JPS6366772B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel crystalline aluminosilicate zeolite and a method for producing the same. More specifically, the present invention relates to a new zeolite having a crystal structure different from conventionally known crystalline aluminosilicate zeolites and a method for producing the same. In this specification, unless otherwise specified, crystalline aluminosilicate zeolite will be simply referred to as zeolite. Zeolites are natural or synthetic
It contains cations such as Na, K or hydrogen ions, and has a three-dimensional network structure mainly composed of SiO ₄ and AlO _4. SiO ₄ and AlO ₄ are tetrahedral cross-linked through O. It is characterized by having a highly arranged structure. This crystalline zeolite is uniform in size and has an extremely large number of pores, and is used as a molecular node, and is also used as a catalyst or carrier in various synthetic fields. In particular, synthetic crystalline zeolite is extremely uniform, highly pure, and has excellent properties. Therefore, many synthetic zeolites and methods for producing the same have been proposed. For example, so-called silica-rich crystalline zeolites with a SiO ₂ /Al ₂ O ₃ ratio of at least 10 have high stability and high acidity, and are suitable for selective adsorption, for example.
Cracking, hydrocracking, isomerization,
It has high activity as a catalyst for hydrocarbon conversions such as alkylation. Many crystalline zeolites with a high silica content have been proposed, mainly ZSM-based zeolites. Crystalline zeolite with a high silica content is produced by the action of alkali metal cations and other cations used in combination with silica sources and alumina sources, but it can also be obtained by using other types and combinations of cations. The structure and properties of crystalline zeolites are different. Conventionally, as other cations used in combination with alkali metal cations, specific quaternary ammonium has been used (for example, Japanese Patent Publication No. 10064/1980, Japanese Patent Application Laid-Open No. 67298/1983, Japanese Patent Application Laid-open No. 51-6729). 67299
(see Japanese Patent Application Publication No. 1987-25097), those using tertiary amines (see Japanese Patent Application Laid-open No. 47-25097),
There are known methods that use a class amine (see JP-A-50-54598), and those that use an alkyldiamine having 2 to 20 carbon atoms (see JP-A-53-134799). As a result of our research on new zeolites and their production methods, the present inventors have discovered that when a certain quaternary ammonium ion is used in combination with an alkali metal cation, a crystalline zeolite with a completely different structure from that of conventional zeolites can be produced. It has been found that the zeolite obtained is stable and homogeneous and has excellent activity in the conversion of certain hydrocarbons. That is, the present invention is based on the following formula (1) M _2/o O.Al _{2 O 3} . One or more valent cations, X represents 10 or more. ] It is a crystalline aluminosilicate zeolite having a composition represented by the following and an X-ray lattice spacing substantially represented by the following values. In the present invention, such zeolite is referred to as TPZ-2. According to the present invention, the crystalline aluminosilicate zeolite is a composition containing an alkali metal ion source, an organic nitrogen-containing cation source, a silica source, an alumina source, and water, each component being expressed in molar ratio. Below, SiO ₂ /Al ₂ O ₃ = 10 or more R / (Si + Al) = 1 × 10 ^-4 ~ 1 OH ^{- /} (Si + Al) = 0.1 ~ 0.5 H ₂ O / (Si + Al) = 5 ~ 100 OH ^- / H ₂ O = 1 × 10 ^-3 ~ 1 × 10 ^-1 [However, R in the formula is the general formula R ₁ R ₂ R ₃ N+ (CH ₂ ) mN+
R ₄ R ₅ R ₆・2X ^- and (m is 2 or 3, R ₁ to _{R 6} are the same or different alkyl groups having 1 to 4 carbon atoms, but one of them may be a hydrogen atom, X is a halogen atom) ammonium ion based on an organic nitrogen-containing cation source selected from the group OH ^-
represents an alkali metal ion and a hydroxyl group based on the ammonium ion of R. ] can be obtained by maintaining a composition in the range of 80° C. or higher for a sufficient period of time to form crystals. Such crystalline zeolite (TPZ) according to the present invention
-2) is a zeolite with a high silica content, and is a zeolite with a high silica content, which is the conventionally known ZSM-5, ZSM-11, ZSM-
12. It shows a completely different X-ray diffraction pattern from ZSM-based zeolites such as ZSM-38 and Zeta 3 type zeolite, and its characteristics are also different. The method for producing crystalline zeolite according to the present invention and the characteristics of the zeolite will be explained in detail below. Crystalline zeolite (TPZ) which is the object of the present invention
As mentioned above, 2) is a composition containing an alkali metal ion source, an organic nitrogen-containing cation source, a silica source, an alumina source, and water, and each component is expressed in molar ratio as follows: SiO ₂ / Al ₂ O ₃ = 10 or more R / (Si + Al) = 1 × 10 ^-4 ~ 1 OH ^{- /} (Si + Al) = 0.1 ~ 0.5 H ₂ O / (Si + Al) = 5 ~ 100 OH ^- /H ₂ O = 1 × 10 ^-3 to 1 x 10 ^-1 [However, the definitions of R and OH ^- in the formula are the same as above] By maintaining the composition at a temperature of 80 ° C. or higher for at least a sufficient time to form crystals. Manufactured. The silica source may be any one commonly used in zeolite production, such as silica powder colloidal silica, dissolved silica, silicic acid, and the like. To explain these specific examples in detail, as the silica powder, precipitated silica produced by a precipitation method from an alkali metal silicate group such as aerosil silica, fuming silica, and silica gel is suitable;
Colloidal silica can be used in various particle sizes, for example, from 10 to 50 microns. Also, as dissolved silica, Na ₂ O or K ₂ O1
Examples include water glass silicates, alkali metal silicates, silicates obtained by dissolving silica in alkali metal hydroxides, containing 1 to 5 mol, especially 2 to 4 mol, of SiO ₂ per mole. However,
Among these, colloidal silica is preferred. The alumina source may be any one commonly used in the production of zeolites, such as aluminum salts such as chlorides, nitrates, and sulfates; for example, colloidal alumina, pseudoboehmite,
Boehmite, γ-alumina, α-alumina, β-
Examples include alumina in a hydrated or hydrateable state such as alumina trihydrate; sodium aluminate, among which sodium aluminate or aluminum salts are preferred. Further, part or all of the alumina source may be used as an aluminosilicate compound as shown in the silica source described above. The ratio of the silica source to the alumina source in the raw material mixture of the present invention is such that the SiO ₂ /Al ₂ O ₃ (molar ratio) is 10 or more, expressed as SiO ₂ and Al ₂ O ₃ , respectively;
Particularly preferred is a range of 10 to 1000. On the other hand, the alkali metal is preferably added in the form of a salt readily soluble in water or in the form of a hydroxide. As the alkali metal cation source, for example, sodium hydroxide, potassium hydroxide, sodium or potassium aluminate, sodium or potassium silicate are added, and it is especially effective that the alkali metal is sodium. And desirable. In the present invention, the source of ammonium ions (R) used together with the alkali metal ions has the general formula R ₁ R ₂ R ₃ N + (CH ₂ ) mN + R ₄ R ₅ R ₆ .
2X ^- and (m is 2 or 3, R ₁ to _{R 6} are the same or different alkyl groups having 1 to 4 carbon atoms, but one of them may be a hydrogen atom, X is a halogen atom) An organic nitrogen-containing compound selected from the group consisting of: The source of such ammonium ions (R) is preferably N, N, N, N', N',
N'-hexaalkyl-1,2-ethanediammonium, N,N,N,N',N',N'-hexaalkyl-1,3-propanediammonium or N,N,N,N',N ',N'-hexaalkylphenylmethane ammonium or a combination of two or more thereof can be used, especially N,N,N,
N',N',N'-hexaalkyl-1,3-propanediammonium is preferred. The alkyl group forming these ammoniums has 1 to 1 carbon atoms.
4, preferably 1 to 2. Preferred examples include N,N,N,N',N',N'-hexamethyl-1,2-ethanediammonium, N,
N, N, N', N', N'-hexamethyl-1,3-
Propanediammonium or N, N, N, N',
N′,N′-hexamethyldiphenylmethane ammonium is mentioned. The ammonium in the present invention does not necessarily need to be mixed with the raw material mixture and used, but a compound that forms such ammonium in the raw material mixture may be added to form the diammonium in the mixture. You may let them. For example, NNN′N′-tetraalkyl 1,3-
An alkylating agent such as propanediamine and an alkyl halide may be added and these may be reacted with each other to form N,N,N,N',N',N'-hexaalkyl-1,3-propanediammonium. good. The molar ratio of such diammonium (R) to the sum of silica and alumina (expressed as Si+Al) is in the range of 1×10 ^-4 to 1, preferably 5×
10 ⁻⁴ to 0.5, particularly preferably 1×10 ⁻³ to 1
It is appropriate to use the range of ×10 ^-1 . Furthermore, in the raw material mixture of the present invention, the ratio of hydroxyl groups (OH ^- ) based on alkali metal ions and ammonium ions is in the range of 0.1 to 0.5 in molar ratio to (Si + Al), preferably 0.15.
A range of ~0.45 is advantageous. Further, the molar ratio of hydroxyl groups (OH ^- ) based on alkali metal ions and the diammonium ions to water in the raw material mixture is in the range of 1 x 10 ^-3 to 1 x 10 ^-1 ,
It is desirable to control the amounts of water and cations so that they are preferably in the range of 1 x 10 ^-3 to 1 x 10 ^-2 . Furthermore, in the raw material mixture in the present invention, the molar ratio of water to (Si + Al) is in the range of 5 to 100,
It is preferable to use a range of 10 to 50, especially
A range of 15 to 40 gives favorable results. In the present invention, the alkali metal ion source, organic nitrogen-containing cation (R), silica source, alumina source, and water as described above are used as a raw material mixture in the proportions as described above, and the mixture is used to form crystalline zeolite. The reaction temperature is preferably maintained at a temperature and for a period of time sufficient to achieve this reaction, and the preferred reaction temperature is 80°C or higher, with 100 to 200°C being particularly advantageous. The reaction time is usually 5 hours to 100 days, preferably 10
time to 50 days, particularly preferably 1 day to 7 days,
The autogenous pressure or higher pressure is applied, and it is generally carried out under the autogenous pressure, but it may also be carried out under an inert gas atmosphere such as nitrogen gas. The reaction for forming crystalline zeolite is continued by heating the raw material mixture to the desired temperature and, if used, under stirring until crystalline zeolite is formed. After crystals have thus formed, the reaction mixture is cooled to room temperature and filtered, e.g.
Wash with water until the crystals are less than / cm and separate the crystals.
Furthermore, if necessary, the crystals may be dried at room temperature or under normal pressure or reduced pressure, for example, at 50 DEG C. or higher for about 5 to 24 hours. In the thus obtained crystalline zeolite, the cations are composed of alkali metal ions and organic nitrogen-containing ions, and for example, it is possible to exchange ions with an aqueous NH ₄ Cl solution and replace the cation sites with ammonium ions. can. The crystals thus obtained may be calcined at a temperature of 100 to 600°C, preferably 300 to 500°C, for 8 to 24 hours, preferably 8 to 16 hours, and this calcination is also included in the present invention. The present invention provides an alkali metal ion, a divalent ammonium ion, or a monovalent ion in crystalline zeolite.
It also includes a method of ion-exchanging some or all of the valent ammonium ions with at least one other cation. Examples of ion-exchangeable cations include monovalent cations such as lithium, silver, and ammonium; divalent alkaline earth metal cations such as magnesium, calcium, and barium, and trivalent cations such as aluminum;
Group metal ions such as cobalt, nickel, platinum, palladium; cations of rare earth metals may also be used. Rare earth metals include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terebrium, scandium, yttrium, and the like. In the case of exchanging the various cations, conventional methods may be used, and the crystalline zeolite may be contacted with a water-soluble or water-insoluble medium containing an aqueous solution containing the desired cation.
Such contact treatment can be accomplished either batchwise or continuously. By performing the above-mentioned ion exchange, the crystallinity of the crystalline zeolite of the present invention may be increased, and the activity may be improved. Prior to performing the above-mentioned crystalline zeolite formation reaction, if powder particles of crystalline zeolite, which is the target product, are present in the raw material mixture, not only will the zeolite formation reaction rate be increased, but also the particle size will be large. Zeolite is obtained. Therefore, it is often desirable to mix powder particles of the desired crystalline zeolite into the raw material mixture. The crystalline aluminosilicate zeolite (TPZ-2) thus obtained according to the present invention exhibits a characteristic X-ray diffraction lattice, as is clear from the examples shown below, and is resistant to xylene isomerization and transalkylation. Shows effective activity as a catalyst. Furthermore, the crystalline zeolite of the present invention can also be used as a catalyst for the synthesis of xylene by a disproportionation reaction of toluene or a methylation reaction of toluene using a methylating agent. Thus, the crystalline zeolite (TPZ-
2) is the following formula (1) M _2/o O・Al ₂ O ₃・XSiO ₂ ...(1) [However, the formula is expressed in the form of an oxide in an anhydrous state, and M is one or more cations, X represents 10 or more. ] and has an X-ray lattice spacing substantially represented by the following values: 4.27±0.1 4.10±0.05 3.90±0.05 2.50±0.03. As described above, the crystalline zeolite of the present invention has a characteristic X-ray diffraction pattern and is clearly distinguished from conventionally known zeolites with a high silica content. The characteristic peaks of the X-ray lattice spacing of the crystalline zeolite of the present invention are as described above, and the strengths and weaknesses of each peak are as follows. 4.27±0.1 Strong 4.10±0.05 Very Strong 3.90±0.05 Moderate 2.50±0.03 Moderate These values were determined by standard techniques. The irradiation beam was a copper Kα twin beam, and a self-recording scintillation counting spectrophotometer was used. The peak height ( ) and 2θ (θ is the black angle) were read from the spectrophotometer chart. From this relative strength
100×/ ₀ ( ₀ is the height of the strongest line or peak)
and d(observed), the lattice spacing in Angstroms corresponding to the recorded lines, was calculated. As long as the characteristic peak of the X-ray lattice spacing is substantially observed, the zeolite falls within the scope of the present invention. In addition, the X-ray diffraction diagram of the zeolite of the present invention includes:
In some cases, many weak peaks may be observed in addition to the above-mentioned peaks, but the presence or absence of these peaks does not essentially affect the identification of the zeolite of the present invention. It should be noted that the characteristic peak of the X-ray lattice spacing is characteristic of all varieties of crystalline zeolites of the present invention. Replacing sodium ions with other ions causes a slight shift in the lattice spacing,
It was found that they showed essentially the same pattern, with only small changes such as slightly different relative intensities. The zeolite of the present invention has _the following chemical formula (1) M _{2/o O.Al 2} O 3 Yes, M represents one or more n-valent cations, and X represents 10 or more. ] In the above formula (1), X is 10 or more, preferably 10 to
A value in the 1000 range is particularly preferred since it provides a zeolite with excellent properties. M represents one or more n-valent cations, and the cations include hydrogen ions, ammonium ions, alkali metal ions, organic nitrogen-containing ions, alkaline earth metal ions, and group metals of the periodic table. The ion may be one or a mixture of two or more of ions, rare earth metal ions, and other metal ions. Particularly preferred are those containing at least one of hydrogen ions, group metal ions, and rare earth metal ions, as they have various interesting activities, and those containing group metal ions are particularly preferred for reactions such as hydrocarbon conversion. It can be advantageously used as a catalyst. Furthermore, the zeolite of the present invention may support other metals or metal oxides in a physically mixed state. The crystalline zeolite of the present invention is stable and uniform, and has excellent characteristics, so it can be used in various fields. For example, even if heat treated at 800° C. for 12 hours or more, the X-ray diffraction pattern described above does not substantially change, which in itself is understood to be extremely thermally stable. Further, the crystalline zeolite of the present invention is extremely porous and has excellent shape selectivity depending on the pore size. Furthermore, the crystalline zeolite of the present invention can be used, for example, for isomerization, disproportionation, alkylation of alkylbenzenes,
It has excellent properties as a catalyst for hydrocarbon transformations such as transalkylation, and as a selective adsorbent. The present invention will be described in detail below with reference to Examples. Example 1 To 800 ml of an ethanol solution of 25 g of N,N,N',N'-tetramethyl-1,3-propanediamine,
Add 70 g of methyl iodide. It generates a gentle heat for about 3 hours and a precipitate is formed, but the light is blocked and it continues for about 1 hour.
Continue stirring for days. The white powder produced is divided into three parts,
After washing with acetone and drying under reduced pressure, N,N,N,N',N',N'-hexamethyl-1,3-propanediammonium salt was obtained almost quantitatively. 100 g of silica sol (Catalyst Kasei Catalyst S-30L SiO ₂ 30wt%) was used as the silica source, and sodium aluminate (Na ₂ O manufactured by Wako Pure Chemical Industries, Ltd.) was used as the alumina source.
1.27 g of Al ₂ O ₃ =1.56:1), 4.16 g of caustic soda (95% kinetic grade, manufactured by Wako Pure Chemical Industries, Ltd.) as an OH ^- source, and N, N, N, synthesized as above as an organic ammonium source.
Add 4.14 g of N', N', N'-hexamethyl-1,3-propanediammonium salt to 150 ml of pure water to prepare a gel. The composition of this product, expressed in molar ratio, is: SiO ₂ /Al ₂ O ₃ = 100 Ammonium salt / Si + Hl = 0.02 OH ^- /Si + Al = 0.20 H ₂ O / Si + Al = 24.0 OH ^- /H ₂ O = 8.4 × 10 ^-3 It was hot. This gel was placed in a 500 ml stainless steel autoclave and reacted for one week at 160° C. under autogenous pressure while being gently stirred. The reaction product was taken out, separated into three parts, thoroughly washed with pure water until the washing solution became less than 50 μ/cm, and dried overnight at 60°C to form crystalline zeolite.
25.2g of TPZ-2 was obtained. The composition of this TPZ-2 is: 0.35RO; 0.55Na ₂ O; Al ₂ O ₃ ; 81.3SiO ₂ ;
8.0H ₂ O (R represents N,N,N,N',N',N'-hexamethyl-1,3-propanediammonium group). The X-ray diffraction data are shown in Table 1 and the chart is shown in Figure 1.

[Table] / ₀ in the table indicates the intensity ratio (%) when the strongest peak is taken as 100. (The same applies hereinafter.) Furthermore, even when heated in air at 800° C. for 12 hours, the X-ray diffraction data is essentially the same as this one, indicating good heat resistance. Example 2 120 g of silica sol was used as the silica source, and aluminum sulfate 18 hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the alumina source.
(special grade) 2.00 g, 6.11 g of caustic soda as an OH ^- source, and N,N,N,N',N',N'-hexamethyl-1, synthesized in Example 1 as an organic ammonium source.
3-4.97g of propanediammonium salt in 200ml of pure water
ml and prepared a gel. The composition of this product is expressed in moles as follows: SiO ₂ /Al ₂ O ₃ = 200 ammonium salt/Si + Al = 0.02 OH ^- /Si + Al = 0.20 H ₂ O / Si + Al = 26.0 OH ^- /H ₂ O = 7.7 x 10 ^-3. It was hot. 31.0 g of TPZ-2 was obtained in the same manner as in Example 1. The composition of this is 0.23RO; 1.03Na ₂ O; Al ₂ O ₃ ; 124.4SiO ₂ ;
It was 16.6H ₂ O. Table 2 shows the X-ray diffraction data and chart.
It is shown in Figure-2.

[Table] Even after heat treatment at 800°C as in Example 1, the X-ray diffraction data remained unchanged, indicating good heat resistance. Example 3 As a silica source, 300 g of silica sol, as an alumina source, 9.99 g of aluminum sulfate 18 hydrate, as an OH ^- source, 17.94 g of caustic soda, and as an organic ammonium source, N, N, N, N', synthesized in Example 1,
12.42 g of N',N'-hexamethyl-1,3-propanediammonium salt was added to 450 ml of pure water to prepare a gel. The composition of this product, expressed in moles, is: SiO ₂ /Al ₂ O ₃ = 100 ammonium salt / Si + Al = 0.02 OH ^- /Si + Al = 0.20 H ₂ O / Si + Al = 24.0 OH ^- /H ₂ O = 8.4 × 10 ^-3 Ta. This gel was prepared in the same manner as in Example 1 using a 1-volume stainless steel autoclave to obtain 84.6 g of TDZ-2.
I got it. The composition of this is: 0.37RO; 0.63Na ₂ O; Al ₂ O ₃ ; 73.7SiO ₂ ;
It was 5.2H ₂ O. The X-ray diffraction data and chart are shown in Table 3 and Figure 3.

[Table] As in Example 1, even after heat treatment at 800°C, the X-ray diffraction data remains unchanged, indicating good heat resistance. Examples 4 to 10 The results of repeated synthesis in the same manner as Examples 1 and 2 are shown in Table 4 together with Examples 1 to 3.

[Table] Examples 11 to 13 Three types of divalent organic ammonium salts, namely N, N, N, N', N', N'-hexamethyl-1,2-ethanediammonium, were prepared in the same manner as in Example 1. salt,
N,N,N,N',N',N'-hexamethyldiphenylmethanediammonium salt, and N,N'-diethyl-N,N,N',N'-tetramethyl-1,
3-Propanediammonium salt was synthesized. Zeolite was synthesized in the same manner as in Example 1 using each of these salts. The composition and X-ray diffraction data of these gels are shown.
5, 6, 7, and 8.

【table】

【table】

【table】

[Table] Example 14 TPZ-2 obtained in Examples 1, 2, 3, and 5
After firing at 500℃ for 6 hours, ammonium chloride 10%
Ion-exchange with an aqueous solution under reflux to form the ammonium form, dry again and then bake at 500°C for 6 hours to form the hydrogen form.
Obtained TPZ-2. The sodium content of this product is extremely low as shown in Table 9, indicating that ion exchange is almost complete. Moreover, the X-ray diffraction of this H ⁺ -TPZ-2 is essentially the same as that before ion exchange, and this was
It remained unchanged even after heat treatment.

[Table] Example 15 TPZ-2 obtained in Example 3 was replaced with H ⁺ -TPZ-2 in the same manner as in Example 14.
It was treated with 1N hydrochloric acid at 70°C for 20 hours. The composition of this material is shown in Table 10.

【table】

[Table] This dealuminized TPZ-2 was also essentially the same as the original X-ray diffraction, and furthermore, it was unchanged when heat treated at 800°C. Example 16 H ⁺ -TPZ-2 obtained in the same manner as Example 14
The pellets were pelletized, the particle size was adjusted to 10 to 20 meshes, and the pellets were calcined at 450°C for 8 hours. This catalyst was packed into a glass reaction tube and heated to 430℃.
Mixed xylene was fed at WHSV=2, and xylene isomerization reaction was performed. The results are shown in Table-11.

【table】 [Brief explanation of drawings]

Figure 1 is an X-ray diffraction chart of the crystalline zeolite obtained in Example 1, Figure 2 is an X-ray diffraction chart of the crystalline zeolite obtained in Example 2, and Figure 3 is an X-ray diffraction chart of the crystalline zeolite obtained in Example 2. This is an X-ray diffraction chart obtained in 3.

Claims (1)

[Claims] 1 The following formula (1) M ₂ /nO・Al ₂ O ₃・XSiO ₂ ...(1) [However, the formula is expressed in the form of an oxide in an anhydrous state, M represents one or more n-valent cations, and X represents 10 or more. ] A crystalline aluminosilicate zeolite having a composition represented by the following and an X-ray lattice spacing substantially represented by the following values: 2. The crystalline aluminosilicate zeolite according to item 1, wherein M is a hydrogen ion and/or a metal ion. 3. The crystalline aluminosilicate zeolite according to item 1, wherein M is at least one ion selected from the group consisting of hydrogen ions, alkali metal ions, alkaline earth metals, group metal ions, and rare earth metal ions. 4. The crystalline aluminosilicate zeolite according to item 1, wherein M contains at least a group metal ion. 5. The crystalline aluminosilicate zeolite according to items 1 to 4, wherein X is in the range of 10 to 1000. 6. The crystalline aluminosilicate zeolite according to items 1 to 4, wherein X is in the range of 10 to 500. 7 A composition containing an alkali metal ion source, an organic nitrogen-containing cation source, a silica source, an alumina source, and water, each component expressed in molar ratio as follows: SiO ₂ /Al ₂ O ₃ = 10 or more R/(Si+Al)=1 _× ^10-4 ~1 OH ^- /(Si+Al)= _0.1-0.5 H2O/(Si+Al)=5-100 OH- ^/ H2O=1× ^10-3 ~1×10 ^-1 [However, R in the formula is the general formula R ₁ R ₂ R ₃ N+ (CH ₂ ) mN+
R ₄ R ₅ R ₆・2X ^- and (m is 2 or 3, R ₁ to _{R 6} are the same or different alkyl groups having 1 to 4 carbon atoms, but one of them may be a hydrogen atom; X is a halogen atom) ammonium ion based on an organic nitrogen-containing cation source selected from the group consisting of: OH ^- represents an alkali metal ion and a hydroxyl group based on the ammonium ion of R; ] The following formula (1) M ₂ /nO・Al ₂ O ₃・XSiO ₂ ……( 1) [However, the formula is expressed in the form of an oxide in an anhydrous state, M represents one or more n-valent cations, and X represents 10 or more. ] A method for producing a crystalline aluminosilicate zeolite having a composition represented by the following and an X-ray lattice spacing substantially represented by the following values: 8 R is N, N, N, N', N', N'-hexaalkyl-1,2-ethanediammonium ion, N, N, N, N', N', N'-hexaalkyl- Item 7, which is at least one ammonium ion selected from the group consisting of 1,3-propanediammonium ion and N,N,N,N',N',N'-hexaalkyldiphenylmethane ammonium ion. The method for producing the crystalline aluminosilicate zeolite described. 9 The ammonium ion (R) is N, N, N,
N', N', N'-hexamethyl-1,2-ethanediammonium ion, N, N, N, N', N', N',
At least one ammonium ion selected from the group consisting of -hexamethyl-1,3-propanediammonium ion and N, N, N, N', N', N', -hexamethyldiphenylmethane ammonium ion. A method for producing a crystalline aluminosilicate zeolite according to item 7. 10 The OH ^- is a sodium ion and N, N,
N, N', N', N', -hexamethyl-1,2-ethanediammonium ion, N, N, N, N',
N', N', -hexamethyl-1,3-propanediammonium ion and N, N, N, N', N',
8. The method for producing a crystalline aluminosilicate zeolite according to item 7, wherein the hydroxyl group is based on at least one ammonium ion selected from the group consisting of N'-hexamethyldiphenylmethane ammonium ion.