JPH1160577A - Organic template for synthesizing zeolite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To use a substituted salt of 2,7-diazaspiro[4,4]nonanium as an organic template for synthesizing a zeolite having a large crystal size. SOLUTION: A substituted salt of 2,7-diazaspiro[4,4]nonanium [preferably, 2,2,7,7-tetrasabstituted salt of formula I (R<1> is a benzyl nonsubstituted or substituted with one to five 1-4C alkyls; R<2> to R<4> are each H, a benzyl nonsubstituted or substituted with one to five 1-4C alkyls, or a 1-6C alkyl) is used as an organic template. The substituted salt is obtained, for example, by reducing an imide body of formula II (e.g. 2,7-dibenzyl-2,7- diazaspiro[4,4]nonane-1,3,6,8-tetraone) to provide a disubstituted amine of formula III (e.g. 2,7-dibenzyl-2,7-diazaspiro[4,4]nonane), and treating the disubstituted amine with anhydrous hydrogen chloride to provide the disubstituted salt, and further reacting the disubstituted amine with an alkyl halide of a regulated amount to provide the trisubstituted salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an organic template useful in the synthesis of zeolite, a method for synthesizing zeolite using the same, and a ZSM obtained by the synthesis method.
-12 type zeolite.

[0002]

2. Description of the Related Art In recent years, many attempts have been made to use zeolites as catalysts for various organic reactions. Since zeolite has a uniform pore structure, chemical composition, and chemical properties that are easy to control, and the size of the microspace that serves as the reaction field can be determined by the synthesis method, it is expected to be applied to shape-selective reactions. Have been. In addition, zeolite having few crystal defects and a large crystal size is expected to be applied as an adsorption separation membrane or a catalyst having a long life. One of them is a zeolite called ZSM-12. Normal Z
In the synthesis of SM-12, a triethylmethylammonium salt or a tetraethylammonium salt is often used as an organic template. However, the Z obtained by this method
SM-12 has a major axis of 20 μm × a minor axis of 5 μm,
An organic template capable of synthesizing ZSM-12 having a larger crystal size has not been found so far.

[0003]

SUMMARY OF THE INVENTION The present invention provides a novel organic template for zeolite synthesis comprising a substituted salt of 2,7-diazaspiro [4,4] nonanium, a method for synthesizing zeolite using the template, and Novel ZSM- with a large crystal size obtained by the synthesis method
A type 12 zeolite is provided.

[0004]

SUMMARY OF THE INVENTION The present invention relates to the following. 1) An organic template for zeolite synthesis, comprising a substituted salt of 2,7-diazaspiro [4,4] nonanium. 2) The above substituted salt of 2,7-diazaspiro [4,4] nonanium is represented by the following general formula (1)

[0005]

Embedded image (Wherein, R ¹ represents a benzyl group unsubstituted or alkyl group having 1 to 4 carbon atoms is five substituents from 1, R ² ~
R ⁴ is a hydrogen atom, an unsubstituted or benzyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms or a benzyl group having 1 to 5 carbon atoms;
-6 represents a linear or branched alkyl group. ) The organic template for synthesizing zeolite according to 1) above, which is a substituted salt of 2,7-diazaspiro [4,4] nonanium represented by the following formula: 3) The above ² ) wherein R ^{2 to} R ⁴ are unsubstituted or a benzyl group substituted with 1 to 5 alkyl groups having 1 to 4 carbon atoms or a linear or branched alkyl having 1 to 6 carbon atoms. The organic template for synthesizing the zeolite according to the above. 4) The organic template for zeolite synthesis according to 1) to 3) above, wherein the anion is a hydroxyl ion, a halogen ion, a sulfate ion or a p-toluenesulfonic acid ion. 5) The organic template for zeolite synthesis according to 4) above, wherein the anion is a hydroxyl group ion. 6) A method for synthesizing zeolite, wherein the organic template for synthesizing zeolite is brought into contact with a silica source and / or an alumina source to perform hydrothermal synthesis. 7) ZSM-12 having a crystal size of 50 μm or more in major axis
Type zeolite.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The substituted salt of 2,7-diazaspiro [4,4] nonanium used in the present invention has at least one substituent at the nitrogen atom. Preferably, the following general formula (1)

Embedded image Is a substituted salt of 2,7-diazaspiro [4,4] nonanium. Here, R ¹ is a benzyl group or an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, etc.). Preferred examples include a benzyl group,
3,5-dimethylbenzyl group. R ^{2 to} R ⁴ are a hydrogen atom, a substituted or unsubstituted benzyl group described above for R ¹ , or a linear or branched alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, n -Propyl group, isopropyl group, n-butyl group, isobutyl group,
sec-butyl group, t-butyl group, n-pentyl group, n
-Hexyl group and the like. ). Preferred examples are a lower alkyl group, a benzyl group and a substituted benzyl group.

It is synthetically preferable that R ¹ and R ³ , and R ² and R ⁴ are the same substituent. It is preferable that R ¹ and R ² are different from each other, and similarly that R ³ and R ⁴ are different from the viewpoint of zeolite synthesis. More preferably, 2,2,7,7-tetrasubstituted salts are preferred.

Examples of the anion include a hydroxyl ion, a halogen ion, a sulfate ion and a p-toluenesulfonic acid ion. Preferably it is a hydroxyl group ion. 2,7-diazaspiro [4,4] used in the present invention
The nonanium substituted salt may be synthesized by any method, but the case where R ¹ and R ³ are benzyl groups and R ² and R ⁴ are methyl groups or benzyl groups is shown by the following reaction route.

[0009]

Embedded image

In the reaction route, when the tertiary amine is quaternized with an alkyl halide without using another base as a catalyst, the reaction temperature range is optimally from 0 to 100 ° C. In the reaction, soda lime may be used without a catalyst or as a catalyst. In that case, the preferred amount of the catalyst is 5 to 60 wt%. As the reaction solvent, a common organic solvent such as an acetate such as methyl acetate and ethyl acetate, a ketone such as methyl ethyl ketone and acetone, an alcohol such as methanol, ethanol and propanol can be used.
Among them, methanol is most suitable in terms of operability and yield.

The desired disubstituted salt is obtained by treating the disubstituted amine (3) obtained by reducing the imide compound (2) with anhydrous hydrogen chloride, and the disubstituted amine (3) has an amount of an alkyl halide. Is adjusted to give the desired trisubstituted salt. In this case, it is necessary to perform separation from the tetra-substituted salt by a conventional method. Further, by ion-exchanging a halogen ion which is an anion of the substituted salt of 2,7-diazaspiro [4,4] nonanium obtained by the above-mentioned method using a conventionally known method such as an ion-exchange resin. Can be converted into another anion to obtain a desired anion salt.

In the method for synthesizing zeolite using the organic template for synthesizing zeolite of the present invention, the organic template of the present invention is brought into contact with a silica supply source and / or an alumina supply source in the presence of water to perform hydrothermal synthesis. Suitable silica sources include silicates such as sodium silicate and potassium silicate, silica hydrogel, fumed silica, silicic acid, colloidal silica, tetraethyl silicate, tetramethyl silicate, tetrabutyl silicate, tetraisopropyl silicate Alkyl silicate,
Silica precursor, silica hydroxide. Suitable alumina sources include alumina salts such as sodium aluminate, alkoxyaluminums such as isopropoxyaluminum, and aluminum hydroxide.

In the method for synthesizing zeolite using the organic template for synthesizing zeolite of the present invention, the reaction mixture comprising the organic template, the silica supply source and, if necessary, the alumina supply source is used in an amount of 80 to 250 until crystals are formed.
C., more preferably from 120 to 180.degree. C., for 1 hour to 50 days, preferably 1 to 20 days. Crystal formation is performed at atmospheric pressure or under pressure. The reaction mixture may be stirred or otherwise agitated during crystallization, or may be allowed to stand.

After the crystals have formed, the synthesized zeolite is separated from the reaction mixture by filtration, decantation, centrifugation and the like. The crystals are washed with a suitable solvent, preferably water, and then at 90-250 ° C for 3-24 hours.
Dry under atmospheric pressure or reduced pressure for hours. Since the zeolite thus obtained contains an organic template, it may be used at 300 to 800 ° C.,
The organic template can be removed by calcining at ６００600 ° C. for 10 to 60 hours in an air or nitrogen atmosphere.

The zeolite synthesized by the zeolite synthesis method of the present invention contains SiO ₂ as a main component. If necessary,
Elements such as aluminum, boron, and titanium can be included. According to SEM, the zeolite consists essentially of a single phase, the crystal morphology being twins, in which rod-shaped (Elongated) crystals of about 70 microns in length intersect each other at an angle of 60 °. Starburst as a whole
It is.

[0016]

EXAMPLES Each measurement was carried out using the following equipment. NMR: ALPHA 400 FT-NMR Sp manufactured by JEOL
ectrometer IR: FT-IR Spectromet manufactured by Shimadzu Corporation
er mp: YANACO MP-13 melting point measuring device manufactured by Yanagimoto (company) XRD: Geigerflex X-ray diffractometer manufactured by Rigaku (company)

Example 1 Synthesis of 2,7-dibenzyl-2,7-diazaspiro [4,4] nonane Lithium aluminum hydride (4.01 g, 10
6 mmol) and THF (105 ml) were added, and the mixture was heated to 50 ° C. and stirred. Furthermore, 2,7-dibenzyl-2,7-
Diazaspiro [4,4] nonane-1,3,6,8-tetraone (7.32 g, 20.2 mmol) in THF (3
5 ml) solution was added dropwise over 40 minutes and then refluxed and stirred for 17 hours. After cooling, water (4 ml) was added little by little,
THF (50 ml) was added, and the mixture was stirred for 15 minutes.
% NaOH aqueous solution (4 ml) and water (12 ml) were successively added and stirred for 2 hours. After filtration and concentration under reduced pressure, benzene (10
The oily substance obtained by azeotropic distillation with 0 ml × 2) was redissolved in benzene (150 ml) and dried over potassium carbonate.
By filtration and concentration under reduced pressure, 2,7-dibenzyl-2,7
-Diazaspiro [4.4] nonane (6.10 g, 100
%) As a pale yellow oil.

¹ H-NMR (400 MHz, CDCl ₃ ,
TMS): δ 1.77-1.91 (4H, m, CH ₂
CH ₂ C) [2.42 (2H, d, J = 9.0 Hz) and 2.5
4-2.61 (6H, m), 2CH 2 -N-CH 2] 3.58 (4H, dd, J = 12.9Hz, 15.1H
_{z, 2CH 2 Ph), 7.20-7.30} (10H,
m, Ar-H) ¹³ C-NMR (100 MHz, CDCl ₃ ): δ39.
31 (CH ₂ ), 47.70 (quaternary carbon), 53.7
8, 60.47, 67.39 (each CH ₂ ), 12
6.73, 128.13, 128.64 (CH of benzyl group, respectively), 139.43 (C of benzyl group) IR (neat) [cm ^-1 ] 698, 735, 908,
1028, 1452, 1495, 1715, 2785,
2951

Example 2 2,7-Dibenzyl-2,7-dimethyl-2,7-diazaspiro [4.4] nonanium
Synthesis of Iodide In an eggplant flask, 2,7-dibenzyl-2,7-diazaspiro [4,4] nonane (6.1) obtained by the method of Example 1 was used.
(1 g, 19.9 mmol) was dissolved in methanol (50 ml) and stirred at room temperature. To this solution is added methyl iodide (1
(4.2 g, 100 mmol), and the mixture was covered and stirred with a magnetic stirrer for 24 hours at room temperature. After the reaction, the solvent and excess methyl iodide were distilled off under reduced pressure, and benzene was azeotroped to give 2,7-dibenzyl-2,7-dimethyl-
2,7-diazaspiro [4.4] nonanium iodide (11.84 g, yield 99%) was obtained.

¹ H-NMR (400 MHz, CD ₃ O
D): δ 2.62-2.70 (4H, m, 2CH ₂ CH)
₂ C), 3.11, 3.11, 3.13, 3.17 (6
H, respectively _{s, N-CH 3),} 3.65-3.75,
3.91-4.05, 4.24-4.35 (each 2
H, 4H, 2H, m, 2CH 2 NCH 2), 4.77-
_{4.87 (4H, m, 2CH 2} Ph), 7.50-7.
58, 7.69-7.72 (6H, 4H, m, respectively)
Ar-H) ¹³ C-NMR (100.4 MHz, CD ₃ OD): δ3
7.92, 38.21, 38.72 (C-4, C-
9), 47.83, 48.35, 48.39, 48.6
4 (C-5), 49.9,50.62,50.77,5
1.26 (CH _3), 64.29,64.53,64.
66, 64.84 (C-1, C-6 or C-3, C-
8), 69.09, 69.25, 69.42 (C-3,
C-8 or C-1, C-6), 74.17, 74.3.
8 (CH ₂ Ph), 129.37 (C of benzyl group),
130.46, 131.95, 133.85, 133.
86, 133.90 (CH of benzyl group) IR (KBr) [cm ^-1 ] 704, 770, 916, ¹
213, 1454, 1618, 2961, 3441

Example 3 2,7-Dibenzyl-2,7-dimethyl-2,7-diazaspiro [4.4] nonanium
Synthesis of hydroxide 2,7-dibenzyl-2,7-dimethyl-2,7-diazaspiro [4.4] nonanium obtained by the method of Example 2
Iodide (18.08 g, 30.6 mmol) was dissolved in distilled water (600 ml), and ion-exchange resin (Mitsubishi Chemical, DIAION, SA10A, H type) (245)
g) and distilled water (200 ml) were added, and the mixture was stirred at room temperature for 3 days. After filtration, the mixture was concentrated to 75 ml under reduced pressure, diluted to 120 ml with distilled water, and 2,7-dibenzyl-2,7-dimethyl-2,7-diazaspiro [4.4] nonanium
An aqueous solution of the hydroxide was obtained. Titration with 0.05 M HCl determined a concentration of 0.227 mmol / g and a yield of 87%.

Example 4 2,2,7,7-Tetrabenzyl-2,7-diazaspiro [4.4] nonanium bromide In an eggplant flask, 2,7-dibenzyl-2,2 obtained by the method of Example 1 was used. 7-diazaspiro [4.4] nonane (6.7
0 g, 21.9 mmol) was dissolved in ethyl acetate (50 ml), and benzyl bromide (9.36 g,
54.7 mmol) and stirred under reflux for 2 days. After allowing to cool, the crude crystals obtained by filtration were mixed with ethanol (300 m
l) Recrystallization from ethyl acetate (100 ml) -diethyl ether (10 ml) gave 2,2,7,7-tetrabenzyl-2,7-diazaspiro [4.4] nonanium.
Bromide (9.12 g, 67% yield) was obtained.

M. p. 210.0-212.0 ° C. ¹ H-NMR (200 MHz, CD ₃ OD (δ 3.35
ppm)): δ 1.24 to 1.54 (4H, m, 2CH
_{2 CH 2 C), 3.58-3.85 (} 4H, m, 2CH
₂ N), 3.78,3.93 (each 2H, d, J =
14.1 Hz, 2CH ₂ N), 4.61, 4.75 (2H, d, J = 12.9 Hz, 2CH ₂ Ph, respectively),
4.76 (4H, s, 2CH2Ph), 7.49-7.
76 (20H, m, Ar-H) ¹³ C-NMR (50.3 MHz, CD ₃ OD (δ49.
0 ppm)): δ 36.23, 59.66, 68.02,
68.20, 69.55 (CH ₂ each), 49.5
9 (quaternary carbon), 129.16, 129.50, 13
0.76, 130.89, 132.22, 132.4
7, 134.47, 134.76 (C of benzyl group) IR (KBr) [cm ^-1 ] 706, 768, 1026
1458, 2963, 3462

Example 5 Synthesis of 2,2,7,7-tetrabenzyl-2,7-diazaspiro [4.4] nonanium bromide 2,2,7,7-tetrabenzyl obtained by the method of Example 4 2,7-diazaspiro [4.4] nonanium bromide (9.12 g, 14.1 mmol) was added to distilled water (200 m
l) and ion-exchange resin (Mitsubishi Chemical, DI
AION, SA10A, OH type) (77 g), distilled water (10
0 ml) and stirred at room temperature for 3 days. After filtration, concentrate under reduced pressure to 20 ml, dilute to 50 ml with distilled water,
An aqueous solution of 2,2,7,7-tetrabenzyl-2,7-diazaspiro [4.4] nonanium bromide was obtained.
Titration with 0.05M HCl, concentration 0.250mmol
/ G, yield 92%.

Example 1 An aqueous solution of 2,7-dibenzyl-2,7-dimethyl-2,7-diazaspiro [4,4] nonanium hydroxide obtained by the method of Example 3 in a jar made of Teflon (0.2
3.99 g (1.0 mmol), 3
0.13 g (1.0 mmol) of 2 wt% NaOH is weighed out and 5.31 g of ion-exchanged water (500 mmol in total).
And stirred for 15 minutes. Cab-O-SilM5
(Fumed silica manufactured by CABOT) 0.60 g (1
0 mgeq. ) Was added and the mixture was further stirred for 3 hours. The resulting gel was sealed in a quartz tube and left in an oven at 150 ° C. for 20 days. The resulting precipitate was collected by filtration, washed with ion-exchanged water, and dried at room temperature. Analysis by XRD confirmed that it was ZSM-12 (Table 1). From the SEM photograph, the crystal is Starbu
rst, the total length was 70 μm.

[0026]

[Table 1]

Comparative Example 1 An aqueous solution of trimethylene (1,1-dimethylpiperidinium) hydroxide (0.249 mm) was placed in a Teflon jar.
ol / g) 2.41 g (0.6 mmol), 32 wt%
0.75 g (6 mmol) of NaOH is weighed out, and 8.79 g (total 640 mmol) of ion-exchanged water is added to add 10%.
Stir for a minute. To this, Cab-O-SilM5 (CABOT
1.20 g (20 mg eq.)
Was added and the mixture was further stirred for 1 hour. The resulting gel was sealed in a quartz tube and left in an oven at 150 ° C. for 6 days. The resulting precipitate was collected by filtration, washed with ion-exchanged water, and dried at room temperature. XR
Analysis by D confirmed that it was ZSM-12 (Table 2). From the SEM photograph, the crystals were aggregates having a shape close to a sphere and 3 μm in diameter.

[0028]

[Table 2]

Comparative Example 2 An aqueous solution of sodium silicate (silica 28.7 wt%, Na
₍₂ O 9.5 wt%) 4.21 g and ion-exchanged water 5.65
g of the mixture, 1.68 g (8.6 mmol) of triethylmethylammonium bromide and 5.14 of ion-exchanged water.
g of the mixed solution was added. After the resulting gel was stirred for 10 minutes, a mixed solution of 0.394 g (3.9 mmol) of 97% sulfuric acid and 4.63 g of ion-exchanged water was gradually added, and pH = 1.
0.97, and the mixture was further stirred for 1 hour. The gel was transferred to an autoclave containing a Teflon liner and left in an oven at 150 ° C. for 10 days. The resulting precipitate was collected by filtration, washed with ion exchanged water, dried at room temperature, analyzed by XRD,
It was confirmed to be M-12 (Table 3). From the SEM photograph, the crystals were Elongated type, 18 × 5 μm.

[0030]

[Table 3]

COMPARATIVE EXAMPLE 3 In a 500 ml polypropylene container, 3.57 g (89.25 mmol) of sodium hydroxide was charged with 25 parts of ion-exchanged water.
g of sodium aluminate (42.8 wt% of alumina, 33.7 wt% of Na ₂ O) and 20.06 g of tetraethylammonium bromide (95.45 m2).
mol) and 60 g of ion-exchanged water were sequentially added, followed by stirring for 5 minutes. Add colloidal silica (LuDox HS) to this solution.
-40 (Dupont), silica 40 wt%) 76.5
g (1.27 mol) was added and stirred for 40 minutes. The container was capped and left at 100 ° C. for 90 days. The resulting precipitate was collected by filtration, washed with ion-exchanged water, dried at room temperature, and analyzed by XRD to confirm that it was ZSM-12 (Table 4). From the SEM photograph, the crystals were aggregates that were nearly spherical, and the diameter of the aggregates was 0.5 μm.

[0032]

[Table 4]

Example 2 A 2,7-dibenzyl-2,7-dimethyl-2,7-diazaspiro [4,4] nonanium hydroxide aqueous solution obtained by the method of Example 3 in a Teflon jar (0.25%) was prepared.
3.99 g (1.0 mmol), 32
0.10 g (0.8 mmol) of wt% NaOH, Na _{2
B 4 O 7 · 10H 2 O38.1mg} (0.1mmol)
5.31 g of ion-exchanged water (500 mm in total)
ol) and stirred for 5 minutes. Cabosil M50.6
0 g (10 mg eq.) Was added, and the mixture was further stirred for 3 hours.
The resulting gel is sealed in a quartz tube and placed in an oven at 150 ° C.
It was left for one day. The resulting precipitate was collected by filtration, washed with ion-exchanged water, and dried at room temperature. Analysis by XRD confirmed that it was ZSM-12 (Table 5). Si / B = 40.4 (ICP) From the SEM photograph, the crystals were aggregates having a diameter of 10 μm.

[0034]

[Table 5]

[0035]

According to the present invention, 2,7-diazaspiro [4,
4] A zeolite can be synthesized by using a novel organic template for synthesizing a zeolite comprising a substituted salt of nonanium, and in particular, a new and effective ZS having a large crystal size can be used.
An M-12 type zeolite can be provided.

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[Procedure amendment]

[Submission date] September 18, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The substituted salt of 2,7-diazaspiro [4,4] nonanium used in the present invention has at least one substituent at the nitrogen atom. Preferably, the following general formula (1)

Embedded image Is a substituted salt of 2,7-diazaspiro [4,4] nonanium. Here, R ¹ is unsubstituted or has 1 carbon atom.
A benzyl group in which 1 to 5 alkyl groups (eg, methyl group, ethyl group, etc.) are substituted with 1 to 5 alkyl groups; Preferred examples are a benzyl group and a 3,5-dimethylbenzyl group. R ^{2 to} R ⁴ are a hydrogen atom, the substituted or unsubstituted benzyl group described above for R ¹ or a C ¹ to C 6
Linear or branched alkyl group (for example, methyl group, ethyl group, n-propyl group, isopropyl group,
n-butyl group, isobutyl group, sec-butyl group, t-
Butyl group, n-pentyl group, n-hexyl group and the like. ). Preferred examples are a lower alkyl group, a benzyl group and a substituted benzyl group.

Claims (7)

[Claims] 1. An organic template for zeolite synthesis, comprising a substituted salt of 2,7-diazaspiro [4,4] nonanium. 2. The substituted salt of 2,7-diazaspiro [4,4] nonanium is represented by the following general formula (1): (Wherein, R ¹ represents a benzyl group unsubstituted or alkyl group having 1 to 4 carbon atoms is five substituents from 1, R ² ~
R ⁴ is a hydrogen atom, an unsubstituted or benzyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms or a benzyl group having 1 to 5 carbon atoms;
-6 represents a linear or branched alkyl group. 2. The organic template for zeolite synthesis according to claim 1, which is a substituted salt of 2,7-diazaspiro [4,4] nonanium represented by the formula: 3. The above-mentioned R ^{2 to} R ⁴ are an unsubstituted or substituted benzyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms or a linear or branched alkyl having 1 to 6 carbon atoms. The organic template for synthesizing a zeolite according to claim 2. 4. The organic template for zeolite synthesis according to claim 1, wherein the anion is a hydroxyl ion, a halogen ion, a sulfate ion or a p-toluenesulfonic acid ion. 5. The organic template for synthesizing zeolite according to claim 4, wherein the anion is a hydroxyl ion. 6. A method for synthesizing zeolite, comprising bringing the organic template for synthesizing zeolite into contact with a silica supply source and / or an alumina supply source to perform hydrothermal synthesis. 7. ZSM-12 type zeolite having a crystal size of 50 μm or more in a major axis.