JP2522354B2 - 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 alumina pretreated with an alkali metal salt of carbonic acid or aluminate and an alkali metal hydride at a specific temperature. The present invention relates to a method for producing a solid base by heating it.

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

As such a solid base, conventionally, a catalyst in which an alkali metal is dispersed in a carrier having a large surface area, such as activated carbon, silica gel, or alumina, is known (J. Am. Chem. So.
c., 82 , 387 (1960)). However, such a solid base in which an alkali metal is dispersed in a carrier has a big problem in terms of operability and safety since it ignites and deactivates when contacted with air. Moreover, the catalytic ability was also unsatisfactory.

The present inventors have already found a new catalyst that uses alumina, alkali metal hydroxide, and alkali metal as a raw material as a solid base that has solved these drawbacks, and this one not only exhibits high catalytic activity but also in air. Does not ignite,
It has been found that it is safer and is excellent as an industrial catalyst (Japanese Patent Publication No. 50-3274). However, it is not always sufficiently satisfactory in terms of using an alkali metal as a raw material.

On the other hand, a solid base in which an alkali metal hydride is carried 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.

As a result of intensive studies to find out a better solid base, the present inventors have obtained by heating an alumina pretreated with an alkali metal salt of carbonic acid or aluminate with an alkali metal hydride under a specific temperature. Solid base is
Not only does it exhibit extremely high activity by itself, but it can be handled safely, and it has been found to be extremely excellent as an industrial catalyst, and the present invention has been completed by further various studies.

<Means for Solving Problems> That is, according to the present invention, alumina pretreated with an alkali metal salt of carbonic acid or aluminate is heated with an alkali metal hydride at a temperature of 200 to 450 ° C. in an inert gas atmosphere. The present invention provides an industrially excellent method for producing a solid base.

Examples of the alkali metal hydride that is a raw material of the solid base in the present invention include hydrides of Group I sodium, potassium and the like. Two or more kinds of alkali metal hydrides can be used. Alkali metal hydride is usually 2 to 15 wt% with respect to alumina, preferably 4 to
10 wt% is used.

As the alumina pretreated with an alkali metal salt of carbonic acid or aluminate, for example, alumina pretreated with an alkali metal carbonate or aluminate of Group I of the periodic table such as sodium, potassium, lithium, rubidium and cesium. Is mentioned.

As the alumina to be treated, various forms of alumina other than α-alumina are used, and in particular γ-, χ-, ρ-, η-
A high surface area alumina such as a mold is preferably used.
A water-containing product can also be used. Alumina interacts with alkali metal hydrides, carbonic acid alkali metal salts, aluminate alkali metal salts, etc. to form a kind of new bond and also serves as a carrier. Alumina-containing materials such as alumina silicate can also be used, but the above-mentioned alumina is preferable.

The pretreatment of alumina is usually carried out by impregnating the aqueous solution of the alkali metal salt and then calcining.
The amount of alkali metal salt impregnated is usually 5 to 5 with respect to alumina.
It is 30 wt%, preferably 5 to 25 wt%, and the firing temperature is usually 300 to 700 ° C.

The solid base of the present invention is prepared by heating an alkali metal hydride and alumina pretreated with an alkali metal salt of carbonic acid or aluminate at a specific temperature in an inert gas atmosphere. Examples of nitrogen include nitrogen, helium, and argon.

The preparation temperature of the solid base of the present invention is extremely important, especially the temperature at which the alkali metal hydride and the alumina pretreated with the alkali metal salt are heated, and the catalyst activity is significantly affected. The adjusting temperature is 200 to 450 ° C, preferably 220 to 400 ° C, more preferably 250 to 400 ° 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 and the like, but 15 minutes to 10 hours is usually sufficient.

Thus, the solid base of the present invention is produced.The solid base is considered to form new active species by the action of alumina and alkali metal salt and alkali metal hydride, such as ammonia and hydrazine. Since the desired reaction can be completed without an auxiliary agent and in a small amount, it is used in various reactions on an industrial scale.

For example, it can be used for various reactions such as isomerization of olefins and various condensation reactions promoted by a base. Among them, it exhibits an excellent catalytic action for olefin isomerization, and can efficiently isomerize an olefin into a more stable internal olefin.

When olefins are isomerized, the amount of the solid base of the present invention to be used is usually 1/1000 to 1/1 / the raw material olefin.
It is 20 weight, and 1/500 to 1/100 weight is sufficient. The isomerization temperature does not need to be particularly warmed because the reaction proceeds sufficiently even at room temperature, but it may be warmed depending on the purpose.
It is usually carried out in the temperature range of -30 to 120 ° C, preferably -10 to 100 ° C.

The raw material olefin for the isomerization reaction is, for example, 1
-Butene, 1-pentene, 1-hexene, 1-heptene, 1-nonene, 1-decene, 2-methyl-1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl Chain compounds such as -1-pentene, 2-methyl-1-pentene and 2,3-dimethyl-1-butene, aromatic compounds such as allylbenzene and allyltoluene, 2-
Isopropenyl norbornane, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 6-
Crosslinked ring compounds such as methyl-5-vinylnorbornene, cyclic compounds such as methylenecyclopentane and methylenecyclohexane, 1,4-pentadiene, 1,5-hexadiene, 2,
5-dimethyl-1,4-hexadiene, 2,5-dimethyl-1,5
-A terminal olefin compound such as a non-conjugated olefin such as hexadiene, a double bond other than the terminal such as 4-methyl-2-pentene, and 5- (2-propenyl) -2-norbornene, and an isomer at a more stable position. The compound which can be converted is mentioned.

An inert medium, if necessary, such as pentane, hexane,
The reaction can be carried out by diluting it with a hydrocarbon solvent such as cyclohexane, heptane, dodecane, etc., but after the reaction, the desired high-quality isomerized olefin can be obtained only by separating the catalyst. You may select the solvent used by.

The isomerization reaction can be carried out by a batch method or a continuous method, and it is also effective to pretreat the raw material with a drying agent such as alumina in advance for the isomerization. In order to carry out isomerization more safely and surely, it may be carried out under an inert gas atmosphere.

The isomerization reaction product is analyzed by a known method such as gas chromatography and is easily separated from the catalyst by filtration, decantation or the like.

Thus, an isomerized olefin can be obtained, but if the solid base catalyst of the present invention is used, the activity is remarkably high even without an auxiliary agent such as ammonia or hydrazine, so that the isomerization reaction can be completed very efficiently even with a small amount of catalyst. You can Moreover, the target product is selectively produced with almost no by-products such as polymerized products, and a high-quality target product can be obtained only by separating the catalyst.

<Effects of the Invention> The solid base of the present invention has a remarkably high activity by itself, and has an advantage that it can be efficiently handled, and can be handled safely.

In addition, since an alkali metal hydride that can be easily handled and easily obtained can be used as a raw material, the present invention is also advantageous in this respect.

<Example> Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples.

Reference example 1 Sodium aluminate 23.5g and water 200m in a 300ml flask
l was added to dissolve sodium aluminate. Then, 109 g of γ-alumina was added thereto, and the water was distilled off under reduced pressure while heating and stirring at 60 ° C. to obtain 133.3 g of powder.

Reference Example 2 In the same manner as in Reference Example 1 except that 15 g of sodium carbonate was used instead of sodium aluminate, 123.3 g of powder was obtained.

Example 1 25 g of the powder obtained in Reference Example 1 was placed in a 100 ml flask, heated at 450 ° C. for 2 hours while stirring in a nitrogen stream, and then allowed to cool.

Next, add 1.1 g of sodium hydride (a commercially available product was washed by adding hexane under a nitrogen atmosphere, filtered, dried after removing mineral oil), heated to 350 ° C with stirring and heated at the same temperature for 1 hour. After stirring, the mixture was allowed to cool to obtain 24.1 g of solid base.

Examples 2 to 7 and Comparative Examples 1 to 4 The solid bases shown in Table 1 were obtained in the same manner as in Example 1 except that shown in Table 1.

Reference Example 3 Under a nitrogen atmosphere, 0.21 g of the solid base prepared in Example 1 was placed in a 150 ml flask, 76.0 g of 5-vinyl-2-norbornene (purity 99.9%) was added thereto, and the mixture was heated at 15 to 20 ° C. for 10 hours. It was stirred.

After the reaction, the reaction solution was analyzed by gas chromatography to find that it was 5-vinyl-2-norbornene (hereinafter, VN
B) 0.5% and 5-ethylidene-2-norbornene (hereinafter referred to as ENB) 99.4%. The catalyst is filtered off 7
5.4 g of product was obtained.

Reference Examples 4 to 13 VNB was isomerized in the same manner as in Reference Example 3 except that shown in Table 2. The results are shown in Table-2.

Reference Example 14 Made of glass with an inner diameter of 5 mmΦ and a length of 100 mm with a jacket tube In a tube of 1., the solid base prepared in Example 1 under a nitrogen atmosphere.
96 g was filled.

Cooling water of 15 to 20 ° C is poured into the outer tube, and 3.4 g from the upper part of the inner tube
VNB (purity 99.9%) was introduced at a flow rate of / hr.

The composition of the reaction liquid flowing out from the lower part of the reactor was as follows.

Time (hr) VNB (%) ENB (%) 15 0.3 99.5 25 0.3 99.5 35 0.3 99.5 45 0.3 99.5 Total outflow amount was 151.7 g, and ENB average purity was 99.5%.

Reference Example 15 Under a nitrogen atmosphere, 0.25 g of the solid base prepared in Example 1 was placed in a 100 ml flask, 17.5 g of 4-methyl 1-1 pentene was added thereto, and the mixture was stirred at 215 to 20 g for 16 hours.

After the reaction, the reaction solution was analyzed by gas chromatography to find that 4-methyl-1-pentene 0.4%, 4-methyl-2-pentene 8.9% and 2-methyl-2-pentene 90.
It was 5%.

Reference Example 16 0.25 g of the solid base prepared in Example 2 was placed in a 200 ml flask under a nitrogen atmosphere, 36.2 g of 4-methyl-1-pentene was added thereto, and the mixture was stirred at 15 to 20 ° C. for 8 hours.

When the reaction solution was analyzed in the same manner as in Reference Example 15, 4-methyl-1-pentene 0.4% and 4-methyl-2-pentene 9.4
%, 2-methyl-2-pente 90.2%.

Reference Example 17 Under a nitrogen atmosphere, 0.3 g of the solid base prepared in Comparative Example 1 was placed in a 100 ml flask and 4-methyl-1-pentene was added thereto.
6 g was added and the mixture was stirred at 15 to 20 ° C for 48 hours.

After the reaction, when analyzed in the same manner as in Reference Example 15, 4-methyl-1-pentene 90.7%, 4-methyl-2-pentene 5.8
% And 2-methyl-2-pentene 3.3%.

Reference Example 18 Under a nitrogen atmosphere, 0.25 g of the solid base prepared in Example 5 was placed in a 100 ml flask, 18 g of 4-methyl-1-pentene was added thereto, and the mixture was stirred at 15 to 20 ° C. for 16 hours.

When the reaction solution was analyzed in the same manner as in Reference Example 15, 4-methyl-1-pentene 0.5% and 4-methyl-2-pentene 8.9
% And 2-methyl-2-pentene 90.4%.

Reference Example 19 Under a nitrogen atmosphere, 0.25 g of the solid base prepared in Example 4 was placed in a 200 ml flask, 36.3 g of 4-methyl-1-pentene was added thereto, and the mixture was stirred at 15 to 20 ° C. for 8 hours.

After the reaction, when analyzed in the same manner as in Reference Example 15, 4-methyl-1-pentene 0.4% and 4-methyl-2-pentene 8.8
% And 2-methyl-2-pentene 90.6%.

Reference Example 20 0.31 g of the solid base prepared in Comparative Example 3 was placed in a 100 ml flask under a nitrogen atmosphere, 6 g of 4-methyl-1-pentene was added thereto, and the mixture was stirred at 15 to 20 ° C. for 48 hours.

When the reaction solution was analyzed in the same manner as in Reference Example 15, 4-methyl-1-pentene 89.3% and 4-methyl-2-pentene 6.
7% and 2-methyl-2-pentene 3.8%.

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Claims (1)

(57) [Claims] 1. Production of a solid base characterized in that alumina pretreated with an alkali metal salt of carbonic acid or aluminate is heated with an alkali metal hydride at a temperature of 200 to 450 ° C. in an inert gas atmosphere. Method.