JPS59184722A - Manufacture of crystalline metallosilicate - Google Patents

Abstract

PURPOSE:To obtain useful silicate as a catalyst, catalytic carrier and adsorbent shown by a specified formula, by heating and sllowing a mixture of silica source, alkaline earth metallic source, specified metallic source excluding Si and Al water and methanol toreact with each other in a limited ratio. CONSTITUTION:Crystalline metallosilicate shown by a formula (M is alkali metal and/or alkaline earth metal; X is >=1 kinds of metals of the I B, IIB, III-V, VIB, VIIB, VIII groups in the periodical table except Si and Al: (p), (q) are respectively 0.3-3.0, >=10; (m), (n) are respectively the atomic valence of M, X) is made by heating and allowing a mixture of silica source, metallic source, X source, water and methanol to react with each other. The quantity ratio of silica source to M source is 0.1-3 by the molar ratio of M2/m0/SiO2 and the quantity ratio of silica source to X source >=5 by the molar ratio of SiO2/Xm/2. And methanol/SiO2, methanol/water are respectively 1-100, 0.1- 10.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing crystalline metallosilicates.

Various crystalline metallosilicates are widely used in fields such as adsorbents, catalysts, and catalyst supports by effectively utilizing their molecular sieving and solid acid functions.

A large number of such crystalline metallosilicates are known, including naturally occurring ones and synthetic ones.

Synthetic products are generally made from silica (Sigh) source ♂ alumina (A
It is produced by reacting various metal sources, mainly lzO3, in a predetermined ratio in an aqueous solution. Recently, a method for reacting by adding a predetermined amount of alcohol to this aqueous solution has been developed (U.S. Pat. No. 4,199,556, JP-A-52-438).
(See Publication No. 00).

All of the crystalline mecrosilicate obtained by these methods are known as crystalline aluminosilicate, which is known as ZSM.
It has the same crystal structure as Zeolite-5 and Zeta-3 (both trade names).

In addition, in the presence of a relatively large amount of methanol, the silica source,
We have proposed a method for producing a new crystalline aluminosilicate by reacting an alumina source, an alkali metal source or an alkaline earth metal source, and water (Japanese Patent Application No. 1983-
16395).

The present invention is based on the crystalline aluminosilicate and its crystal structure and molecule 1 proposed in the above-mentioned Japanese Patent Application No. 16395/1982.
The object of the present invention is to provide a novel method for producing a crystalline metallosilicate which has the same effect as No. 11, but does not contain aluminum (A7) as a skeleton component.

That is, the method of the present invention is as follows: (wherein M represents an alkali metal and/or an alkaline earth metal;
At least one metal belonging to Group 1, Group 1, Group 2B, Group 2B, or Group 2 (excluding silicon and aluminum).

); p and q are 0.3 to 3.0 and 10, respectively.
m and n represent the valences of M and This is a method for producing a crystalline metallosilicate, characterized in that the mixture is reacted while being heated.

The crystalline metallosilicate obtained in the present invention is shown in the following table: (However, in the table, 1 is very strong, 1 is strong, and is moderate.

The weak indications are 70-100.40-50.15, respectively.
~40. Represents relative intensity from o to 15. ) It has a crystal structure shown as

In the method of the present invention, first, an aqueous mixture is prepared by mixing the 2M silica source, the X source, water, and methanol in a quantitative ratio that satisfies the molar ratios described below.

Of these five types of components, the silica source 2M source and the X source both serve as skeleton components of the target crystalline metallosilicate.

The silica source used in the present invention is not particularly limited, and may include silica powder, silicic acid, colloidal silica, dissolved silica, and the like. Among these, fused silica is preferred. The dissolved silica may be, for example, a water glass containing from 1 to 5 moles of 5i per 201 moles of Na2O or a silica salt of an alkali metal.

M sources include sodium hydroxide, potassium hydroxide, sodium silicate, and sodium aluminate.

Compounds of alkali metals such as potassium silicate, lithium hydroxide, cesium hydroxide, and rubidium hydroxide; and compounds of alkaline earth metals such as calcium nitrate, calcium chloride, barium bromide, and strontium chloride, respectively, or selected as appropriate. You can list two or more things. Sodium is particularly preferred as the M source in the method of the present invention.

When the ratio of silica source and M source in an aqueous mixture is expressed in the form of Si02 r M20 (m is the valence of M), the relationship is satisfied when the molar ratio of M20/5i02 is 1 to 3. is set within the range. Preferably 0.2
~1. These M sources may be appropriately selected in relation to the type of M contained in the crystalline metallosilicate having the intended composition to be produced. In the method of the present invention, it is particularly preferable to use it in the form of an oxide.

X sources are Groups IB, JIB, III, and ■ of the periodic table.

Group V r At least one member belonging to Group ■B, ■B, or ■group
oxides of metals in rows (excluding Si and At),
Examples include hydroxides, chlorides, nitrates, and sulfates, or an appropriate combination of two or more of these. These X sources may be appropriately selected in relation to the type of X contained in the crystalline metallosiligate having the desired composition to be manufactured.

In the method of the present invention, it is particularly preferable to use it in the form of an oxide.

The quantitative ratio of the silica source and the X source in the aqueous mixture is such that the molar ratio of SiO2/XOn is 5 or more when expressed in the form of Sigh and XOI (n is the valence of X), respectively. Set. Preferably 20-1000
It is better to be within the range of .

In the aqueous mixture according to the present invention, methanol is not contained as a component of the target crystalline metallosilicate, but it plays an important function in forming the crystal structure of the crystalline metallosilicate in the entire manufacturing process. It is an ingredient. In the method of the present invention, the amount of methanol used is methanol/81 (h is 1
~100 It is necessary that methanol/water satisfies the relationship of 0.1 to 10. Preferably methanol/5iO
z is 3-60. Methanol/water is a methanol needle in the range of 0.2-5.

The aqueous mixture according to the present invention is reacted under the reaction conditions described below to form the crystalline metallosilicate of the present invention, and in this case, the amount of hydroxyl groups in the aqueous mixture is determined in a molar ratio of hydroxyl groups/5i02. 0.01-0.5. Preferably, it is adjusted to satisfy the relationship of 0.01 to 0.3.

In such an aqueous mixture, if the quantitative ratio of each component is out of the range that satisfies the above-mentioned relationships, or if even one of the relationships is not satisfied, the method of the present invention will not meet the objectives. It is not possible to form crystalline metallosilicates with a composition and crystal structure that

The aqueous mixture may be prepared by separately preparing a solution of each component, or by preparing a mixed solution of each component by appropriately combining them, and finally mixing them as a whole.

In the method of the present invention, the components are then reacted while heating the aqueous mixture prepared as described above.

The reaction is carried out, for example, in an autoclave, and the reaction conditions include a temperature of 100 to 300°C, preferably 1
The reaction time is 20 to 200°C, reaction time is 5 hours to 10 days, preferably 10 hours to 5 days, and the pressure is not particularly limited and is usually autogenous pressure. The reaction is usually carried out under stirring.

After the reaction is completed, the reaction mixture is washed with water and heated to a specified temperature (usually 120℃).
The desired crystalline metallosilicate can be obtained by drying at a temperature of about 30°F (°C).

Although the crystalline metallosilicate of the present invention does not contain At as a skeleton component, it has the same crystal structure as that proposed in Japanese Patent Application No. 57-16395, is a solid acid, and is useful in the chemical industry in general, especially It is useful as a catalyst catalyst carrier and adsorbent in the fields of petroleum refining and petrochemical industries.

The present invention will be explained in more detail below based on examples.

Example 1 Boron oxide 1.4 F (0.02 mol) was dissolved in sulfuric acid (97
% concentration) 17.6 F (0,17 mol) and water 15
A solution A was prepared in which 0.0 g (8.33 mol) was dissolved. Water glass 2112 consisting of 29.0 parts by weight of silicon dioxide, 9.4 parts by weight of sodium oxide, and 61.1 parts by weight of water (silicon dioxide: 1.02 mol, sodium oxide: 3.2
A solution B was prepared by dissolving 96 moles of water (7.16 moles) in 96 moles of water (5.33 moles).

Solution A and solution B were gradually dropped into the reaction container and mixed by stirring. Then, dilute sulfuric acid was added to adjust the overall pH to 8.
5, methanol 376-(9.3 mol) was added thereto and mixed, and the whole was placed in an autoclave with an internal volume of 1 t and heated at 170°C under self-pressure while stirring for 20°C.
Allowed time to react.

The resulting reaction mixture was filtered to remove the solid content, which was dried at 120° C. for 6 hours to obtain 530y of crystalline silicate.

After calcining this product at 550°C for 6 hours, the composition is 1
．． '3 Ivy with Na2O・B2O3・1255iOz.

Further, the X-ray diffraction pattern of this product is shown in the figure and Table 1.

Table 1 The amount of boron oxide in solution A is 0.7 f (0,01
A crystalline silicate was produced in the same manner as in Example 1, except that the amount was (mol). Composition after firing is 1.5N
It was a2O fist 1h03・1625iOz. The X-ray diffraction pattern of this product is shown in Table 2.

Table 2 Example 3 Ferric nitrate (nase hydrate) 8.08f instead of boron oxide
A crystalline silicate was produced in the same manner as in Example 1 except that (0.02 mol) was used.

The composition after firing is 1.2 NazO'Fe2O3" 8
It was 1.78io2j. The X-ray diffraction i4 turn of this product is shown in Table 3.

Example 4 Chromium nitrate (9 water 4) s, o instead of boron oxide.

Example 1 except that f (0.02 mol) was used
Crystalline silicate was produced in a similar manner.

The composition after firing is 2.8 Na2O@Crz03”
It was 75.88 iO2. X-ray diffraction of this item No. 4
The turns are shown in Table 4.

Example 5 Crystalline silicate was produced in the same manner as in Example 1, except that the pH of the mixture of solution A and solution B was adjusted to 10.5, and the composition after firing was as follows: 1.3 Na2
O11B203 ・885io2Ttb Ivy. The X-ray diffraction of this product is shown in Table 5.

Table 5 Crystalline silicate was produced in the same manner as in Example 1, except that the pH of the mixture of solution and solution B was adjusted to 7.5. The composition after firing is 2, I Na2
O@B2O3' 128 S ioz. The X-ray diffraction pattern of this product is shown in Table 6.

Table 6 Example 7 Crystalline silicate was produced in the same manner as in Example 1, except that instead of the reaction temperature of 170'C and the reaction time of 20 hours in Example 1, the reaction time was 140C and 4 days. Manufactured. The composition after firing is 1.3Na20・B2O3”102
Si02T6tsu7,z. The xs diffraction pattern of this vo is shown in Table 7.

Example 8 Solution A is boron oxide 7f (0.01 mol).

Solution B consists of sulfuric acid (97% concentration) 8.8 f (0.09 mol) and water 75 m (4.17 mol), and solution B contains 29.0 weight J of silicon dioxide and 9.4 N of sodium oxide. Water glass 10 consisting of 61.1% water
It is composed of 5f (silicon dioxide: 0.51 mol, sodium oxide: 0.16 mol, water: 3.56 mol), and the methanol stool volume is 560 m7! (13
A crystalline silicate was produced in the same manner as in Example 1, except that the amount was 9 mol).

The composition after firing is 1. ONa2O@B2O3・109
There was S iCh te. The X-ray diffraction pattern of this product is shown in Table 8.

Table 8 Example 9 Orthophosphoric acid (concentration 85%) 2 instead of boron oxide
．． A crystalline silicate was produced in the same manner as in Example 1 except that 6 F (0.02 mol) was used. The composition after firing is 1.5 NazOe P2O5・85S
It was iO+. The X-ray diffraction pattern of this product is shown in Table 9.

Table 9

[Brief explanation of the drawing]

The figure shows an X-ray diffraction pattern of the crystalline silica produced in Example 1. ) Procedural amendment dated May 26, 1980, Mr. Kazuo Wakasugi, Commissioner of the Patent Office], Indication of the case, Patent Application No. 59159 of 1981 2, Name of the invention: Process for producing crystalline metallosilicate: 3. Relationship with the case of the person making the amendment Name of the patent applicant Name New Fuel Oil Development Technology Research Association (Name) 5. Date of amendment order A. Spontaneous (5. Number of inventions increased by amendment None 7. Subject of amendment Description Column 8 of Detailed Description of the Invention, Contents of Amendment (1) "The amount of hydroxyl groups is
" is corrected as "The amount of hydroxyl ion is." (2) “Hydroxy group/5iO2” described in page 8, line 8 of the specification
J is corrected as "Hydroxy ion / 5i02 J." (3) On page 8, line 10 of the specification, after "... will be adjusted", "In this case, hydroxide ion / 5i02 J. The stars are calculated from the amounts of acid and base in the raw material mixture.'' Insert. (4) "Dilute sulfuric acid" described on page 10, line 11 of the specification is "5"
Correct to 14.8 gJ of 0% sulfuric acid. (5) “Adjustment” written on page 15, line 3 of the specification is changed to “adjustment (
0.3 g of 50% sulfuric acid was added).” (6) “Adjustment” written on page 16, line 3 of the specification is changed to “adjustment (
50% sulfuric acid 21. (added Og)”.

Claims (1)

[Claims] (In the formula, M represents an alkali metal and/or an alkaline earth metal; X is Group IB of the periodic table. Group nB, Group ■, Group ■, Group ■, Group VIB, Group ■B Or■
represents at least one metal belonging to the group (excluding silicon and aluminum); p and q are each 0.
3 to 3.0, represents a number of 10 or more; m and n are each M. Represents the valence of X. ) A method for producing a crystalline metallosilicate shown in Method for producing silicates.