JPS5940060B2 - Method for supporting metal components on zeolite-based carrier - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for supporting a metal component on a carrier based on Y zeolite, and in particular, a molybdenum compound, a nickel compound, and/or a cobalt compound as a metal component is added to Y zeolite as the metal component. This invention relates to a method for supporting a crystal structure without destroying it.

Zeolites are widely used as catalysts, dehydrating agents, fillers, etc., and because of their high decomposition performance as a component of catalyst compositions, they are used, for example, in catalytic cracking catalysts and hydrocracking catalysts in petroleum refining.

Y is a faujasite type of zeolite.
It is known that zeolite has high decomposition properties but weak crystals, and in order to strengthen this, it is possible to consider methods such as increasing the thermal stability of Y zeolite.

One method for this is to disperse Y zeolite in a metal oxide, typically alumina.

However, when this Y zeolite/alumina is used as a carrier to support a metal component to improve the catalytic function in catalytic cracking, hydrogenolysis, etc., the metal component solution penetrates into the carrier by dipping, spraying, etc. When a so-called impregnation method is adopted, some metal components destroy the crystal structure of Y zeolite.

For example, if a molybdenum compound is supported on a Y zeolite/alumina carrier, the crystal structure of the Y zeolite will be destroyed.

Therefore, since it is operationally easy to support metal components such as molybdenum using a normal impregnation method, the present inventors used this method to prevent Y zeolite from being destroyed and to maintain the interaction between Y zeolite and alumina. As a result of research into methods for supporting molybdenum compounds, nickel compounds, and cobalt compounds, it was discovered that it is effective to further add magnesia as a metal oxide.

The present invention was made based on this knowledge, and includes a molybdenum compound, a nickel compound, and a carrier made of ammonium type Y zeolite, alumina, and magnesia.
The present invention relates to a method for supporting a metal component on a zeolite-based carrier, which is characterized by impregnating it with a cobalt compound or a cobalt compound.

The zeolite used in the present invention is Y zeolite among those belonging to the natural or synthetic faujasite type.

It is desirable that the cations of the Y zeolite be exchanged with ammonium ions as much as possible to reduce the sodium content remaining in the Y zeolite to 0.5% by weight or less.

Needless to say, during this operation, care must be taken not to destroy the Y zeolite crystals, including the effect on operations in subsequent steps.

The carrier in the present invention is a mixture of the above-mentioned Y zeolite with alumina and magnesia, which are metal oxides. For example, the above-mentioned Y zeolite is dispersed in alumina hydrosil or alumina organosol, and a magnesium salt aqueous solution is added thereto. After mixing, NH, OH or NaO
Add an alkaline aqueous solution such as H to gel, dehydrate, wash,
Obtained by drying, shaping, and baking.

In addition, when magnesia is fired to form an oxide, only the metal oxide remains, and the rest must be volatilized.In addition to the water-soluble salts mentioned above (for example, magnesium chloride),
It may be an inorganic salt or an organic salt.

The above mixing ratio of zeolite and alumina is based on the total weight of zeolite and alumina.
0% by weight, preferably within the range of 10-50% by weight.

Also, the amount of magnesia is 5 to 20% by weight, preferably 8 to 20% by weight, based on the total weight of zeolite and alumina.
It is within the range of 15% by weight.

In the present invention, at least two kinds of metal components are supported on the carrier made of the above-mentioned zeolite, alumina, and magnesia to form a catalyst.

These metal components are molybdenum, which belongs to group II B of the periodic table and is known as a hydrogenation component, and nickel and cobalt, which belong to group II of the periodic table.

As molybdenum, compounds such as ammonium paramolybdate, molybdic acid, and molybdenum trioxide are used, and ammonium paramolybdate is preferred.

For nickel and cobalt, compounds such as nitrates, carbonates, and oxalates are used.

The amount of supported metal components is based on the weight of the carrier made of zeolite/alumina and magnesia, and molybdenum is in the range of 5 to 35% by weight, preferably 8 to 20% by weight, and nickel and/or cobalt is in the range of 1 to 20% by weight. It may be within the range of 15% by weight, preferably 2 to 10% by weight.

When the hydrogenation component metal is supported on the zeolite, alumina, and magnesia carriers, the presence or absence of destruction of the crystal structure of Y zeolite is determined from X-ray diffraction characteristics.

That is, within the range of diffraction angle 2θ of 4 to 20°, 2θ is 6.2° [Miller index (1, 1, 1')] and 1
It can be determined based on the degree and presence of the crystal peak at 5.7° [Miller index (3, 3, 1)].

The reason why the method of the present invention can prevent the crystal structure of Y zeolite from being destroyed is thought to be because the addition of magnesia to the carrier component improves the thermal stability of Y zeolite.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples unless the gist thereof is exceeded.

Example 1 Ammonium type Y zeolite was dispersed in alumina sol at a ratio of 30% by weight based on the total weight of alumina, and stirred.

A magnesium chloride aqueous solution was added to this by weight based on the weight of Mg010, and the mixture was stirred.

Next, about 2N ammonia aqueous solution was added to form a gel, and the mixture was dehydrated.

After washing with deionized water, the gel was heated at a temperature of about 120°C for about 15 minutes.
Dry for an hour.

The resulting solid was formed into a powder into a 1.6 x 1.6 mm pellet and fired at a temperature of about 550°C for about 3 hours.

This carrier is immersed in an ammonium molybdate aqueous solution,
After supporting 15 parts by weight of Mo5s based on the carrier, it was once dried and fired, then immersed in an aqueous nickel nitrate solution to support 15 parts by weight of Ni0 based on the carrier, and dried and fired again.

After supporting, drying was carried out at a temperature of about 120°C for about 3 hours, and baking was carried out at a temperature of about 500°C for about 3 hours.

According to the X-ray diffraction characteristics of Y zeolite, the catalyst obtained as described above has a diffraction angle of 2θ in the range of 4 to 2Cf.
is 6.2° [Miller index (1, 1, 1)] and 15.
Since a crystal peak at 7° [Miller index (3, 3, 1)] was observed, it was confirmed that the crystal structure of Y zeolite was not destroyed.

Example 2 A catalyst was prepared basically using the same method as in Example 1, and immersed in an aqueous cobalt nitrate solution instead of an aqueous nickel nitrate solution to support 3% by weight of CoO based on the carrier.

Regarding the obtained catalyst, it was confirmed from the X-ray diffraction characteristics of Y zeolite that the crystal structure of Y zeolite existed without being destroyed, as in Example 1.

Example 3 A catalyst was prepared using basically the same method as in Example 1.

After supporting molybdenum and nickel, it was immersed in an aqueous cobalt nitrate solution to support CoO3 based on the weight of the support.

Regarding the obtained catalyst, it was confirmed from the X-ray diffraction characteristics of Y zeolite that the crystal structure of Y zeolite existed without being destroyed, as in Example 1.

Comparative Example 1 Ammonium type Y zeolite was dispersed in alumina sol at a ratio of 30% by weight based on the total weight of the dispersion and alumina, and stirred.

Next, an approximately 2N ammonia aqueous solution was added without adding a magnesium salt to cause gelation and dehydration.

Hereinafter, a catalyst was prepared by the method of Example 1.

When we investigated the X-ray diffraction properties of this Y zeolite, we found that the diffraction angle 2θ was 6.2° [Miller index (1, 1, 1)] and 15.7° [Miller index No prominent crystal peak of (3,3,1)) was observed, confirming that the crystal structure of Y zeolite was destroyed by this operating method.

Claims (1)

[Claims] 1. A method for supporting metal components on a zeolite-based carrier, which comprises impregnating a molybdenum compound, a nickel compound, and/or a cobalt compound into a carrier made of ammonium-type Y zeolite, alumina, and agnesia.