JPH0696121B2 - Method for producing solid base - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a method for producing a solid base, and more specifically, to alkaline earth metal compounds such as hydroxides, oxides, and alkoxides of alumina and alkaline earth metals, and alkalis. The present invention relates to a method for producing a solid base by heating a metal or an alkali metal such as an alkali metal hydride at a specific temperature.

<Prior Art and Problems to be Solved by the Invention> Solid bases are industrially important catalysts, and are used for reactions such as olefin isomerization, hydrogenation and dehydrogenation.

As such a solid base, a solid base in which an alkali metal is carried on a carrier composed of an alkaline earth metal oxide or an alkaline earth metal oxide and an alkali metal hydroxide is known (Japanese Patent Laid-Open No. 60-94925). 62-81334).
However, such a solid base using an alkaline earth metal oxide has problems that it tends to be condensed into lumps during its preparation and that operability is poor, and that its catalytic ability is not sufficient.

On the other hand, a solid base in which an alkali metal hydride is supported on a carrier such as alumina is also known (Japanese Patent Laid-Open Nos. 53-121753 and 59-134736). However, since such a solid base using an alkali metal hydride exhibits catalytic activity by using a cocatalyst such as ammonia or hydrazine, when using this solid base, ammonia, hydrazine or the like is required separately. In addition to such a problem, a purification device for separating and removing these after the reaction is required, and there is a problem that the operation becomes complicated.

The present inventors have conducted extensive studies to find out a better solid base using an alkaline earth metal compound and an alkali metal, and as a result, alumina is mixed with an alkaline earth metal compound and an alkali metal under a specific temperature. The solid base obtained by heating is not only highly active by itself, but also safe in that it does not ignite on contact with air.
Moreover, the solid base was found to be excellent in operability both during preparation and during use without forming lumps and completing the present invention by further conducting various studies.

<Means for Solving the Problems> That is, according to the present invention, alumina is heated with an alkaline earth metal compound at a temperature of 300 to 600 ° C., and then, in an inert gas atmosphere, alkali metal and / or alkali metal hydride. The present invention provides a method for producing a solid base, which is industrially extremely excellent, in which the compound is heated at a temperature of 200 to 450 ° C.

Alumina, which is a raw material of the solid base in the present invention, preferably has a large surface area, and examples thereof include γ-alumina, χ-alumina, ρ-alumina, and η-alumina. A particle size of about 50 to 400 mesh is preferable from the viewpoint of operability and activity of the obtained solid base.

Examples of the alkaline earth metal compound include oxides, hydroxides, methoxides, ethoxides, and other alkoxides of Group II elements, inorganic salts such as carbonates, formates, acetates, and propionates, and organic acid salts. Examples thereof include oxides, hydroxides, and organic acid salts of magnesium, calcium, barium, and the like. These compounds are usually used as a solution of water, an organic solvent, or the like, or a suspension in which they are finely dispersed. In heating the alumina, the solution or suspension may be added to the alumina stirred at a predetermined temperature, or the alumina is preliminarily loaded with an alkaline earth metal compound using the solution or suspension. After the heating, the heating may be performed. On the other hand, if the alkaline earth metal compound melts at a predetermined temperature that heats the alumina, the alumina can be directly heated.

Examples of the alkali metals include alkali metals of Group I of the periodic table and hydrides thereof, preferably lithium, sodium, potassium and hydrides thereof,
More preferred are sodium, potassium and hydrides thereof. It is also possible to use a mixture of two or more kinds.

The amount of alkaline earth metal compound or alkali metal used relative to alumina is usually 5 to 100 Wt% for the former and 2 to 15 Wt% for the latter.

Examples of the inert gas include nitrogen, helium and argon.

In the present invention, the temperature at the time of preparing the solid base is extremely important, and in particular, the temperature at which the alkali metal acts has a great influence on the catalyst performance.

The temperature at which the alkaline earth metal compound is allowed to heat the alumina is 300 to 600 ° C, preferably 300 to 550 ° C.
The temperature at which the alkali metal is heated is usually 200 to 450 ° C., preferably 250 to 400 ° C., more preferably 280.
To 350 ° C.

By preparing a solid base at such a temperature, a solid base having a remarkably high activity which has never been obtained can be obtained, and the target reaction can be efficiently completed with a small amount of catalyst.

The heating time varies depending on the selected temperature conditions, etc.
The step of heating the alumina to the alkaline earth metal compound for about 0.5 to 10 hours and the step of allowing the alkali metal to act on the alumina for about 5 to 300 minutes are sufficient.

Thus, the solid base of the present invention is produced. It is considered that alumina, alkaline earth metal compounds and alkali metals act on each other to form a new active species, such as ammonia, hydrazine and the like. It can be used for various industrial-scale reactions because the desired reaction can be completed without using any auxiliary agent and even in a small amount.

For example, it can be used for various reactions such as isomerization of olefins and various condensation reactions promoted by a base. Above all, it shows an excellent catalytic action for olefin isomerization, for example, in the case of isomerizing a terminal olefin into an internal olefin,
Particularly, for isomerization from an alkenyl bridged ring compound to an alkylidene bridged ring compound, isomerization proceeds only by bringing them into contact with each other at room temperature.

<Effects of the Invention> The solid base of the present invention has advantages such as not only that it exhibits remarkably high activity by itself, but also that it does not ignite when contacted with air and is safe.

In addition, the solid base has advantages that it does not form a lump and has good fluidity, and that it has excellent operability both during preparation and during use.

<Example> Hereinafter, the present invention will be described in more detail with reference to Examples.
The invention is not limited to the examples.

Example 1 (1-1) 10 g of light-baked magnesia was crushed in a mortar and suspended in 400 g of water, and 100 g of γ-alumina (containing 2.2% of water) was added thereto with stirring. Then, the water was distilled off under reduced pressure at 60 ° C. to obtain 119.5 g of powder.

(1-2) 25 g of the powder obtained in (1-1) was calcined under a nitrogen gas stream at 510 ° C. for 2 hours with stirring and then cooled to 300 ° C.,
1.2 g of metallic sodium was added, and the mixture was stirred at the same temperature for 30 minutes. It was cooled to room temperature to give 21.4 g of off-white solid base.

Comparative Example 1 15.2 g of the same magnesia used in Example 1 was calcined under a nitrogen gas stream at 510 g ° C. for 2 hours while stirring. Then
After the temperature was lowered to 300 ° C., 0.73 g of metallic sodium was added, and the mixture was stirred at the same temperature for 30 minutes. Uniform stirring was difficult, but it was cooled to room temperature and 15.2 g of a gray powder solid base was obtained.

Examples 2-3, Comparative Examples 2-3 In (1-2) of Example 1, the temperature at the time of adding metallic sodium and the stirring temperature after that are 300 to 170 degreeC, and 25.
Solid bases shown in Table 1 were obtained in the same manner as in (1-2) of Example 1 except that the temperature was changed to 0 ° C, 400 ° C, and 510 ° C, respectively.

Example 4 (4-1) 115.2 g of powder was obtained in the same manner as in (1-1) except that 15 g of magnesium hydroxide was used in place of magnesia in (1-1) of Example 1.

(4-2) 25 g of the powder obtained in (4-1) was calcined under a nitrogen gas stream at 510 ° C. for 3 hours with stirring, and then cooled to 360 ° C.,
Sodium hydride (1.3 g) was added, and the mixture was stirred at the same temperature for 30 minutes.
This was cooled to room temperature to obtain the solid base shown in Table 1.

Example 5 25 g of the powder obtained in (1-1) of Example 1 was calcined under a nitrogen gas stream at 510 ° C. for 3 hours with stirring, then cooled to 310 ° C., and then 1.4 g of potassium hydride was added. The mixture was stirred at the same temperature for 30 minutes. This was cooled to room temperature to obtain the solid base shown in Table 1.

Example 6 (6-1) In the same manner as (1-1) except that 12.1 g of calcium oxide was used in place of magnesia in (1-1) of Example 1.
113 g of powder were obtained.

(6-2) 25 g of the powder obtained in (6-1) was calcined under a nitrogen gas stream at 510 ° C. for 2 hours with stirring, and then cooled to 310 ° C.,
1.4 g of metallic potassium was added, and the mixture was stirred at the same temperature for 30 minutes. This was cooled to room temperature to obtain the solid base shown in Table 1.

Reference Example 1 Under a nitrogen atmosphere, 0.20 g of the solid base prepared in Example 1 and 74 g of 5-vinyl-2-norbornene (hereinafter referred to as VNB) were added to a 200 ml flask and stirred at 15 to 20 ° C. for 8 hours.

Then, the catalyst was filtered off to obtain 73.3 g of a reaction liquid.
When this was analyzed by gas chromatography,
5-Ethylidene-2-norbornene (hereinafter referred to as ENB) 99.
It was 4% and VNB 0.5%.

Reference Examples 2 to 9 Using the solid bases prepared in Examples 2 to 6 and Comparative Examples 1 to 3, VNB was isomerized in accordance with Reference Example 1 except for the conditions shown in Table 2.

The results are shown in Table 2.

Reference Example 10 In a 100 ml flask, under a nitrogen atmosphere, 0.2 g of the solid base prepared in Example 1 and 30 g of 4-methyl-1-pentene were placed, and 15-20
Stirred for 16 hours at ℃. After filtering off the solid base, the reaction mixture was analyzed by gas chromatography to find that 4-methyl-1-pentene 0.4%, 4-methyl-2-pentene 9.1%, 2-methyl-pentene
2-pentene was 90.3%.

Reference Example 11 0.22 g of the solid base prepared in Example 1 and 2,3-dimethyl-1-butene (2,3-dimethyl-1-butene 99.4%, tetramethylethylene 0.6%) prepared in Example 1 in a 100 ml flask under a nitrogen atmosphere. 41 g
Was charged and stirred at 15 to 20 ° C. for 16 hours. After filtering off the solid base,
When the reaction solution was analyzed by gas chromatography, it was found that
3-Dimethyl-1-butene 7.3%, tetramethylethylene 92.
It was 7%.

Example 7 γ-in a solution of 4.6 g of barium hydroxide octahydrate and 100 g of water
26.5 g of alumina was added, and this was concentrated to dryness under reduced pressure at 60 ° C. while stirring.

Then, this was stirred under a nitrogen atmosphere at 500 ° C. for 1.5 hours, cooled to 290 ° C., 2 g of metallic potassium was added, and stirring was continued at the same temperature for 0.2 hours. This was cooled to room temperature to obtain a blue-gray powder solid base.

Reference Example 12 Under a nitrogen atmosphere, 0.24 g of the solid base prepared in Example 7 and 121.6 g of VNB were added to a 200 ml flask, and the mixture was stirred at 20 to 25 ° C for 3 hours.

Then, the catalyst was filtered off to obtain 120.9 g of a reaction solution. The analysis results were ENB 99.1% and VNB 0.6%.

Example 8 20 g of γ-alumina and 10.6 g of magnesium acetate tetrahydrate were stirred at 470 ° C. for 4 hours under an air stream.

Then, after cooling to 300 ° C. under a nitrogen stream, 2.52 g of metallic potassium was added thereto, and stirring was continued at the same temperature for 0.2 hours. This was cooled to room temperature to obtain a blue-gray powder solid base.

Reference Example 13 Under a nitrogen atmosphere, 0.25 g of the solid base prepared in Example 8 and 122.9 g of VNB were added to a 200 ml flask, and the mixture was stirred at 20 to 25 ° C for 2 hours.

Then, the catalyst was filtered off to obtain 122.1 g of reaction liquid. The analysis results were ENB 99.3% and VNB 0.4%.

Example 9 The procedure of Example 7 was repeated except that 1.59 g of sodium metal was used in place of potassium metal, and the temperature at the time of adding this and the stirring temperature after that were 300 ° C., which was an off-white powder. Of solid base was obtained.

Reference Example 14 Under a nitrogen atmosphere, 0.25 g of the solid base prepared in Example 9 and 74.2 g of VNB were added to a 200 ml flask, and the mixture was stirred at 20 to 25 ° C for 24 hours.

Then, the catalyst was filtered off to obtain 73.4 g of reaction liquid. The analysis results were ENB 99.4% and VNB 0.5%.

Example 10 The procedure of Example 8 was repeated except that 1.4 g of metal sodium was used instead of potassium metal to obtain a solid base of gray powder.

Reference Example 15 Under a nitrogen atmosphere, 0.25 g of the solid base prepared in Example 10 and 76 g of VNB were added to a 200 ml flask and stirred at 20 to 25 ° C for 24 hours.

Then, the catalyst was filtered off to obtain 75.1 g of a reaction liquid. The analysis results were ENB 99.6% and VNB 0.3%.

Claims (1)

[Claims] 1. Alumina containing an alkaline earth metal compound of 300
A method for producing a solid base, which comprises heating at a temperature of ˜600 ° C. and then heating the alkali metal and / or hydride of an alkali metal at a temperature of 200˜450 ° C. in an inert gas atmosphere.