JPH02138228A - Preparation of inner olefin - Google Patents

Abstract

PURPOSE:To provide the subject compound safely in high efficiency and yield in a small amount of a catalyst by isomerizing an olefin in the presence of a solid base prepared by thermally treating alumina with an alkaline earth metal compound and an alkali metal under a specific temperature. CONSTITUTION:An olefin is isomerized in the presence of a solid base as a catalyst to provide the objective compound, the solid base being prepared by reacting alumina with an alkaline earth metal compound at 300-600 deg.C, preferably at 300-550 deg.C, and subsequently reacting the reaction product with an alkali metal and/or an alkali metal hydride at 200-450 deg.C, preferably at 250-400 deg.C, especially 280-350 deg.C, in an atmosphere of an inert gas. The temperature of the isomerization is usually -30-120 deg.C, preferably -10-100 deg.C. The used solid base catalyst is used in an amount of 1/3000-1/50 pt.wt., preferably 1/2000-1/100 pt.wt. based on the raw material.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for producing internal olefins, and more particularly to a method for producing more stable internal olefins by isomerizing olefins in the presence of a specific catalyst. It is.

<Prior Art 1 Problems to be Solved by the Invention> Various methods are known for isomerizing olefins into more stable internal olefins. However, in the known method,
Generally, it has the disadvantage that it often involves the decomposition of olefins, the formation of unnecessary olefin polymers, and the by-products of undesirable products such as randomization, and is subject to economically disadvantageous limitations. There is.

As catalysts for such isomerization reactions, liquid bases such as mixtures of alkali metal hydroxides and aprotic organic solvents, alkali metal amides and amines, or organic alkali metals and aliphatic amines are known. however,
Methods using such liquid base reagents do not have sufficient catalytic activity, require large amounts of expensive reagents, and are difficult to separate and recover from the reaction mass, requiring complicated separation. There is a problem that not only a recovery process is required but also a large amount of energy is consumed.

A method using a solid base in which an alkali metal is supported on a nail body composed of an alkaline earth metal oxide or an alkaline earth metal oxide and an alkali metal hydroxide is also known (Japanese Unexamined Patent Publication No. 60-94925, 62-81334) However, such solid bases using alkaline earth metal oxides tend to condense and form lumps during preparation, resulting in poor operability and insufficient catalytic ability. there were.

On the other hand, a method using a solid base in which an alkali metal hydride is supported on a carrier such as alumina is also known (Japanese Unexamined Patent Publication No. 53
-121753 publication, 59-134736 publication)
However, such a solid base using an alkali metal hydride exhibits catalytic activity when used together with a co-catalyst such as ammonia or hydrazine. In addition to the problem of requiring such substances, a purification device for separating and removing these substances after the reaction is also required, and the operation becomes complicated.

The present inventors have described the production of internal olefins using solid bases made from alkaline earth metal compounds and alkali metals such as alkali metal hydrides and alkali metals.
As a result of further investigation to find a more industrially superior method, we found that the solid base obtained by heating alumina with alkaline earth metal compounds and alkali metals at a specific temperature is extremely expensive even when used alone. Not only does it exhibit isomerization activity, but it is also safe without igniting even when it comes in contact with air.
In addition, they discovered that the cough solid base does not form lumps, has good fluidity, and is excellent in operability both during ill production and use, and after further various studies, they completed the present invention.

<y! , Means for Solving the Problem> That is, the present invention isomerizes the double bonds of olefins and produces more stable internal olefins by adding 300% of an alkaline earth metal compound to alumina as a catalyst.
An industry characterized by using a solid base that is heated at a temperature of 600 to 600°C, and then heated to an alkali metal and/or alkali metal hydride at a temperature of 200 to 450°C in an inert gas atmosphere. This provides a method for producing internal olefins that is extremely superior in terms of performance.

The alumina that is the raw material for the solid base in the present invention preferably has a wide surface area, such as T-alumina, χ-alumina, ρ-alumina, η-alumina, and the like. The particle size is preferably about 50 to 400 mesh from the viewpoint of operability and the activity of the solid base obtained.

As an alkaline earth metal compound, for example,
Examples include oxides of group elements, alkoxides such as hydroxides, methoxides, and ethoxides, inorganic acid salts such as carbonates, formates, acetates, propionates, and organic acid salts, but preferably magnesium, calcium, These are oxides, hydroxides, and organic acid salts of barium, etc. These compounds are usually used as a solution in water, an organic solvent, or the like, or as a suspension in which they are finely dispersed. When heating alumina, the solution or IG suspension may be added to the alumina stirred at a predetermined temperature, or the solution or M suspension may be used to preliminarily add alkaline earth to the alumina. After supporting the metal compound, heating may be applied.On the other hand, when the alkaline earth metal compound melts at a predetermined temperature at which it is applied to alumina, it is possible to directly apply heating to the alumina.

Examples of alkali metals include alkali metals of Group 1 of the periodic table and their hydrides, preferably lithium, sodium, potassium and their hydrides,
More preferred are sodium, potassium and their hydrides. It is also possible to use a mixture of two or more young.

The amount of alkaline earth metal compound and 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 during the preparation of the solid base is extremely important, and in particular, the temperature at which the alkali metals are allowed to act has a large effect on the catalyst performance.

The temperature at which the alumina is heated with the alkaline earth metal compound is 3007'J to 600°C, preferably 300 to 550°C. The temperature at which the alkali metals are heated is usually 200 to 450°C, preferably 250 to 400°C, more preferably 280 to 350°C.

It is.

If a solid base is prepared at such a temperature, a solid base with extremely high activity never seen before can be obtained, and the desired reaction can be efficiently completed with a small amount of catalyst.

Heating time varies depending on the temperature conditions selected, but usually
It is sufficient to heat the alumina with the alkaline earth metal compound for about 0.5 to 10 hours, and to apply the alkali metals to the alumina for about 5 to 300 minutes.

The solid base used in the present invention is thus produced, but
It is thought that the solid base is formed by the interaction of alumina, alkaline earth metal compounds, and alkali gold Ktq to form new active species, and it is possible to carry out the desired reaction without the use of auxiliary agents such as ammonia or hydrazine, and even in small amounts. It can be completed. Furthermore, the solid base is safe without any risk of ignition, and has excellent fluidity, so it is used in various reactions on an industrial scale.

The present invention uses such a solid base to isomerize olefins into more stable internal olefins. Examples of such raw material olefins include l-butene, l-pentene, 1-hexene, 1-heptene, and 1-heptene. Nonen,■
-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, allyltoluene, 2-isopropenylnorbornane, 5-isopropenyl-2-norbornene, 5-
Bridged ring compounds such as vinyl-2-norbornene and 6-methyl-5-vinylnorbornene, cyclic compounds such as methylenecyclobencune and methylenecyclohexane, 1,4-penkdiene, 1,5-hexadiene, 2,5-dimethyl-
In addition to terminal olefin compounds such as non-conjugated olefins such as 14-hexadiene and 2,5-dimethyl-1,5-hexadiene, terminals such as 4-methyl-2-pentene and 5-(2-propenyl)-2-norbornene, etc. Examples include compounds that have a double bond and can be isomerized to a more stable position.

Further, in producing internal olefins, the amount of solid base catalyst used is usually 1/3000 to 1150, preferably 1/2000 to 1/6, of the raw material.
100 weight.

Regarding the isomerization temperature, there is no particular need to heat it as the reaction proceeds sufficiently at room temperature, but depending on the purpose it may be heated. Usually -30 to 120 degrees Celsius, preferably -
It is carried out at a temperature range of 10 to 100°C.

If necessary, the reaction can be carried out by diluting with an inert medium, for example, a hydrocarbon 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. , for isomerization,
It is also effective to pre-treat the raw material with a desiccant such as alumina or molecular sheep. In order to carry out isomerization more safely and reliably, 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> In this way, internal olefins that are isomerized to a more stable position, which is the object of the present invention, can be obtained, but according to the method of the present invention, ammonia, hydrazide 7, etc. (7) can be obtained without using an auxiliary agent and with a small amount of catalyst. The isomerization reaction of olefins can be completed extremely efficiently even in small amounts, and internal olefins can be obtained in high yields with almost no by-products such as polymers.
Furthermore, since the reaction can proceed safely without any danger of ignition, it is extremely useful as an industrial method for producing internal olefins.

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

Reference Example 1 Lightly calcined magnesia IQg was crushed in a mortar and suspended in 400 g of water, and then T-alumina (moisture 2
．． 2% containing) 100g was added at 0 then 60'C.

Water was distilled off under reduced pressure to obtain 119.5 g of powder.

25 g of the powder obtained in (1-1) was calcined at 510°C for 2 hours while stirring under a nitrogen gas flow, and then the temperature was lowered to 300°C, and 1.2 g of metallic sodium was added thereto for 3 hours at the same temperature.
Stirred for 0 minutes. This was cooled to room temperature to obtain 21.4 g of a solid base as an off-white powder.

Reference Example 2 15.2 g of the same magnesia used in Reference Example 1 was calcined at 510 g'C for 2 hours under a nitrogen gas stream while stirring. Next, after the temperature was lowered to 300'C, 0.73 g of metallic sodium was added and stirred at the same temperature for 30 minutes. Although it was difficult to stir uniformly, this was cooled to room temperature and 15.2
g of a gray solid base was obtained.

Reference Examples 3 to 6, in (1-2) of Reference Example 1, the temperature when adding metallic sodium and the subsequent stirring temperature were changed from 300'C to 170'C, 250'C, 400'C, and 510'C. The solid bases shown in Table 1 were obtained in the same manner as in Reference Example 1 (1-2) except for the respective changes.

Reference Example 7 115.2 g of powder was obtained in the same manner as in Reference Example 1 (1-1) except that 15 g of magnesium hydroxide was used instead of magnesia.

25 g of the powder obtained in (7-1) was calcined at 510°C for 3 hours with stirring under a nitrogen gas flow, and then the temperature was lowered to 360°C, and 1.3 g of sodium hydride was added thereto for 3 hours at the same temperature.
Stirred for 0 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 Reference Example 1 (1-1) was calcined at 510'C for 3 hours without stirring under a stream of nitrogen gas, and then the temperature was lowered to 310°C, followed by 1.5 g of potassium hydride. 4 g was added and stirred at the same temperature for 30 minutes. This was cooled to room temperature to obtain the solid base shown in Table 1.

The mixture was stirred for 30 minutes according to Table 1. This was cooled to room temperature to obtain the solid base shown in Table 1.

Reference Example 9 1g In (1-1) of Example 1, except that 12.1g of oxidizing power lucium was used instead of magnesia (1-1)
In the same manner as above, 113 g of powder was obtained.

25 g of the powder obtained in (9-1) was calcined at 510'C for 2 hours under a nitrogen gas stream without stirring, and then at 310'C.
After the temperature was lowered to , 1.4 g of metallic potassium was added and at the same temperature Example 1. 0.20 g of the solid base prepared in Reference Example 1 and 74 g of 5-vinyl-2-norbornene (hereinafter referred to as VNB) were placed in a 200 rnl flask under a nitrogen atmosphere. Add 15-20
'C'7' Stirred for 8 hours.

Then, the catalyst was filtered off to obtain 73.3 g of reaction liquid. When this product was analyzed by gas chromatography, it was found that 5-ethylidene-2-norbornene (hereinafter referred to as ENB)
Toy value) was 99.4%, and VNB was 0.5%.

Examples 2 to 6, Comparative Examples 1 to 3 Using the solid bases produced in Reference Examples 2 to 9, VN[l was isomerized according to Example 1 except for the conditions shown in Table 2. .

The results are shown in Table 2.

Example 7 Solid base 0.28 and 4-methyl-1-pentene 30 were individually packaged in Reference Example 1 in a 100 d flask under nitrogen atmosphere.
g and stirred at 15 to 20°C for 16 hours. After filtering off the solid base, the reaction solution was analyzed by gas chromatography, and it was found that 4-methyl-! -Pentene 0.4%, 4-methyl-2-pentene 9.1%, 2-methyl-2-pentene 9
It was 0.3%.

Example 8 In a 100 d flask under a nitrogen atmosphere, 0.22 g of the solid base prepared in Reference Example 1 and 2,3-dimethyl-1-butene (99.4% of 2,3-dimethyl-1-butene, tetramethyl Add 41g of ethylene (0.6%) to 15-20℃.
The mixture was stirred for 16 hours. After filtering off the solid base, the reaction solution was analyzed by gas chromatography and found to contain 7.3% of 2.3-dimethyl-1-butene and 92% of tetramethylethylene.
It was 7%.

Reference Example 9 26.5 g of T-alumina was added to a solution consisting of 4.6 g of barium hydroxide octahydrate and 100 g of water, and the mixture was concentrated to dryness at 60° C. under reduced pressure while stirring.

Next, this material was stirred at 500°C for 1.5 hours under a nitrogen atmosphere, then cooled to 290°C, and 2 g of metallic potassium was added.
was added, and stirring was continued at the same temperature for 0.2 hours.

This was cooled to room temperature to obtain a solid base as a blue-gray powder.

Example 9 0.24 g of the solid base prepared in Reference Example 9 and 121.6 g of vNB were added to a 200 mN flask under a nitrogen atmosphere, and the mixture was stirred at 20 to 25°C for 3 hours.

Next, the catalyst was filtered off to obtain 120.9 g of the reaction solution.6 The analysis results were as follows: EN! 199.1%, VNB O, 6%
Met.

Reference Example 10 20 g of γ-alumina and magnesium acetate tetrahydrate 10.
6 g was stirred at 470° C. for 4 hours under a stream of air.

Next, 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 solid base as a blue-gray powder.

Example 10 In a 200 d flask under a nitrogen atmosphere, 0.25 g of the solid base prepared in Reference Example 10,! :VNB 122.9
g was added thereto, and the mixture was stirred at 20-25°C for 2 hours.

Next, the catalyst was filtered off to obtain 122.1 g of the reaction solution, and the analysis results showed that EM [l 99.3%, VNII O
,4%.

Reference Example 11 The procedure was carried out in accordance with Reference Example 9, except that 1.59 g of metallic sodium was used instead of metallic potassium, and the temperature at the time of adding this and the subsequent stirring temperature were 300 ° C. A solid base was obtained as an off-white powder.

Example 11 0.25 g of the solid base prepared in Reference Example 11 and 74.2 g of VNB were added to a 200 d flask under a nitrogen atmosphere, and the mixture was stirred at 20-25°C for 24 hours.

Next, the catalyst was filtered off to obtain 73.4 g of reaction solution.
The analysis results were 99.4% ENB and 5% VNnO.

Reference Example 12 The procedure of Reference Example 10 was followed except that 1.4 g of metallic sodium was used instead of metallic potassium, and a gray powder solid base was obtained.

Example 12 0.25 g of the solid base prepared in Reference Example 1O and 176 g of VN were added to a 200 m flask under a nitrogen atmosphere.
Stir at 0-25°C for 24 hours.

Next, the catalyst was filtered off to obtain 75.1 g of a reaction solution.The analysis results were EN899.6%, VNBO, 3%.

Claims (1)

[Claims] In producing stable internal olefins by isomerizing olefins, alumina is heated with an alkaline earth metal compound as a catalyst at a temperature of 300 to 600°C, and then an alkali metal and/or alkali is added to the alumina in an inert gas atmosphere. A method for producing an internal olefin, characterized by using a solid base obtained by heating a metal hydride at a temperature of 200 to 450°C.