JPH02153817A - Crystalline metal silicate and its manufacturing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to SiO4 tetrahedron, and its combination with ZnO4°F e
04, one or more tetrahedrons selected from Cr O4+ G a O4r B O4, or these and AlO4
The present invention relates to a crystalline metal silicate consisting of tetrahedrons and a method for producing the same. This crystalline metal silicate of the present invention may be collectively referred to as "TMS-14" hereinafter.

Zeolite is an aluminosilicate in the
Al bonded by sharing oxygen atoms with each other
It has a three-dimensional bone t8 structure of O4 and SiO4 tetrahedrons.

TMS-14 of the present invention replaces some or all of the AlO4 tetrahedrons in the three-dimensional framework of zeolite with Zn, Fe, Cr.
A crystalline metal silicate having uniformly sized pores in which oxygen tetrahedrons of one or more metals selected from , Ga, , B are substituted. These crystalline metal silicates have adsorption properties and catalytic performance that cannot be obtained with conventional zeolites, and are therefore useful as molecular sieves, blue absorption agents, or catalyst components for hydrocarbon conversion reactions.

<Prior art> As the crystalline silicate containing a metal in its skeleton that has been known so far, a zeolite ZSM-5 structure containing iron is disclosed in JP-A-61-77618. However, zeolite ZSM-5, ZSM・containing iron, boron or gallium is disclosed in Japanese Patent Application Laid-open No. 113716/1983.
-11 or ZSM-12 structures are disclosed.

However, these have different structures from the TMS-14 of the present invention.

JP-A-55-149119 discloses the T M of the present invention.
An aluminosilicate zeolite is disclosed that has a powder X-ray diffraction pattern similar to S-14. This zeolite contains aluminum and silicon in its framework, but no zinc, iron, chromium, gallium or boron.

<Problem to be solved by the invention> In zeolite, that is, aluminosilicate, Sio 7
/A There were limits to the control of the suction characteristics and catalyst performance by controlling the 1203 ratio. By having a zeolite structure and containing different atoms in the crystal lattice, the present inventors have developed a crystalline structure that has pore size and solid acid properties that cannot be obtained with conventional zeolites, that is, adsorption properties and catalytic performance. As a result of extensive research aimed at synthesizing metal silicates, the present invention was achieved.

Means and Effects for Solving the Problems The novel substance of the present invention contains in its crystal lattice, in addition to silicon, one or more metals selected from zinc, iron, chromium, gallium, and boron, or these and aluminum. containing H, expressed as the molar ratio of oxides, (1±0.3)M,...O a Z n O b T 2 0 .

(1-a-b) A120s 'xsio2 (wherein a,
b satisfies 0≦a≦1.0≦b≦1, and o<
A number where (a+b)≦1, X is 5000-2500a
≧X≧(50-25a), M is at least one cation, T is one or more metals selected from Fe, Cr, Ga, and B, and n is the valence of M. It is a crystalline metal silicate characterized by having a chemical composition on an anhydrous basis as shown in Table 1, 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 Plane spacing d (A) Peak intensity 11.67±0.65 M~S 10.11±0.50W-M 5.84±0.15 W 4.17±0.07 5-VS 3.89f0.07 VS 3.59±0.06 W 2.84±0.04 W (In the table, W, M, S, and VS are each weak.

If the above X is less than 5O-25a, it cannot have the powder X-ray diffraction pattern shown in Table 1, and on the other hand, 5000-
If it exceeds 2,500a, it becomes virtually indistinguishable from that made only of SiO2, and it becomes difficult to provide the properties aimed at by the present invention.

The method for producing the crystalline metal silicate TMS-14 of the present invention will be described below.

Tetramethylammonium compound; silicon source; zinc, iron,
A metal source of chromium, gallium, boron with I PI or higher or a metal source of these and aluminum; a hydroxy ion source; and water are mixed to form a composition represented by the following molar ratio, Si/Q 25-3000OH-/
S i 02 0.04-0.1O
H20/S i 02 15~60T MA
/ S i O20,05~1.0 (however, Q is A
I + Z n * Fe + Cr +
Ga, B's IP! In the above (excluding those consisting only of Al), TMA represents a tetramethylammonium compound. The same applies hereinafter)), the reaction mixture is maintained at a temperature of 100°C to 200°C to crystallize, and then the T
MS-14 can be obtained.

Tetramethylammonium compound, silicon source, zinc source, iron source, chromium proof, gallium source, boron source, aluminum source,
The hydroxy ion source is not particularly limited.

For example, as the tetramethylammonium compound, a tetramethylammonium halide or hydroxide can be used. As the silicon source, water glass, sodium silicate, colloidal silica, amorphous silica, fumed silica, etc., which are conventionally used in zeolite production, can be used. As the zinc source, iron source, chromium source, gallium source, boron source and aluminum source, salts, oxides, hydroxides, etc. containing these metals can be used. Hydroxy ions can be obtained by adding hydroxides of alkali metals, alkaline earth metals, ammonium, etc., or by adding alkaline raw materials as other raw materials, such as tetramethylammonium hydroxide as a tetramethylammonium compound.
It is introduced by using water glass, sodium silicate, etc. as a silicon source.

Tetramethylammonium hydroxide, water glass.

When using highly alkaline raw materials such as sodium silicate, in addition to the above raw materials, in order to obtain suitable reaction conditions,
Neutralization with acids such as sulfuric, phosphoric, or hydrochloric acids may be necessary.

The composition of the reaction mixture, expressed in molar ratios, should be as follows:

Si/Q 25~3000OH-/S
i02 0.04~0.1OH, O/5i02 1
5-60 TMA/SiO20.05-1.0 This is because when the value of Si/Q is less than 25, crystallization does not proceed. Moreover, if the value of O H-/S IO2 is smaller than 0.04, crystallization will not proceed, and if it is larger than 0.10, silicate with a different structure will be generated as a by-product. H2
If the value of 0/S i 02 is less than 15, a reaction mixture with a suitable viscosity cannot be obtained, and if it is greater than 60, the desired product can be obtained, but the yield is low and it is not efficient.

When the value of TMA/5in2 is less than 0.05, silicate minerals are produced as a by-product, and when it is more than 1.0, the desired product can be obtained, but it is not economical.

If the reaction mixture is heterogeneous, impurities may be produced as by-products, so these raw materials are preferably added with stirring until the final reaction mixture is substantially homogeneous.

The final reaction mixture thus obtained is crystallized in a sealed pressure vessel made of stainless steel lined with an inert plastic material, such as polytetrafluoroethylene, to prevent contamination with impurities. Crystallization is preferably carried out under natural pressure by maintaining the temperature at 100°C to 200°C until crystals of TMS-14 form. Generally, TMS-14 can be obtained by standing at this temperature for about 2 hours to about 300 hours. The product is recovered by conventional separation methods such as filtration or centrifugation.

X-ray diffraction of the products herein was performed using Phlflip
Powder X-ray diffractometer PW1700 manufactured by S Company. Note that a Cu K-a ray is used as a radiation source, an edible divergence slit is used, and the X-ray irradiation area on the measurement sample is kept constant to determine Δp1.

<Effects of the Invention> TMS-14 produced as described above contains tetramethylammonium ion or its compound in its pores. TMS-14 containing this organic matter is
If necessary, by firing at 350°C to 600°C,
This organic matter can be decomposed and removed. TMS-14
The powder X-ray diffraction pattern of is not essentially changed by this firing.

The TMS-14 from which organic substances have been removed can then be subjected to an ion exchange operation to control its pore diameter and absorption characteristics, and can be effectively used as a variety of absorption separation agents.

Also ammonium hydroxide, ammonium sulfate.

Alternatively, it can be converted into an ammonium form by ion exchange with an aqueous solution of an ammonium salt such as ammonium nitrate, and then ammonia is removed by calcination at 400°C to 700''C to form a hydrogen form with high catalytic activity, which can be used as a solid acid catalyst. Furthermore, a desired catalytically active component such as platinum can be introduced by ion exchange or support, and used as a catalyst for various reactions such as hydrocarbon conversion reactions.

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 Water glass (S i 02-29, 30 wt%
.

N a 2 0-9. 35wt%, A12o, -0
゜016 wt%, H, 0-61,334 wt%).

A reaction mixture having the following composition was prepared by mixing chromium trichloride, sulfuric acid (95%), tetramethylammonium chloride, and pure water.

S i / Cr 50 OH- / S i 02 0.06 H20/SiO□ 45 TMA"/5iO70,4 (TMA+ represents tetramethylammonium ion. The same applies hereinafter.) This reaction mixture is sealed in an autoclave, The mixture was heated to 160"C under natural pressure with constant stirring and maintained at this temperature for 1 DEG to obtain a crystalline product. This was filtered and dried at 110°C.

Chemical analysis revealed that this product had the following molar composition of the anhydride base:

0.92 (TMA) 20' 0.17N a 2
0''Cr203 110s fo2 This product was the chromosilicate TC3-14 of the present invention having the powder X-ray diffraction pattern shown in Table 2.

Table 2 d (A) Relative strength (%) 11.69 54 10.11 20 7.19 8 6.44 5 5.85 12 5.40 4 4.17 86 3.89 100 3.57 19 3.40 10 3, 24 9 2.85 14 2.47 4 S i / Z n 3
0OH-/S i02 0. 08H20/
S i O□ 45T M A ”/S
i 02 0゜3 This reaction mixture was sealed in an autoclave and heated to 170℃ under natural pressure with constant stirring.
and held at this temperature for 8 days to obtain a crystalline product. This was filtered, washed with water, and then dried at 110°C.

This product had the following molar composition in anhydride groups according to chemical analysis.

0.8ti (TMA) 20 φ0.19N a 2
0.ZnO pot 32SiO2 This product was the zincosilicate TZS-14 of the present invention having the powder X-ray diffraction patterns shown in Table 3.

Example 2 A reaction mixture having the following composition was prepared in the same manner as in Example 1, except that zinc chloride was used instead of chromium trichloride.

Table 3 d (A) Relative strength (%) 11.70 17 10.13 10 Example 3 Except for using gallium oxide instead of chromium trichloride,
A reaction mixture having the following composition was prepared in the same manner as in Example 1.

S i / G a 50 OH- / S i 02 0. 06H20/S
i 02 45 TMA" / S i O This was filtered, washed with water, and then dried at 110°C.

According to chemical analysis, this product had the following molar composition of anhydride.

0.98 (TMA) 20 ・0.09N a 20
-Ga 203 l1ls l 02 This product was the gallosilicate TGS-14 of the present invention having the powder X-ray diffraction pattern shown in Table 4.

Table 4 d (A) 11.68 10.11 7, 18 6, 09 5, 84 4, 65 4, 17 3, 89 3, 59 3, 40 3, 36 3, 23 2, 84 2, 47 2, 39 Relative strength (%) d (A) 11.67 10.10 7, 18 5, 82 4, 17 3, 89 3, 59 3, 39 3, 22 2, 84 2, 47 2, 39 Table 5 Relative strength (%) Example 4 A reaction mixture having the following composition was prepared in the same manner as in Example 1, except that iron trichloride was used instead of chromium trichloride.

Si/Fe 100OH-/S
The reaction mixture of i 02 0,08 H20/S io2 45 TMA" / S io After filtering and washing with water,
It was dried at 110°C.

Chemical analysis revealed that this product had the following molar composition based on anhydride groups.

0.91 (T MA) 20 ・0.2ON a 2
0 .F e203 195s i 02 This product was the iron silicate TFS-14 of the present invention having the powder X-ray diffraction pattern shown in Table 5.

Example 5 Example 1 except that boric acid was used instead of chromium trichloride.
A reaction mixture having the following composition was prepared in the same manner as above.

S i / B 50 OH- / S i 02 0. 06H20/S
i O245 TMA' /S io2 0.3 The reaction mixture was sealed in an autoclave, heated to 160° C. under natural pressure with constant stirring, and maintained at this temperature for 10 [1] to give a crystalline product of 11? Ta. This was filtered for 4'i, washed with water, and then dried at 110°C.

According to chemical analysis, this product had the following molar composition of anhydride.

0.95 (TMA) 20 ・0.16N a 20
-B 20 i 103S io 2 This product was the borosilicate TBS-14 of the present invention with the powder X-ray diffraction pattern shown in Table 6.

d (A) 11.60 10.02 7, 12 5, 82 4, 17 3, 89 3, 59 3, 42 3, 36 3, 22 2, 83 2, 47 2, 38 Table 6 Relative strength (%) Example 6 A reaction mixture having the following composition was prepared in the same manner as in Example 1, except that zinc chloride and gallium oxide were used instead of chromium trichloride.

S i / Z n 100 S i / G
a 100OH-/S i 02 0.
08 H20/SiO245 TMA” /S i 02 0.4 This reaction mixture was sealed in an autoclave, heated to 160° C. under natural pressure with constant stirring, and maintained at this temperature for 1011 to obtain a crystalline product. This was filtered, washed with water, and then dried at 110°C.

Chemical analysis revealed that this product had the following molar composition of anhydride groups.

(1,9(1(TMA) 20 jar 0.15N a 2
0 ・0, [13ZnO-0,37Gaz 03 70
．． 9S i OtThis product is a zincogallosilicate TZGS of the present invention having a powder X-ray diffraction pattern shown in Table 7.
-14.

d (A) 11.69 10.12 7, 20 6,09 5,85 4, 65 4, 18 3,89 3,60 3, 39 2,85 2, 63 2,47 2,40 Relative strength (%)

Claims (2)

[Claims] (1) Expressed in molar ratio of oxides, (1±0.3)M_2_/_aO・aZn0・bT_2O_3・(1-a-b)Al_2O_3・xSiO_2 (where a and b are 0≦a≦1 , a number that satisfies 0≦b≦1 and 0<(a+b)≦1, x is 5000-250
A number that satisfies 0a≧x≧(50-25a), M represents at least one kind of cation, and T represents Fe, Cr, Ga, B.
Powder X-ray powder containing one or more metals selected from A crystalline metal silicate characterized by having a diffraction pattern. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the table, W, M, S, and VS represent weak, medium, strong, and very strong, respectively) (2) A tetramethylammonium compound; a silicon source; a metal source of one or more of zinc, iron, chromium, gallium, boron or these and aluminum; a hydroxy ion source; and water, mixed at the following molar ratio: The composition shown is: Si/Q 25-3000 OH^-/SiO_2 0.04-0.10 H_2O/SiO_2 15-60 TMA/SiO_2 0.05-1.0 (however, Q is Al, Zn, Fe, 1 of Cr, Ga, B
Seeds and above (excluding those consisting only of Al),
TMA stands for tetramethylammonium compound. ), and the reaction mixture was heated to 100°C.
A method for producing a crystalline metal silicate according to claim 1, characterized in that the temperature is maintained at a temperature of from 200°C to 200°C.