JPS63260809A - Crystalline boroaluminosilicate and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled substance having fine pore diameter and excellent adsorption characteristics and catalytic characteristics and useful as a molecular sieve, adsorbent, catalyst component, etc., by mixing an organic cation source, an Si source, an Al source, a B source, an alkali ion source, etc., and water and crystallizing the obtained reaction mixture at a specific temperature. CONSTITUTION:An organic cation source (e.g. tetramethylammonium chloride), an Si source (e.g. amorphous silica), an Al source (e.g. alumina sol), a B source (e.g. boric acid or its salt) and one or more alkali ion sources selected from alkali or alkaline earth metal ion source, NH4 ion source, etc., (e.g. NaOH) are added to water and uniformly mixed to obtain a reaction mixture having a molar composition of formula I (R is organic cation; M' is alkali ion; n' is atomic valence of M'). The mixture is crystallized by maintaining at 100-250 deg.C for 2-200hr preferably under atmospheric pressure and the objective porous substance is separated and recovered from the product. The obtained substance exhibits a powder X-ray diffraction pattern shown in the Table II (W, M, S and VS represent 'weak', 'middle', 'strong' and 'very strong', respectively) in unbaked state and has a chemical composition of formula III (0<a<1; x>=15; M is cation; n is atomic valence of M) in an anhydrous state.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a crystalline boroaluminosilicate porous body containing boron and aluminum, and a method for producing the same. , hereinafter collectively referred to as "TSBS-12". Zeolites are generally aluminosilicates, consisting of 810 and Si bound together by sharing oxygen atoms with each other.
It has a three-dimensional skeleton of a 04H hedron.

TSBS-12 of the present invention is a boroaluminosilicate that contains Bo4 tetrahedron in its three-dimensional skeleton in addition to AlO2,5i04 and has uniform pores. These porous boroaluminosilicate materials have adsorption properties that cannot be obtained with conventional zeolites.

Since it has catalytic performance, it is useful as a molecular sieve, an adsorbent, or a catalyst component for hydrocarbon addition reactions.

[Prior art] Zeolite, ie, aluminosiligate, has S1/A! There are limits to the control of pore diameter or catalyst performance by controlling the ratio. Therefore, research is being conducted with the aim of obtaining pore diameters or catalytic performance that cannot be obtained with zeolites by replacing aluminum in the framework with other elements. As an example, US Pat. No. 4,269,813 describes a crystalline boron-containing metallosiligate having the structure of zeolite ZSM-5.

[Problems to be Solved by the Invention] The present inventors have discovered that conventional zeolites and metallosilicates have a zeolite-type structure and contain atoms of different metals in addition to silicon and aluminum in the crystal lattice. The present invention was achieved as a result of intensive research aimed at synthesizing metallosiligates with pore diameters and solid acid properties, that is, adsorption properties and catalytic performance, which had never been possible before.

[Means for solving problems] The novel material of the present invention contains silicon in its crystal lattice.

Contains boron and aluminum, that is, expressed as the molar ratio of oxides, (1±0.3)M2/nO・aB203 ・(1-a)
A12o3-xsio2 (in the formula, a is a number of O<a<1, X is a number of 15 or more,
M represents at least one kind of cation, n represents the valence of M) and has a chemical composition on an anhydrous basis of (M represents at least one cation, n represents the valence of M), and has substantially the interplanar spacings listed in Table 1 in the unfired state. Powder X-ray diffraction This is a porous crystalline boroaluminosilicate characterized by having a geometric shape.

Table 1 Powder X-ray diffraction pattern spacing d (A) Peak intensity 8.85±0.
20 W 8.27±0.2OS 6.53±0.10 M 6.19+0.1OS 4.44±0.07 3 4°3440.07 3 4.02±0.07 VS 3.86±0. 05 3 3.69+0.05 W 3.53±0.05 M 3.25±0.05 W (In the table, W, M, S, and VS are each weak.

Medium 1 represents strong, very strong) Cation M is not particularly limited, but may be an organic cation.

Alkali metal ions, alkaline earth metal ions.

They are cations such as ammonium ions and hydrogen ions, or mixtures of these cations.

Further, the method of the present invention includes a silicon source: a boron source; an aluminum source; an organic cation source; and an alkali metal ion.

Any one or more of alkaline earth metal ions and ammonium ion sources; and water are mixed to form the following composition of silicon, aluminum and boron expressed in molar ratio of oxides: 5102/(Aβ203-8203) 5-5000 B O/ (Al1203+ 8203 >0.00
1-0.99 0H-/HOO, 012-0.045 M', 0/5IO20-1,0 -2/n H2O/5102 10-50 R/(S10 +Al2O3+B203) 0.01-1
,0 (wherein, R represents an organic cation, M' represents one or more of alkali metal ions, alkaline earth metal ions, and ammonium ions, and n' represents the valence of M'). was prepared, and the reaction mixture was heated to 100
This is a method for producing TSBS-12 characterized by maintaining the temperature at a temperature of 0.degree. C. to 250.degree.

The silicon source, boron source, aluminum source, organic cation source, alkali metal ion, alkaline earth metal ion, or ammonium ion source is not particularly limited. For example, as a source of alkali metal ions, alkaline earth metal ions, or ammonium ions, hydroxides of the ions or neutral salts thereof can be used. As the silicon source, water glass, colloidal silica, amorphous silica, fumed silica, etc., which are conventionally used in zeolite production, can be used. Boric acid or borates can be used as the boron source. As the aluminum source, alumina sol, pseudoboehmite, sodium aluminate, aluminum hydroxide, aluminum oxide, aluminum sulfate, etc., which are conventionally used in zeolite production, are used. The organic cation source used is one containing nitrogen or phosphorus.

Preferably, it is provided by introducing its hydroxide or halide with tetramethylammonium ion.

If the reaction mixture is heterogeneous, impurities may be replicated, so these raw materials are added under stirring, and the intermediate mixture until all of the respective raw materials are added and the final reaction mixture after the addition of the raw materials are substantially It is preferable to stir until the mixture becomes homogeneous.

The final reaction mixture thus obtained is crystallized in a closed pressure vessel made of stainless steel and lined with an inert plastic material, such as polytetrafluoroethylene, to prevent contamination with impurities.

During crystallization, the temperature must be between 100°C and 250°C. If it is less than 100°C, crystallization will take too long, and if it exceeds 250"C, crystallization will proceed in a short time, but impurities will be generated. This is because it becomes easier.

Regarding pressure, although pressure may be applied during crystallization, it is preferably carried out under natural pressure.

Crystallization is carried out by holding under the above conditions for usually about 2 hours to about 200 hours. The crystallization time depends on the crystallization temperature, but if it is too short, no crystallization occurs, and if it is too long, impurities are likely to be generated.

The product may be recovered by conventional separation methods such as transient or centrifugation.

TSBS-12 thus obtained contains the organic matter used as a mineralizer in its pores. This organic substance can be removed if necessary, but it is not removed by treatment such as ion exchange, but by calcination at a common calcination temperature, that is, a temperature of 450 to 650°C. The X-ray diffraction pattern of TSBS-12 is due to this calcination.
Substantially unchanged.

Do not use CuK-α radiation for X-ray diffraction of the product.

As is known to those skilled in the art, the determination of the parameter 2θ is subject to total human and lfiM errors, which can impose an error of approximately 0.4° on each recorded value of 2θ. Furthermore, the recorded values of 2θ and peak intensity may vary depending on the composition of the skeleton of the substance, the type of cations, the degree of heat treatment, etc. This error, of course, introduces uncertainty into the d-spacing and relative intensity values calculated from each recorded value. However, this uncertainty is not sufficient to prevent the novel materials of the present invention from being distinguished from prior art materials.

[Effects of the Invention] TSBS-12 containing the above-mentioned organic cations is decomposed and removed by firing at 450 to 650°C in an air stream as necessary, and then treated with, for example, ammonium hydroxide, ammonium sulfate or After converting it into an ammonia type by ion exchange with an ammonium salt such as ammonium nitrate, ammonia is removed by firing at 450 to 650°C to obtain active hydrogen type TSBS-12.

This hydrogen type TSBS-12 has BO/(A
10 +8203) The acid strength can be changed continuously by changing the molar ratio.

Even in conventional aluminosilicate, SiO/
It is possible to control the acid strength by changing the Al2O3 molar ratio, but aluminosilicate is SIOZA12
It is known that as the molar ratio of 03 increases, the hydrophilicity of 03 decreases.

However, the TSBS-12 of the present invention makes it possible to control acid strength and maintain its hydrophilicity, which was not possible with conventional aluminosilicate.
For example, by controlling the acid strength in a hydrocarbon addition reaction, the selectivity of the reaction can be advantageously influenced.

TSBS-12 is prepared by ordinary ion exchange, impregnation, etc.
It supports desired metal ions and can be used as a catalyst component.

TSBS-12 also exhibits unique performance as an adsorbent.The interplanar spacing in the X-ray powder diffraction pattern of TSBS-12 continuously decreases as the molar ratio of 8203/(Al103 +B2 a3) in the crystal increases. Therefore, the TSBS-12 of the present invention allows the pore diameter to be controlled by controlling the B2o3/(AI2203+B203) molar ratio in the crystal.

Even in conventional aluminosilicate, SiO/
It is possible to control the pore diameter by changing the Aβ203 molar ratio, but as mentioned above, aluminosilicate
With the increase of iO2/A2203 molar ratio, its hydrophilicity decreases; however, the TSBS of the present invention
-12 makes it possible to control the pore diameter and maintain its hydrophilicity, which could not be achieved with conventional aluminosilicate, and can favorably affect the selectivity of adsorbed molecules.

Moreover, TSBS-12 of the present invention can be produced by the method of the present invention.

[Examples] In order to explain the present invention more specifically, Examples are shown below, but the present invention is not limited to the following Examples.

Example 1 5.24 g of sodium hydroxide (98% NaOH);
0.13 g of boric acid was dissolved in 111.6 g of water. Amorphous silica (SiO = 87.7 wt%,
Ai203=0゜5 wt%, H20=11-8
vv t%) 21.7 g: was added, and finally 11.0 g of tetramethylammonium chloride was added to prepare a reaction mixture having the following composition.

5in2/(Ai)203+8203)=149B
203/(A1203+8203)=0.500H-/
H20=0.02O N a20/ S l 02 = O-40H2
0/Sio2 = 20 TMA”/(SiO+A, g O÷B 203) = 0
．． 31 (TMA”; tetramethylammonium ion.

The same applies hereinafter) This reaction mixture was sealed in an autoclave, heated to 160° C. under natural pressure with constant stirring, and maintained at this temperature for 69 hours to obtain a crystalline product. After filtering and washing with water, 11
It was dried at 0°C.

Chemical analysis revealed that this product had the molar composition shown in Table 8.

This was also a boroaluminosilicate of the present invention having the X-ray diffraction pattern shown in Table 2.

Table 2 Shiizuki juLLI 19 8.28 41 6.60 21 6.48 23 6.13 45 5, 62 8 5.37 8 4, 62 7 4.45 49 4.41 49 4.17 47 4.02 100 3.95 51 3.89 71 3.83 27 3.69 17 3.54 31 3.42 5 3, 30 15 3, 25 19 3.11 15 3, 05 3 3. 01 7 2, 99 8 2, 98 8 2, 95 9 2.87 15 2, 82 6 2.78 12 2, 76 14 2, 70 8 2, 62 3 Example 2 Using the same raw materials as Example 1 A reaction mixture was prepared with the following molar composition.

5102/(Ai203 +8203)=14.3820
3/(Ai203 +B203 > =0.95O
H-/H20=0.02ONaO/Si02=0,40
H20/5102 =20 TMA+/(S1o +Aβ o +B203)=0.
32 The reaction mixture was sealed in an autoclave, heated to 160° C. under natural pressure with constant stirring, and maintained at this temperature for 68 hours to obtain a crystalline product. After filtering and washing with water, 11
It was dried at 0°C.

Chemical analysis revealed that this product had the molar composition shown in Table 8.

This was also a boroaluminosilicate of the present invention having the X-ray diffraction pattern shown in Table 3 and FIG.

Table 3 Stop-"ノ"-Shiitake 8.83 18 8, 23 37 6, 48 33 6, 16 44 5, 59 10 5, 33 6 4, 59 8 4.41 47 4, 27 42 4 , 04S 59 4, 00 100 3, 95 78 3, 84 60 3.82S , 48 3, 67 14 3, 51 20 3.41 5 3, 23 21 3.08 11 2, 99 10 2, 94 8 2. 91 9 2, 85 16 2, 81 62.76
11 2.74 13 2, 67 10 2.61 3 S indicates that it was observed as a shoulder.

Example 3 Using the same raw materials as in Example 1, a reaction mixture with the following molar composition was prepared.

SiO/(AJ2203-1-8203)=14.3B
O/(AI2203+8203) =0,
950H-/H20=0.022 Na20/SiO2=0.67 H20/5102=30 TMA+/(SlO+Al2O3+B2o3)=0.3
1 This reaction mixture was sealed in an autoclave, heated to 180° C. under natural pressure with constant stirring, and maintained at this temperature for 24 hours to obtain a crystalline product. After filtering and washing with water, 11
Dry at 0°C.

Chemical analysis revealed that this product had the molar composition shown in Table 8.

Moreover, this was the boroaluminosilicate of the present invention having the X-ray diffraction pattern shown in Table 4.

Table 4 Ni IAI Masatsuki JLLI Gokami 8.80 21 8.20 43 6.46 33 6.15 49 5, 59 9 5, 33 7 4, 58 6 4.43 45 4.27 42 4.00 Zo.

3.963 85 3, 83 63 3, 67 14 3, 51 23 3.41 5 3, 23 22 3.08 11 2.98 11 2, 90 90 2, 85 14 2゜　74　　　　　13 2, 67 10 2.61 3 S indicates that it was observed as a shoulder.

Example 4 Prepare a reaction mixture using the same starting materials as in Example 1 and having the following molar composition.

S i 02 / (A12o3±8203)=14.
3B203/(A12o3±8203)=0.950H
”/H20=0.027 N a O/ S i 02 = 0, 53
HO/ S i O2= 20 T M A ” / (S iO+ A fl O+
B203)=0. 12 This reaction mixture was sealed in an autoclave, heated to 180° C. under natural pressure with constant stirring, and maintained at this temperature for 47 hours to obtain a crystalline product. After filtering and washing with water, 11
It was dried at 0°C.

Chemical analysis revealed that this product had the molar composition shown in Table 8.

Moreover, this was the boroaluminosilicate of the present invention having the X-ray diffraction pattern shown in Table 5.

Table 5 Stop-1 artificial 8.84 19 8.25 46 6.50 36 6.17 55 5.61 10 5, 34 9 4, 59 7 4.41 51 4.28 48 4.053 54 4.01 100 3.95 71 3゜84　　　　　69 3.82S 36 3.68 14 3, 51 28 3, 42 6 3.24 22 3.08 13 2, 99 10 2, 94 7 2.91 9 2.85 16 2, 81 6 2.77 12 2.74 14 2.67 12 2.61 3 S indicates that it was observed as a shoulder.

Example 5 23.4 g of sodium hydroxide (98% Na0H) and
2.2g of boric acid and 3.8g of sodium aluminate (
Aβ203=18.80wt%, N a 20 =
19.16wt%, H20=62.04wt%),
Dissolved in 516.2g of water. Amorphous silica (SIO2=87.7wt%1A1203=0.5
wt%.

H20=11, 8 wt%) was added, and finally 52.3 g of tetramethylammonium chloride was added to prepare a reaction mixture having the following composition.

S i 02 / (Al103 + 8203)
= 50-0B203/(A1203 + B203) = 0
．． 600H-/H20=0.02ONa2o/Si02=0.40H
20/5i02 =20 TMA+/(SlO+Aβ203+B2o3)=0.3
1 This reaction mixture was sealed in an autoclave, heated to 160° C. under natural pressure with constant stirring, and maintained at this temperature for 140 hours to obtain a crystalline product. After filtering and washing with water, 1
Do not dry at 10°C.

Chemical analysis revealed that this product had the molar composition shown in Table 8.

This was also a boroaluminosilicate of the present invention having the X-ray diffraction pattern shown in Table 6.

Table 6 Stop-"No+ ■j"L [Yu3nee 8.90
15 8.27 39 6.53 27 6.20 52 5, 62 9 5, 37 8 4, 62 7 4.44 47 4. 30 50 4, 08 44 4, 03 100 3, 99S 68 3, 95 58 3, 88 66 3, 83 34 3, 70 15 3, 54 30 3, 43 6 3.28 15 3, 25 20 3.11 14 3, 00 92, 96
8 2, 93 9 2, 87 16 2, 83 7 2, 78 12 2, 76 142.69
11 2, 62 3S indicates that it was observed as a shoulder.

Example 6 In Example 5, the molar composition of the reaction mixture was changed to SiO/(
Aβ203+B203); 50.0B203/(A
1203 +B203 N: Mini 0. 300H-/
H20=0.02O Na20/SiO2=0.40 H2o/5102 =20 TMA”/(SiO+Aβ203 + B 203 )
= 0.31, the same operation as in Example 5 was performed to recover the product.

Chemical analysis revealed that this product had the molar composition shown in Table 8.

Moreover, this is the boroaluminosilicate of the present invention having the X-ray diffraction pattern shown in Table 7 and FIG.

Table 7 Stop-worker top 111 Eu 10 40 4.04 100 4.00 60 3.97 58 3.89 66 3.84 30 3.71 15 3.55 28 3°45 9 3, 29 14 3.27 19 3, 12 14 3, 06 4 3, Of 8 2.98 8 2, 94 9 2.88 16 2, 85 6 2.79 12 2, 76 13 2.70 10 2, 63 3 Table 8 Molar composition of product t(TMA) 0 mNa2O・aB2o3・(1a)
A 1203 ・xS i 02

[Brief explanation of drawings]

FIGS. 1 and 2 are diagrams showing powder X-ray diffraction patterns of boroaluminosilicate obtained in Example 2 and Example 6, respectively.

Claims (1)

[Claims] (1) Expressed in molar ratio of oxides, (1±0.3)M_2_/_nO・aB_2O_3・(
1-a) Al_2O_3・xSiO_2 (in the formula, a is a number of 0<a<1, x is a number of 15 or more,
M represents at least one kind of cation, and n represents the valence of M. ) A porous crystalline boroaluminosilicate having a chemical composition on an anhydrous basis, and having a powder X-ray diffraction pattern substantially including the interplanar spacings shown in Table 1 in an unfired state. Table 1 Powder X-ray diffraction pattern spacing d(A) Peak intensity 8.85±0.20 W 8.27±0.20 S 6.53±0.10 M 6.19±0.10 S 4.44 ±0.07 S 4.34±0.07 S 4.02±0.07 VS 3.86±0.055 S 3.69±0.05 W 3.53±0.05 M 3.25±0 .05 W (In the table, W, M, S, and VS represent weak, medium, strong, and very strong, respectively.) (2) Organic cation source; silicon source; aluminum source; boron source; alkali metal ions, alkaline earth metal ions, and ammonium ion sources; and water to form the following composition SiO_2/(Al_2O_3+B_2O_3) 5 to 5, with silicon, aluminum, and boron represented by the molar ratio of oxides.
000 B_2O_3/(Al_2O_3+B_2O_3)0.
001~0.99 OH^-/H_2O 0.012~0.045M'_2
＿／＿n＿′O/SiO_2 0〜1.0H_2O/S
iO_2 10~50 R/(SiO_2+Al_2O_3+B_2O_3)0
．． 01 to 1.0 (However, R represents an organic cation, M' represents one or more of alkali metal ions, alkaline earth metal ions, and ammonium ions, and n' represents the valence of M'.) prepare a reaction mixture with 100
1. A method for producing porous crystalline boroaluminosilicate, which comprises maintaining the temperature at a temperature of 0.degree. C. to 250.degree. (3) The method for producing porous crystalline boroaluminosilicate according to claim 2, wherein the organic cation is a tetramethylammonium ion.