohol, the reaction conditions are a temperature of 200°C to 550°C, a pressure of 60 atm,
0.5h ~ 50h-1 W, H, S, VL, 2
The aromatic compound/alkylating agent molar ratio is ˜200.

When the conversion is an isomerization of an aromatic compound such as xylene, the reaction conditions are a temperature of 150° C. to 500° C., a temperature of 60° C.
Pressure below atm, W of 0.2 h-' ~ 100 h
, H, S, and V. When the conversion is isomerization of paraffins or olefins, the reaction conditions are from 40°C to 400°C.
°C, pressure below 60 atm, 0.1 h"" ~ 20
．． h”-177) There are W, H, S, V Te.

When the conversion is a disproportionation of an aromatic compound such as toluene, the reaction conditions are a temperature of 300° C. to 600° C., a temperature of 0.5
h"" ~20 N' 17) There are W, H, S, V, and Te.

Furthermore, the crystalline silicate of the present invention can also be used in a contact membrane wax that takes advantage of its shape selectivity. The reaction conditions in this case are a temperature of 200 to 500°C and a temperature of 100 at.
m or less pressure, 0.1 to 20 h W, H, S, V,
It is.

Furthermore, the crystalline silicate of the present invention has extremely high activity in the reaction of synthesizing aromatic compounds or lower olefins from alcohols or ethers, and the reaction conditions in this case are a temperature of 300 to 600 °C, a temperature of 100 °C Pressure below ATM, 0.1h to 200h W, H, S,
V.

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Crystalline silicate was synthesized as follows.

Water glass, lanthanum chloride, cerium chloride, water at 36N
a2O@(0,5La203-0.506203)-8
08iO281600H20, then add an appropriate amount of hydrochloric acid to the mixture so that - is around 9, and then add propylamine and propyl bromide as organic compounds to the total number of moles of La205ICe203. 20 times as much, mixed well, and placed in a 500cc stainless steel autoclave.

While stirring the above mixture at about 500 rpm,
The reaction was carried out at 0°C for 5 days. After cooling, the solid content was filtered by 1, washed thoroughly with water until the - of the washing water became about 8, and heated at 110°C for 12
It was dried for an hour and fired at 550°C for 3 hours.

The crystal grain size of this product is around 1μ, and the composition excluding organic compounds is expressed in dehydrated form as follows: 0.4 Na20-(0,5La203-0.5C62
05)-80SiO2. This is called crystalline silicate 1.

When synthesizing this crystalline silicate 1, the same results can be obtained even if nitric acid is used instead of hydrochloric acid among the raw materials, lanthanum nitrate is used instead of lanthanum chloride, or silica sol is used instead of water glass. silicate was obtained.

Furthermore, similar silicates were obtained by reacting at 170°C or 180°C for 2 days instead of at 160°C for 5 days as the hydrothermal synthesis conditions.

Repeat the same operations as for crystalline silicate 1, except that the amounts of lanthanum chloride and cerium chloride added when preparing the raw materials for crystalline silicate 1 were converted into the molar ratio of LaO and Ce2O33 and changed as shown in Table 2. , 'l to prepare crystalline silicates 2 to 6 as shown in Table 2.

When preparing crystalline silicate 6, instead of cerium chloride, ferric chloride, ruthenium chloride, neodymium chloride, titanium chloride, vanadium chloride, quam chloride, antimony chloride, or aluminum chloride was used as Ce in terms of oxide.
Crystalline silicate 7-16°24 was prepared by repeating the same operation as crystalline silicate 6 except that the same number of moles as 2O3 was added. The composition of these crystalline silicates excluding organic compounds is expressed as the molar ratio of oxides (dehydrated form): (0,3-0.5)Na20-(0,9La205-0
．． 1M203)-80SiO2. Here M is F
e* Ru z N d e T i # V y
CrH5blAI! (Crystalline silicate 7-15.2
4).

The procedure for preparing crystalline silicate 1 was repeated, except that instead of propylamine and propyl bromide in crystalline silicate 1, the organic compound shown in Table 3 was added 20 times the number of moles of lanthanum oxide, and the crystallinity shown in Table 3 was obtained. Silicates 14-22 were prepared.

Table 3 The compositions of these crystalline silicates 14 to 20 excluding organic compounds are expressed as molar ratios of oxides (dehydrated form): (0,1 to 0.6) Na20/(0,5La203/0
．． 5Ce205)・80S102.

In addition, in crystalline silicate 2, S 102 at the time of preparation
/ La 205 ratio to 20. ．． 200 or 240
The same operation as for crystalline silicate 2 was repeated except that the powder X-ray cycle W patterns of crystalline silicate 2, 1, and 22° or more of crystalline silicate 1 to 23 satisfied the patterns shown in Table 1. The content of 5102 is 90
It was confirmed that it was a crystalline material with a weight percent or more.

Comparative Example In Example 1, using aluminum chloride instead of lanthanum chloride and heptasum chloride, and keeping the other inorganic compounds the same, 36 Na O@A/203-805in2e 160
0 H2O2 molar ratio, and an appropriate amount of hydrochloric acid was added to this to make the - of the above mixture around 9. Tetrapropylammonium bromide was mixed with At2 as an organic compound.
The same operation as in Example 1 was repeated except that 0.3020 times the amount was added.

The composition of this product excluding organic compounds, expressed as the molar ratio of oxides (in dehydrated form), is '10.
5 Na2O"A/203s805in2, the X-ray pattern of this powder was

23M - described in Publication No. 10064/1983
5 (hereinafter, the product obtained in this comparative example will be referred to as ZSM-5).

Example 2 The crystalline silicate synthesized in Example 1 and the zeolite ZSM-5 synthesized in Comparative Example were immersed in 1N hydrochloric acid.
It was treated at 0°C for 7 days. After washing this through the mouth, 110
Catalysts (1-3
(molded to the proverbial size) was used to react with methanol.

The reaction conditions were normal pressure, 370°C, L, H, S, V, (liquid hourly space velocity) 2 h-', and the results shown in Table 4 were obtained.

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4? r qQ, n 'y to 6't'? 1,)'? /
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Example 3 Using a catalyst in which the crystalline silicate 1 synthesized in Example 1 was activated in the same manner as in Example 2, experiments were conducted on the reactions shown in Table 5, and the results shown in Table 5 were obtained.

As is clear from the above examples, the crystalline silicate of the present invention is a highly active and highly selective catalyst for the synthesis reaction of aromatic hydrocarbon mixtures from methanol and the conversion reactions of various organic compounds. It is.

In the examples, the case where crystalline silicate is used alone is described, but it is also possible to use it in combination with a binder etc. that has been conventionally used for catalyst molding. It goes without saying that a commonly used ion exchange treatment or the like may be performed to improve the performance.

In addition, the crystalline silicate of the present invention has properties such as having a uniform pore diameter of 5 to 7A and adsorbing organic compounds but hardly adsorbing water. It is also possible to use it as an adsorbent for separating mixed liquids or mixed gases.

Continued from page 1 0 Inventor: Minoru Koikeda 1625-43 Kamigo-cho, Totsuka-ku, Yokohama @ Inventor: Takashi Suzuki No. 15, Nishikigaoka, Kohoku-ku, Yokohama City Procedural Amendment (Method) S. 70, 1982 Kazuo Chikusugi, Commissioner of the Japan Patent Office, 1. Indication of the case, Patent Application No. 173455 of 1982, 2. Title of the invention, Crystalline silicate and its manufacturing method 3. Person making the amendment. Relationship with the case. Patent applicant. Address: 1-4-2-4 Uchikanda, Chiyoda-ku, Tokyo, Agent II, % #4, 24-11 Toranomon-chome, Minato-ku, Tokyo
M book a supplement oP1s.

(1FK unchanged) Title of the invention Crystalline silicate and method for producing the same 2-% Scope of evacuation (1) In dehydrated form, expressed as molar ratio of oxides (10 soil a4) VoOs(al, am On” bC
@@Os @CMbOs 3”yS to.

A crystalline silicate with the chemical composition of

(2I Silica supply, lanthanum and/or cerium supply, 11111s metal and/or τ lumina vessel-1
Preparing a reaction mixture containing water and a compound containing 11 or 100% silicic acid, this mixed VM crystalline silicate is formed over a period of time and recombinantly added. In form IIA, expressed as the molar ratio of llide;
i ” bC @ x Oi・CI M x o s )
B10° In the above formula, R: 1111 or more monovalent or divalent cation n: R atom - M: 1t! II or higher 5iIIItl transition metal ions and/or aluminum ions a+b+o嘗1 1>O b>.

O>O Head +-〉0 A method for producing a crystalline silicate having a chemical composition of

3.Details of the Invention The present invention relates to a Wfr-like crystalline silicate and a method for producing the same.

Molecu 2 soap type crystalline zeolite is well known and an important commercial product. As a group of compounds, if Molecular Sieve Zeolite Co., Ltd. all-aluminum, 5i04 and Ato are bonded by covalent bonding of key atoms such that the ratio of silicon atoms to oxygen atoms is 1=2; from a rigid three-dimensional network structure of tetrahedrons. It is an aluminosilicate. Ato;
Tetrahedrons are usually valence-balanced by bonding with cations, and the cations are alkali or alkaline earth metal cations in most naturally occurring zeolites, but in synthetic zeolites or ionic exchange treatments. Essentially any metal cation, hydrogen, ammonium, or organic cation of suitable phosphatide or molecular size can be used.

I used 1 go, Deeren etc.G. It was hoped that there would be no such aromatic hydrocarbon islands that would be introduced in the 51st century. As a result, the generation of carbon was suppressed, and the internal life of the probe was also improved.

In such a combination, if the active atom is considered as the mulberry atom, the addition of substituted aromatic additives will occur due to the change of the mulberry metal to LJO@ and other transition gold-K. #1
This is thought to be due to the suppression of the reaction that increases the amount of gas and the 1-combination reaction of the hydrocarbon molecules.

This was made based on these 5 findings.
,O,*oM,O,)ayam0゜In the above formula, R: 1-
or more than 1s11 or 2 cations n * l I) ill - M21alJ (is more than 5IilAl) (2) source of strength, lanthanum and/or source of ts9m, transition metal and/or l Lumi 1 -1 water resistance and an organic compound containing seed wood or #! element - a reaction mixture containing all v
l, and this mixed capital kkN crystal injection soligate is generated r
In the dehydrated form, heating for a time and degree of eccentricity of %-, expressed as a molar ratio of oxides, (10+14)H,〈i+)*LaLa,t)
,,* bcelol・cMaOsJ・ydiol “1
In the formula, O relates to a method for producing a crystalline silicate having a one-layer chemical composition in which R=1 tank or more.

Source of Silica: Any silica O compound commonly used in Hiro zeolite synthesis may be used, such as solid Hina silica powder, colloidal silica,
Alternatively, silicates such as water glass are used.

The source of lanthanum, yariram or transition metals is not limited to the number of ships produced by the #4 companies.

1*, monovalent or divalent cation (R) in the present invention! :
It refers to ions such as a, alkali metal ions, alkaline earth metal ions, ions of the nine organic compounds mentioned above, or hydrogen ions formed by treatments such as calcination and ion exchange.

The crystalline silicates of the present invention are those in which part or all of the kA in the conventional zeolite) O structure is wrinkled into La, Co, or other transition regions, and furthermore, the
(La103 + Ce!O + MtOs) It is produced starting from a reaction mixture with the following molar composition, with the ratio being 12 or more.

8 iol / (La2O3+ Ce1O1+ Pigeon 01
)12~! $000 (preferably 20-200) OH
”/81O10~to (preferably (12~(La
) HIO/8tO12-1000 (preferably 10
~200) Organic compound/tLa, om+c@to,
) 1 to 100 (preferably 5 to 50) The crystalline silicate of the present invention is prepared by heating the raw material mixture at a temperature sufficient to form a crystalline silicate, and then -hk showing the In the case of ζO, the reaction conditions are 500-600
Ct) temperature, pressure below 100 atm, LLlh
~200h ON, H, 8, V.

Hereinafter, the present invention will be specifically explained with reference to Examples.

implementation? I11 Crystalline silicate was synthesized as follows.

Water glass, lanthanum chloride, cerium chloride, water at 56N
a1O” (CLS La10B”α5CelO1) @8
Ω8i0. -1600H,00 molar ratio, add an appropriate amount of hydrochloric acid to this, and adjust the pH of the mixture to 9.
After that, add propylamine and propyl bromide as organic compounds 20 times the total number of moles of La2O3 and Ce1O@, mix well, and
It was placed in a stainless steel autoclave.

While stirring the above mixture at about 50 OrpmWc,
The reaction was carried out at 0°C for 5 days. After cooling, the solid content was filtered, thoroughly washed with water until the OpH of the washing water became approximately 8, and then heated at 110°C for 1
Dry for 2 hours and bake at 550°C for S hours to form a circle.

Table 5 The composition excluding these OM crystalline silicate 14-2o6 organic compounds is expressed as the molar ratio of oxides (dehydrated form -) (a1-(L4)Na10s(α5La103*α5
Ce10B)-808101 and nine.

In addition, in crystalline silicate 2, El 10H at the time of preparation
/La t 08 ratio to 20,200 or 400
Except for Toshie, crystalline silicate 21, 22 and 25 were prepared by repeating the same procedure as for crystalline silicate 2.

The powder X-ray diffraction patterns of the above crystalline silicates 1 to 25 satisfy the A-turn shown in Table 1), and the content of 8i02 is 90 or more cents i<- cents. My friend who is with me.

Comparative Example In Example 1, using aluminum chloride instead of lanthanum chloride and cerium chloride, and keeping the other inorganic compounds the same, 56Na10.AA, O, .80Si01.16001
(The mixture was prepared in such a way that the ratio was 0, and hydrochloric acid was added in excess to make the OpH of the mixture 911 tlfflK. Then, as an organic compound, tetrapropylammonium bromide was added 20 times that of A401. Repeat the same operation as in Example 1.

The composition of this product, excluding organic compounds, is α5 Na1O'A40 expressed in molar ratio of oxides (in dehydrated form).
g” 808i01 and nine.
The turn is the same as that of ZSM-5 described in Japanese Patent Publication No. 46-10064 (hereinafter, the model obtained in this comparative example will be referred to as ZSM-5).

Run 112 1 ml of 1N salt of 9 crystalline phosphate synthesized in Run 991 and 9 zeolite 28M-5 synthesized in Comparative Example! Soaked in water and treated at 80℃ for 7 days. After passing through a washing port, it was dried at 110° C. for 12 hours and reacted with methanol using a catalyst (1 to 5 cm in size) calcined at 550° C.

The reaction conditions were normal pressure, 570°C, L, n, s, v, (g
(space velocity) 2 h'', and the results shown in Table 4 were obtained.

Claims (2)

[Claims] (1) In the dehydrated form, expressed as the molar ratio of oxides (1,0±04)R2/7nO・[aLa205・bC
A crystalline silicate having a chemical composition of e203.CM2O3]oySlo2. (2) a source of silica, a source of lanthanum and/or cerium, a source of transition metals and/or alumina, water and
In a dehydrated form, characterized in that a reaction mixture containing nitrogen or oxygen-containing organic compounds is prepared and this mixture is heated for a time and at a temperature that results in the formation of crystalline silicates, in a molar ratio of oxides. Express (1, discharge04]R2//rlo・[aLa203・bC
A method for producing crystalline silicate having a chemical composition of e203.CM2O3].yS102.