JPS59184723A - 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 allowing a mixture of silica source, alumina source, alkaline and alkaline earth metallic source, specified metallic source except Si and Al, water and methanol in a limited ratio to react. CONSTITUTION:Crystalline metallo silicate shown by a formula (M is alkali metal and/or alkaline earth meral; X is >=1 king of metals of the I B, IIB, III-V, VIB, VIIB, VIII groups in the periodical table except Si and Al; (p), (q), (r) are respectively 0.01-50.0, 0.1-20.0, 0.1-10; (m), (n) are respectively the atomic valence of M, X) is made by heating and allowing to react a mixture of silica source, alumina source, M source, X source, water and methanol. The quantity ratio of silica source to M source is 0.1-3 by the molar ratio of M2/m/SiO2 and the quantity ratio of silica source to alumina source >=10 by the molar ratio of SiO2/XOm/2. And methanol/SiO2, methanol/water are respectively 1-100, 0.2-5.

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.

Composite products generally consist of a silica (SiO2) source and alumina (A
t20B) Various metals, mainly fc
It is produced by reacting a certain amount of acetate with a predetermined quantity 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.
2-43800).

All of the crystalline metallosilicates obtained by these methods are ZSM-, which is famous as a crystalline aluminosilicate.
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 new method for the total production of crystalline aluminosilicate by reacting an alumina source, an alkali metal source or an alkaline earth metal source, and water.
See No. 16395.

The purpose of the present invention is to provide a method for producing a crystalline metallosilicate having a new composition and having the same crystal structure and molecular sieving action as the crystalline aluminosilicate proposed in the above-mentioned Japanese Patent Application No. 16395/1982. It is.

That is, the method for producing a crystalline metallosilicate of the present invention is as follows: (wherein, M represents an alkali metal and/or an alkaline earth metal; X is a group IB of the periodic table;

Represents at least one metal belonging to Group ■, Group ■, Group V, Group ■B, Group ■B, or Group ■ (excluding silica and aluminum); p, q + r, Each represents a number from 0.01 to 50, 0.1 to 20, and 0.1 to 10; m and n represent the valences of M and X, respectively. ) is the method for producing crystalline metallosilicate,
The method is characterized in that a silica source, an alumina source, an M source, an M source, water, and methanol are mixed, and the resulting mixture is reacted while being heated.

The crystalline metallosilicate obtained in the present invention is shown in the following table: (However, in the table, 9 are very strong, 9 are strong, and are moderate.

Weak indication is 70~100.40~70°15
~40, representing a relative intensity of 0 to 15. ) It has a crystal structure shown as:

In the method of the present invention, first, the above-described silica source, alumina source 2M source, M source, water, and methanol are mixed in a quantitative ratio that satisfies the molar ratios described below to form an aqueous mixture. Prepare.

Among these six types of components, the silica source, the alumina source 1M source, and the M source all 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. Dissolved silica includes, for example, N
A water glass, alkali metal silicate, containing from 5 iOzl to 5 mol per 201 mol of a2O or a2O can be obtained.

Various sources can be used as the alumina source, and examples include aluminum sulfate, aluminum nitrate, pseudoboehmite, boehmite, sodium aluminate, colloidal alumina, and a mixture of two or more of each. can. The quantitative ratio of silica source and alumina source in the aqueous mixture is 1siO□ and At2, respectively.
When expressed in the form of 03, S ioz /) Jt Os
The molar ratio is set to be 10 or more. Preferably, it is within the range of 40 to 1000.

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 lupisoum hydroxide; Compounds of alkaline earth metals such as calcium nitrate, calcium chloride, notrium bromide, and strontium chloride. Alternatively, two or more appropriately selected ones 'ff: can be mentioned. Sodium is particularly preferred as the M source in the method of the present invention.

The quantitative ratio of the silica source and the M source in the aqueous mixture was 5 in2. When expressed in the form of M20 (m is the valence of M), it is set within a range that satisfies the relationship of M to SiO2 molar ratio dE0.1 to 3. Preferably 0.2
0, which is in the range of 1 to 1. These M sources may be appropriately selected in relation to the type of M contained in the crystalline metallosilicate having the target composition to be produced. In the method of the present invention, it is particularly preferable to use it in the form of an oxide.

The X sources are Group IB, Group IIB, Group ■, and Group ■ of the periodic table.

Any of the oxides, hydroxides, chlorides, nitrates, and sulfates of at least one metal belonging to Group ■, Group VfB, Group ■B, or Group ■ (excluding St and At); or Among them, suitable combinations of two or more types can be mentioned. These X sources may be appropriately selected in relation to the type of ML:D contained in the crystalline metallone of the desired composition to be produced.

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

The amount ratio of silica source and alumina source in the aqueous mixture is 5i
02/AL203 is 10 or more, preferably 40 to 100
0, the quantity ratio of the silica source and the X source is k SiO2
, XOn (where n is the valence of X), the molar ratio of SiO2/X0xL is set to be 10 or more. Preferably, it is within the range of 40 to 1000.

In the aqueous mixture according to the present invention, methanol is not contained as a component of the target crystalline metallosilicate, but plays an important function in forming the crystal structure of the crystalline metallosilicate in the entire manufacturing process. Component 3, in the method of the present invention, the amount of methanol used is methanol/5102 expressed in molar ratio.
It is necessary that methanol/water satisfies the relationship of 1 to 100° and 0.1 to 10. Preferably methanol/
S10□ is 3-60. Methanol/water is the amount of methanol in the range of sails 2-5.

The aqueous mixture according to the present invention is reacted under the reaction conditions described below to completely form the crystalline metacosyl-inocate of the present invention. At this time, the amount of hydroxyl groups in the aqueous mixture is expressed as a molar ratio of hydroxyl group/SiO□ is adjusted so as to satisfy the relationship of 0.01 to 0.5 and preferably 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 a crystalline metallosilicate with such a composition and crystal structure.

The aqueous mixture may be prepared by separately preparing a solution of each component, or by preparing a mixed solution of each component in an appropriate combination, 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
20 to 200°C; reaction time is 5 hours to 10 days, preferably 10 hours to 5 days; pressure is not particularly limited and is usually autogenous pressure. The reaction usually proceeds 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).

The crystalline metallosilicate of the present invention is disclosed in Japanese Patent Application No. 57-16
It has the same crystal structure as that proposed in No. 395, and is a solid acid, and is useful as a catalyst, catalyst carrier, and adsorbent in the chemical industry in general, and in particular in the field of petroleum refining and petrochemical industry.

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

Example 1 Aluminum sulfate (18 hydrate) 7.52y (At2
0. .

0.011 mol (in the form of water, 0.20 mol) and 0.7 f (0.01 mol) of boron oxide in the form of sulfuric acid (concentration 97%)
17.61 (0.17 mol) and water 150 tr=l (8
, 33 mol) was prepared. 29.0% by weight of silicon dioxide, 9.4% by weight of IJium oxide,
Water glass 2114 consisting of 61.1% by weight of water (silicium dioxide X: 1.02 mol, sodium #chloride: 32 mol.

Water: 7.16 mol) to 96 rnl (5.33 mol) of water
Leakage B was prepared by dissolving it in

Solution A and solution Bf were gradually added dropwise into the reaction vessel and both were thoroughly mixed by stirring. Then, dilute sulfuric acid was added to adjust the overall pH to 18.
5, then add 376 ml of methanol (9,3
mol) was added and mixed, and the whole was placed in an autoclave with an internal volume of 1 ton and heated at 170°C under autogenous pressure while stirring.
The reaction was allowed to proceed for 0 hours.

The resulting reaction mixture was washed five times with 1.51 g of water, then filtered to remove the solids, and dried at 120° C. for 6 hours. A crystalline silicate of SP was obtained.

After baking this product at 1550°C for 6 hours, the set IffU
, 1. ONa2O” 1.0 B2O3・1.2 A7
20s” 6 songs on Zoo S io2.

A complete diagram of nine turns of X-ray diffraction of this product and Table 1 are also shown.

Table 1 Example 2 Ferric nitrate (nase hydrate) 8.05S in place of boron oxide 0
'Example 1 except that (0.02 mol) was used.
Crystalline silicate was produced in a similar manner.

The composition after firing is 3. I Na, 0 ・2.2 Fe2
O,・1.5 At20. It was @100sio2. The X-ray diffraction values of this product are shown in Table 2.

Table 2 Example 3 Chromium nitrate (nase hydrate) 8.00P as a substitute for boron oxide
A crystalline silicate was produced in the same manner as in Example 1 except that 0.02 mol of CO was used.

The composition after firing is as follows: 3. lNa2O*1.2Cr, 03
m1. lAt20.・It was 1005i02. The X-ray diffraction curve of this product is shown in Table 3.

Example 4 Orthophosphoric acid (concentration 85%) 2 instead of boron oxide
．． A crystalline silicate was produced in the same manner as in Example 1 except that 6r (0.02 mol) was used. The composition after firing is 3. ONa2Oga0.9P205'
It was 1.2A2203・1005in2. The X-ray diffraction pattern of this product is shown in Table 4.

Crystalline silicate was produced in the same manner as in Example 1, except that the total pH of the mixture of solution A and solution B was adjusted to 10.5. The composition after firing is L5 Na2
Om 1.0 B2O3111-3Al2O, * 10
It was 0 Sin.

The X-ray diffraction pattern of this product is shown in Table 5.

Example 6 A 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 -7.5. The composition after firing is 1.7 Na
2Oa O-9B2O5・1+lAt203 @100
S i02 Te Atsuta.

The X-ray diffraction pattern of this product is shown in Table 6.

Example 7 A 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 140° C. and 4 days. Set IN after firing is 1.4Na20・0.8B20a
・It was 1.3AL203・100Si02. The X-ray diffraction pattern of this product is shown in Table 7.

Example 8 Solution A contains 7 g (0.01 mol) of boron oxide and 5 sulfuric acid (
97% concentration) 8.89 (0.09 mol) and water 75
m/ (4.17 mol), solution B consists of 29.0% by weight of silicon dioxide, 9.4% by weight of IJ oxide, 61.1% by weight of water.
05F (silicon dioxide: 0.51 mol, sodium oxide: 0.1'6 mol, water: 3.56 mol), and the amount of methanol used is 560-(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 1,5Na20・0.8B203・1
．． It was 2At203@100SIO2. The entire X-ray diffraction pattern of this product is shown in Table 8.

Table 8

[Brief explanation of drawings]

The figure shows the X-ray diffraction pattern of the crystalline silicate produced in Example 1. Procedural amendment dated May 26, 1980 Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case Patent Application No. 59160 of 19822, Title of invention Process for manufacturing crystalline metallosilicate3, Person making the amendment Case Relationship with Patent Applicant Name New Fuel Oil Development Technology Research Association (Name) 5. Date of amendment order Voluntary 6. Number of inventions increased by amendment None 7. Subject of amendment Detailed explanation of the invention in the specification (1) Specification page 8 18
In lines 19 to 19, "the amount of hydroxyl groups is" is supplemented with "the amount of hydroxyl ions is". (2) "Hydroxy group/510" described in page 8, line 18 of the specification
24 is corrected as [hydroxide ion/5102 J. (3) In the first line of page 9 of the specification, next to “...adjusted.” “In this case, the amount of hydroxyl ions is calculated from the amount of acid and base in the raw material mixture.” Insert "This is what was requested." (4) "3.2 moles" stated on page 10, line 18 of the specification is corrected to "rO,32 moles". (5) "Dilute sulfuric acid" described on page 11, line 3 of the specification
% sulfuric acid 12.0 gJ. (6) “Adjustment” written on page 16, line 3 of the specification is changed to “adjustment (
0.3 g of 50% sulfuric acid was added).” (7) “Adjustment” written on page 17, line 3 of the specification is changed to “adjustment (
21.0g of 50% sulfuric acid was added).”

Claims (1)

[Claims] (In the formula, M represents an alkali metal and/or an alkaline earth metal; X is a group IB or IIB of the periodic table. or represents at least one metal belonging to group III (excluding silicon and aluminum); p, q, and r each represent 01
-50, 0.1-20, 0.1-10; m and n represent the valences of M and X, respectively. ) A method for producing a crystalline metallosilicate,
A method for producing crystalline metallosilicate, which comprises mixing a silica source, an alumina source, an M source, an X source, water, and methanol, and reacting the resulting mixture while heating.