JPH0674141B2 - Activated zeolite and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel activated zeolite and a method for producing the same. More specifically, the present invention is suitable as a catalyst for various reactions, particularly hydrocarbon conversion, an activated zeolite obtained by introducing a sulfone group into an aluminosilicate containing a certain metal element in the crystal lattice, and The present invention relates to a method for easily manufacturing things.

[Conventional technology]

Conventionally, zeolite-based aluminosilicate is an alkali metal salt or alkaline earth metal salt of crystalline hydrous aluminosilicate, SiO ₄ tetrahedron and AlO ₄ tetrahedron are bound together by sharing an oxygen atom, and have a three-dimensional skeleton structure. Make a lattice, dehydrate, add water,
Alternatively, it is known to have a stable crystal structure in which an essential lattice structure change is not observed even by ion exchange.

Since this aluminosilicate has the stable crystal structure as described above, it is used for various purposes by utilizing its characteristics. For example, in the skeleton of the three-dimensional network structure, there are cavities (or channels) of molecular size, and these cavities communicate with the outside through pores of uniform size,
Since the pores have a molecular size and are uniform, the types of molecules that can enter the cavities are limited, so that applications as so-called molecular sieves have been developed. Further, since the AlO ₄ tetrahedron has one negative charge, the corresponding alkali metal ion or alkaline earth metal ion is bound to the tetrahedron, and the water of crystallization is retained by the electrostatic attraction of this metal ion. Since the metal ion has a property of easily exchanging with other metal ions in an aqueous solution, it is used as a water softener, and the water of crystallization destroys the crystal structure by heating. It is widely used as a strong desiccant because it is eliminated and becomes a porous adsorbent.

Furthermore, when the alkali metal ion is exchanged with a divalent or trivalent metal ion or hydrogen ion, a strong solid acid is formed,
Due to its strong acidity, it is used as a solid acid catalyst or catalyst carrier.

By the way, various attempts have been made to introduce halogen into the aluminosilicate to improve its activity. For example, a method of introducing fluorine into a zeolite-based aluminosilicate using aluminum fluorides (Japanese Patent Publication No. 46).
-33219), a method of halogenating a crystalline aluminosilicate or a metal-supported crystalline aluminosilicate with a halogenated hydrocarbon (Japanese Patent Publication No. 49-45477), and a fluorine atom in the aluminum atom of the aluminosilicate zeolite having a mordenite structure. There has been proposed a partially fluorinated mordenite catalyst in which is bonded and a method for producing the same (Japanese Patent Laid-Open No. 59-46138).

[Problems to be solved by the invention]

However, although these halogen-introduced aluminosilicates show some improvement in activity, they are not yet sufficiently satisfactory.

The present invention has been made for the purpose of providing an activated zeolite having a remarkably improved activity.

[Means for solving problems]

The present inventors have conducted extensive studies to achieve the above-mentioned object, and as a result, introduced a certain metal element into the crystal lattice of aluminosilicate, and then contact-treated this metal-containing aluminosilicate with a sulfone group-containing compound. By doing so, it was found that the object can be achieved, and the present invention has been completed based on this finding.

That is, in the present invention, the crystal lattice contains Ib of the periodic table.
Group, Group IIb, Group IIIa, Group IIIb, Group IVa, Group IVb
To provide an activated zeolite obtained by introducing a sulfone group into an aluminosilicate containing at least one metal element selected from the group consisting of Group VIb Group VIb Group VIIb Group VIII metal elements. This is, for example, in the crystal lattice of aluminosilicate,
Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, Group IVb
It can be produced by contacting an aluminosilicate containing at least one metal element selected from the group consisting of metal elements belonging to Group VIb, Group VIIb and Group VIII with a sulfone group-containing compound. it can.

Hereinafter, the present invention will be described in detail.

The aluminosilicate containing a metal in the crystal lattice used in the present invention can be obtained by synthesizing an aluminosilicate in the presence of a metal salt.

There is no particular limitation on the structure of aluminosilicate,
It may be one having the same basic structure as natural forgerthite, or one having a structure such as large pored maledenite, X-type zeolite or Y-type zeolite. In addition, the size of the open pores is generally preferably in the range of 6 to 15Å in order for the sulfone group-containing compound to effectively contact the inner surface of the pores to be sulfonated. Furthermore, SiO ₂ / Al ₂ O ₃ (molar ratio) in the aluminosilicate is usually 10 to 500,
It is preferably selected in the range of 20 to 200.

In the present invention, the metal element introduced into the crystal lattice of the aluminosilicate, Group Ib of the periodic table,
Group IIb, Group IIIa, Group IIIb, Group IVa, Group IVb, Group V
It is selected from metal elements belonging to Group Ib, Group VIIb and Group VIII. As such a metal element, for example, Cu,
Ag, Zn, Cd, B, Ga, In, La, Sn, Pb, Zr, Cr, Mo,
Preferred examples include W, Mn, Re, Fe, Co and Ni. One kind of these metal elements may be introduced, or two or more kinds thereof may be introduced. The introduction amount of these metal elements is
/ Al (molar ratio) is preferably selected to be 0.0001 or more, more preferably 0.01 to 5.

In the present invention, the aluminosilicate containing the metal element in the crystal lattice thus obtained is subjected to a contact treatment with a sulfone group-containing compound to introduce a sulfone group into the aluminosilicate. As the sulfone group-containing compound, for example, CF ₃ SO ₃ H, FSO ₃ H, H ₂ SO _{4 and the} like are preferably used. The contact treatment method and conditions are appropriately selected depending on the kind of the sulfone group-containing compound used. For example, when CF ₃ SO ₃ H or FSO ₃ H is used as the sulfone group-containing compound, the metal-containing aluminosilicate is usually mixed with CF ₃ SO ₄ H or FSO at a temperature in the range of room temperature to 100 ° C. under reduced pressure. ₃ H
A method is used in which it is immersed in a solution such as the above for contact treatment for about 30 minutes to 5 hours, and then dried under reduced pressure at a temperature in the range of 50 to 200 ° C.

On the other hand, when sulfuric acid is used as the sulfone group-containing compound, for example, the metal-containing aluminosilicate is immersed in sulfuric acid of 10 to 36 N, preferably 50 to 300 ° C., more preferably 150 to 230 ° C. 30 minutes to 5 at temperature
After contact treatment for about an hour, it is filtered and preferably
A method is used in which drying is performed under reduced pressure at a temperature in the range of 50 to 200 ° C., if necessary, and then firing is preferably performed at a temperature in the range of 300 to 700 ° C. for about 3 to 10 hours.

In this manner, the sulfone group is introduced into the aluminosilicate by contact-treating the metal-containing aluminosilicate with the sulfone group-containing compound. The sulfone group content in the metal-containing aluminosilicate is preferably in the range of 0.01 to 20% by weight. If this amount is less than 0.01% by weight, the effect of the present invention is not sufficiently exerted, and 20% by weight
If it exceeds, the crystal structure of the aluminosilicate may be destroyed, which is not preferable.

In this way, the obtained activated zeolite of the present invention is an aluminosilicate containing the metal element in the crystal lattice, in which a sulfone group is introduced without destroying its crystal structure, It has a higher catalytic activity than conventional halogenated zeolites and is suitable as a catalyst for various reactions, especially hydrocarbon conversion.

〔Example〕

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) Synthesis of metal-containing aluminosilicate ZrO (NO ₃ ) ₂ .2H ₂ O 5.34 g, H ₂ SO ₄ 17.58 g and morpholine 8.7 g were dissolved in 250 ml of water to prepare a solution A, and water glass 2
Dissolve 10 g in 250 ml of water to prepare solution B, and add 79.0 g of NaCl.
Was dissolved in 122 ml of water to prepare a liquid C. Next, while stirring the C solution at room temperature, the A solution and the B solution were gradually added dropwise at the same time, and the mixed solution was put into an autoclave and stirred at 300 rpm at 170 ° C. Reduction 20
Reacted for hours. After completion of the reaction, the reaction solution was cooled, the solid substance was filtered off, washed with water 1 times 5 times, and then at 120 ° C. for 12 hours.
It was dried for an hour and then calcined in air at 550 ° C. for 6 hours. Then, this was added to 1 N ammonium nitrate solution 1 and ion-exchanged for 10 hours.
It was calcined in air at 550 ° C. for 6 hours. This ion exchange operation was carried out twice to obtain 51 g of zirconium-containing zeolite having a ZrO ₂ content of 6.9% by weight.

(2) Sulfonyl group introduction of metal-containing aluminosilicate 2 g of the zeolite obtained in (1) above was placed in a flask equipped with a dropping funnel, and the inside of the fusco was depressurized and kept at 150 ° C for 2 hours, then cooled to room temperature. In the above, CF ₃ SO ₃ H was added dropwise, and the zeolite was immersed and subjected to contact treatment for 2 hours. Next, the temperature was raised to 100 ° C., and the zeolite was introduced into a sulfo group-introduced zeolite by evacuation until the zeolite was dried. The zirconium content of this product was 6.1% by weight as ZrO ₂ , and the sulfone group content was 0.2% by weight.

(3) Evaluation of sulfone group-introduced zeolite 100 m of the sulfone group-introduced zeolite obtained in (2) above
g was put into a reaction tube of a flow type pulse reactor to decompose n-hexane. The pulse reaction conditions were a helium flow rate of 20 ml / min and a pulse size of 0.5 μ, and a glass chromatograph was used for analysis of the product.

The conversion rate of n-hexane is shown in a separate table.

Example 2 The same operation as in Example 1 was carried out except that FSO ₃ H was used instead of CF ₃ SO ₃ and H in (2) of Example 1. The results are shown in the attached table. The sulfone group content in the sulfone group-introduced zeolite was 0.2% by weight.

Example 3 To 2 g of the zirconium-containing zeolite obtained in (1) of Example 1 was added 20 ml of concentrated sulfuric acid and contact treatment was carried out at 100 ° C. for 2 hours. Then, the solid was collected by filtration and dried at 120 ° C.
The mixture was calcined for 6 hours to obtain a sulfone group-introduced zeolite.
The sulfone group content of this product was 0.2% by weight.

Then, in the same manner as in Example 1, a decomposition reaction of n-hexane was performed. The results are shown in the attached table.

Example 4 The same operation as in Example 3 was performed except that the temperature of the contact treatment with concentrated sulfuric acid was 200 ° C. in Example 3. The results are shown in the attached table. The sulfone group content in the sulfone group-introduced zeolite was 0.8% by weight.

Example 5 The same operation as in Example 3 was performed except that the contact treatment temperature with concentrated sulfuric acid was 250 ° C. in Example 3. The results are shown in the attached table. The sulfone group content in the sulfone group-introduced zeolite was 1.1% by weight.

Example 6 In Example 1, instead of ZrO (NO ₃ ) ₂ .2H ₂ O, Al _{2
(SO 4) 3 · 18H 2} O 7.52g and Fe (NO _{3) 3} except that using 9H ₂ O 8.09 g to prepare a solution A, in the same manner as in Example 1, producing a sulfone group introduced iron-containing zeolite Then, the decomposition reaction of n-hexane was performed. The results are shown in the attached table. The iron content in the sulfonic group-introduced iron-containing zeolite was 15.1 wt% as Fe ₂ O ₃ , and the sulfo group content was 2.7 wt%.

Comparative Examples 1 and 2 Using the metal-containing zeolite that was not subjected to the sulfone group introduction treatment in Examples 1 and 6, a decomposition reaction of n-hexane was performed. The results are shown in the attached table. Comparative Example 1 corresponds to Example 1, and Comparative Example 2 corresponds to Example 6.

[Effects of the Invention] The activated zeolite of the present invention is an aluminosilicate containing a certain metal element in the crystal lattice, in which a sulfone group is introduced without destroying its original prize structure. It has excellent catalytic activity and can be used for various reactions,
In particular, it is suitably used as a hydrocarbon conversion catalyst and has a high practical value.

Claims (3)

[Claims] 1. A group Ib or IIb of the periodic table in a crystal lattice.
Group, Group IIIa, Group IIIb, Group IVa, Group IVb, VIb
An activated zeolite obtained by introducing a sulfone group into an aluminosilicate containing at least one metal element selected from the group consisting of Group VIIb and Group VIII metal elements. 2. A group Ib or IIb of the periodic table in a crystal lattice.
Group, Group IIIa, Group IIIb, Group IVa, Group IVb, VIb
A process for producing an activated zeolite, which comprises subjecting an aluminosilicate containing at least one metal element selected from the group VIIb, VIIb and VIII metal elements to a contact treatment with a sulfone group-containing compound. . 3. The method for producing an activated zeolite according to claim ₂ , wherein the sulfone group-containing compound is CF ₃ SO ₃ H, FSO ₃ H or H ₂ SO ₄ .