JPH0686395B2 - Internal olefin production method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an internal olefin, and more particularly to a method for producing a more stable internal olefin by isomerizing an olefin in the presence of a specific catalyst. Is.

<Prior Art and Problems to be Solved by the Invention> Various methods are known for isomerizing an olefin to a more stable internal olefin. However, in the known method, in general, there is a problem that an undesired by-product of the product such as the decomposition of the olefin, giving an unnecessary polymerization product of the olefin, and randomization is often involved.
Subject to financially unfavorable limitations.

As a catalyst for such an isomerization reaction, a liquid base such as a mixture of an alkali metal hydroxide and an aprotic organic solvent, an alkali metal amide and an amine, or an organic alkali metal and an aliphatic amine is known. However,
In the method using such a liquid base reagent, the catalytic activity is not sufficient and a large amount of expensive reagent is required, and it is difficult to separate and collect the reagent from the reaction mass, and the complexity is separated. There is a problem that not only a recovery process is required but also a large amount of energy is consumed.

There is also known a method of using 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 (JP-A-60-94925 and JP-A-62-92525). -81334 publication). 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 method of using a solid base in which an alkali metal hydride is supported on a carrier such as alumina is also known (JP-A-53-53).
121753 and 59-134736). However,
Such a solid base using an alkali metal hydride shows catalytic activity by using a co-catalyst such as ammonia or hydrazine, so that when using this solid base, ammonia, hydrazine or the like is required separately. In addition to the 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, for the production of internal olefins using a solid base made from an alkaline earth metal compound and an alkali metal hydride, an alkali metal such as an alkali metal,
As a result of further studies to find a more industrially superior method, a solid base obtained by heating alumina with an alkaline earth metal compound and an alkali metal at a specific temperature is remarkably high by itself. Not only does it show isomerization activity, but it does not ignite when in contact with air, so it is safe,
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, in the present invention, by isomerizing the double bond of an olefin to produce a more stable internal olefin, an alkaline earth metal compound is added to alumina at 300 to 600 ° C. as a catalyst. Excellent industrially characterized by using a solid base which is heated at a temperature and then heated at a temperature of 200 to 450 ° C with an alkali metal and / or an alkali metal hydride in an inert gas atmosphere. And a method for producing an internal olefin.

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. The particle size is preferably about 50 to 400 mesh from the viewpoint of operability and activity of the obtained solid base.

Examples of the alkaline earth metal compound include the periodic table II.
Group oxides, hydroxides, methoxides, alkoxides such as ethoxide, carbonates, formates, acetates, inorganic acid salts such as propionates, organic acid salts, and the like, preferably magnesium, calcium, It is an oxide such as barium, a hydroxide or an organic acid salt. These compounds are usually used as a solution of water, an organic solvent, or the like, or a suspension in which they are atomized and 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, when the alkaline earth metal compound melts at a predetermined temperature that causes the alumina to act, the alumina can be directly heated to act on the alumina.

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. Mixtures of two or more can also be used.

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 used in 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 in the solid base, and the desired reaction is completed without an auxiliary agent such as ammonia or hydrazine and even in a small amount. it can. Further, since the solid base is safe with no danger of ignition and has excellent fluidity, it is used for various reactions on an industrial scale.

The present invention uses such a solid base to isomerize an olefin into a more stable internal olefin. Examples of the starting olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-butene. Nonen, 1
-Decene, 2-methyl-1-butene, 3-methyl-1-
Butene, 4-methyl-1-pentene, 3-methyl-1-
Chain compounds such as pentene, 2-methyl-1-pentene, 2,3-dimethyl-1-butene, aromatic compounds such as allylbenzene and allyltoluene, 2-isopropenylnorbornane, 5-isopropenyl-2-norbornene , 5-
Crosslinked ring compounds such as vinyl-2-norbornene and 6-methyl-5-vinylnorbornene, cyclic compounds such as methylenecyclopentane and methylenecyclohexane, 1,4-pentadiene, 1,5-hexadiene and 2,5-dimethyl-1 ,Four
-Terminal olefin compounds such as non-conjugated olefins such as hexadiene and 2,5-dimethyl-1,5-hexadiene, 4-
Methyl-2-pentene, 5- (2-propenyl) -2-
Examples thereof include compounds having a double bond other than the terminal such as norbornene and capable of isomerizing at a more stable position.

The amount of the solid base catalyst used in producing the internal olefin is usually 1/3000 to 1/50 weight, preferably 1/2000 to 1/100 weight, relative to the raw material.

Regarding the isomerization temperature, it is not necessary to heat the reaction because the reaction proceeds sufficiently even at room temperature, but it may be heated depending on the purpose. It is usually carried out in the temperature range of -30 to 120 ° C, preferably -10 to 100 ° C.

If necessary, the reaction can be carried out by diluting it with an inert medium, for example, hydrocarbons such as pentane, hexane, heptane, dodecane, etc., but no medium is sufficient. The method of the present invention can be carried out by either a batch method or a continuous method.
It is also effective to pretreat the raw material with a desiccant such as alumina or molecular sieve in advance. 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 separated from the catalyst by filtration or the like.

<Effects of the Invention> Thus, an internal olefin isomerized to a more stable position, which is the object of the present invention, can be obtained. However, according to the method of the present invention, an extremely small amount of catalyst can be obtained without an auxiliary agent such as ammonia or hydrazine. The olefin isomerization reaction can be completed efficiently, and an internal olefin can be obtained in a high yield with little by-products such as a polymer. In addition, since the reaction can be safely proceeded without danger of ignition, it is extremely useful as a method for industrial production of internal olefin.

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

Reference Example 1 (1-1) 10 g of lightly 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 the temperature was lowered to 300 ° C, and 1.2 g of metallic sodium was added at the same temperature. It was stirred for 30 minutes.
It was cooled to room temperature and 21.4 g of an off-white powder of solid base was obtained.

Reference Example 2 15.2 g of the same magnesia used in Reference Example 1 was fired at 510 g ° C. for 2 hours while stirring under a nitrogen gas stream. 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 to give 15.2 g of gray solid base.

Reference Examples 3 to 6 In (1-2) of Reference Example 1, the temperature at the time of adding sodium metal and the stirring temperature thereafter were 300 ° C to 170 ° C,
Reference example 1 except that the temperature is changed to 250 ℃, 400 ℃, 510 ℃
The solid base shown in Table 1 was obtained in the same manner as in (1-2).

Reference Example 7 (7-1) 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 Reference Example 1.

(7-2) 25 g of the powder obtained in (7-1) was calcined under a nitrogen gas stream at 510 ° C for 3 hours with stirring, and then the temperature was lowered to 360 ° C. And stirred for 30 minutes.
This was cooled to room temperature to obtain the solid base shown in Table 1.

Reference Example 8 25 g of the powder obtained in (1-1) of Reference Example 1 was calcined under a nitrogen gas stream at 510 ° C. for 3 hours with stirring, and then 310 ° C.
After the temperature was lowered to 1.4 g, 1.4 g of potassium hydride 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 9 (9-1) 113 g of powder was obtained in the same manner as in (1-1) except that 12.1 g of calcium oxide was used instead of magnesia in (1-1) of Reference Example 1.

(9-2) 25 g of the powder obtained in (9-1) was calcined under a nitrogen gas stream at 510 ° C. for 2 hours with stirring, and then the temperature was lowered to 310 ° C., and then 1.4 g of metallic potassium was added at the same temperature. It was stirred for 30 minutes. This was cooled to room temperature to obtain the solid base shown in Table 1.

Example 1 0.20 g of the solid base prepared in Reference Example 1 and 5-vinyl-2-norbornene (hereinafter referred to as V
(NB) (74 g) was added and the mixture was 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) was 99.4% and VNB was 0.5%.

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

The results are shown in Table 2.

Example 7 A 100 ml flask was charged with 0.2 g of the solid base prepared in Reference Example 1 and 30 g of 4-methyl-1-pentene under a nitrogen atmosphere.
Stirred at ~ 20 ° C for 16 hours. After the solid base was filtered off, the reaction mixture was analyzed by gas chromatography to find that 4-methyl-1-pentene 0.4% and 4-methyl-2-pentene 9.1
% And 2-methyl-2-pentene 90.3%.

Example 8 0.22 g of the solid base prepared in Reference Example 1 and 2,3-dimethyl-1-butene (2,3-dimethyl-1-butene 99.4%, tetramethylethylene 0.6) in a 100 ml flask under a nitrogen atmosphere.
%) 41 g and the mixture was stirred at 15 to 20 ° C. for 16 hours. After the solid base was filtered off, the reaction mixture was analyzed by gas chromatography to find that it was 7.3% 2,3-dimethyl-1-butene and 92.7% tetramethylethylene.

Reference Example 9 gamma-in a solution consisting 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.

Example 9 To a 200 ml flask, under a nitrogen atmosphere, 0.24 g of the solid base prepared in Reference Example 9 and 121.6 g of VNB were added and 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%.

Reference Example 10 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.

Example 10 Under a nitrogen atmosphere, 0.25 g of the solid base prepared in Reference Example 10 and 122.9 g of VNB were added to a 200 ml flask and 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%.

Reference Example 11 The procedure of Reference Example 9 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. Of solid base was obtained.

Example 11 Under a nitrogen atmosphere, 0.25 g of the solid base prepared in Reference Example 11 and 74.2 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 73.4 g of reaction liquid. The analysis results were ENB 99.4% and VNB 0.5%.

Reference Example 12 The procedure of Reference Example 10 was repeated except that 1.4 g of metal sodium was used instead of potassium metal to obtain a gray powder solid base.

Example 12 Under a nitrogen atmosphere, 0.25 g of the solid base prepared in Reference 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%.

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Claims (1)

[Claims] 1. When isomerizing an olefin to produce a stable internal olefin, alumina is heated with an alkaline earth metal compound at a temperature of 300 to 600 ° C. as a catalyst, and then alkali is added in an inert gas atmosphere. A process for producing an internal olefin, which comprises using a solid base produced by heating a metal and / or alkali metal hydride at a temperature of 200 to 450 ° C.