JPH0248042A - Production of solid base - Google Patents

Abstract

PURPOSE:To prepare a solid base having remarkably high activity by pretreating alumina with an alkali metal carbonate or aluminate in an inert gaseous atmosphere and allowing an alkali metal hydride to act on the pretreated alumina at 200-450 deg.C. CONSTITUTION:An aq. soln. of an alkali metal carbonate or aluminate is impregnated into gamma-, chi-, rho- or eta-alumina having a large surface area and calcining is carried out at 300-700 deg.C in an inert gaseous atmosphere to pretreat the alumina. An alkali metal hydride is allowed to act on the pretreated alumina by heating at 200-450 deg.C to produce a solid base. The alkali metal hydride may be the hydride of Na or K belonging to the group I of the periodic table. The amt. of the alkali metal hydride used is usually 2-15wt.% of the amt. of the alumina.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for producing a solid base, and more specifically, the present invention relates to a method for producing a solid base, in particular, by adding an alkali metal hydride to alumina pretreated with an alkali metal salt of carbonic acid or aluminate at a specific temperature. This invention relates to a method for producing a solid base by applying heat.

<Prior art 2: 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 solid bases, catalysts in which alkali metals are dispersed in carriers with large surface areas, such as activated carbon, silica gel, alumina, etc., have been known (J, Yam, Che.
However, such solid bases in which alkali metals are dispersed in a carrier ignite and become deactivated when they come into contact with air, resulting in problems such as operability and safety. There was a big problem on the front. Moreover, the catalytic ability was also unsatisfactory.

The present inventors have developed a solid base that has solved these drawbacks.
We have already discovered a new catalyst using alumina, alkali metal hydroxide, and alkali metal as raw materials, and this catalyst not only shows high catalytic activity but also does not catch fire even in the air, making it safer and superior as an industrial catalyst. (Japanese Patent Publication No. 50-3274) However, it is not always fully satisfactory in terms of the use of alkali metals as raw materials.

On the other hand, solid bases in which alkali metal hydrides are supported on a carrier such as alumina are also known (Japanese Patent Laid-Open No. 53121753
(No. 59-134736) However, such solid bases using alkali metal hydrides,
Since it exhibits catalytic activity when co-catalysts such as ammonia and hydrazine are used together, when using this solid base, there is the problem that ammonia, hydrazine, etc. are required separately, and these must be separated and removed after the reaction. It also required a purification device for the process, which led to problems such as complicated operations.

The inventors of the present invention have discovered a better solid base (after extensive research, we have found that alumina pretreated with an alkali metal salt of carbonic acid or aluminate is heated with an alkali metal hydride at a specific temperature). They discovered that the obtained solid base not only exhibits extremely high activity on its own, but also can be handled safely and is extremely excellent as an industrial catalyst, and after further various studies, they completed the present invention.

<Means for solving the problem> That is, the present invention heats alumina pretreated with an alkali metal salt of carbonic acid or aluminate 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 characterized by the following.

Examples of the alkali metal hydrides that are raw materials for the solid base in the present invention include hydrides of sodium, potassium, and the like belonging to Group I of the periodic table. Two or more types of alkali metal hydrides can also be used. The alkali metal hydride is usually used in an amount of 2 to 15 wt%, preferably 4 to 10 wt%, based on the alumina.

Alumina pretreated with charcoal M or an alkali metal salt of aluminate is, for example, alumina pretreated with a carbonate or aluminate of an alkali metal such as sodium, potassium, lithium, rubidium, or cesium in Group 1 of the periodic table. Examples include alumina.

As the untreated alumina, various forms of alumina other than α-alumina can be used, and in particular, high surface area alumina such as T-1χρ-1η-type is preferably used. It is also possible to use quartz-containing crystals. Alumina interacts with alkali metal hydrides, alkali metal salts of carbonate, alkali metal salts of aluminate, etc. to form new bonds and also serves as a carrier. Although alumina-containing materials such as , alumina silicate, etc. can also be used, the above-mentioned aluminas are preferred.

Pretreatment of alumina is usually carried out by impregnating it with an aqueous solution of the alkali metal salt and then firing it. The amount of alkali metal salt impregnated is usually 5 to 3 per alumina.
Qwt%, 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 include nitrogen, helium, and argon.

The preparation temperature of the solid base of the present invention is extremely important;
In particular, the temperature at which the alkali metal hydride and alumina pretreated with an alkali metal salt are heated is extremely important, and has a significant effect on the catalytic activity. Adjustment temperature is 2
00 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 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
About 15 minutes to 10 hours is sufficient.

In this way, the solid base of the present invention is produced, and it is thought that alumina, alkali metal salts, and alkali metal hydrides interact with each other to form new active species. Since the desired reaction can be completed without any auxiliary agent and even with a small amount, it is used in various reactions on an industrial scale.

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

When isomerizing olefins, the amount of the solid base used in the present invention is usually 1/1000 to 1/20 of the weight of the raw material olefin, and 11,500 to 1/100 of the weight is sufficient. Further, since the reaction proceeds sufficiently at room temperature, there is no need to particularly heat the isomerization temperature, but it may be heated depending on the purpose. The temperature is usually -30 to 120°C, preferably -10 to 100°C.

In addition, as the raw material olefin for the isomerization reaction, for example, 1-
Butene, 1-pentene, 1-hexene, 1-heptene,
1-Nonene, l-decene, 2-methyl-1-butene, 3
-Methyl-1-butene, 4-methyl-1-pentene, 3
-Methyl-1-pentene, 2-methyl-1-pentene,
2. Calculating compounds such as 3-dimethyl-1-butene, aromatic layer compounds such as allylhenzene and allyltoluene, 2-isopropylnorbornane, 5-vinyl-2-norbornene,
5-isopropenyl-2-norbornene, 6-methyl-
Bridged ring compounds such as 5-vinylnorbornene, cyclic compounds such as methylenecyclopenkune and methylenecyclohexane, 1.4-pentadiene, 1.5-hexadiene, 2.
Terminal olefin compounds such as non-conjugated olefins such as 5-dimethyl-1,4-hexadiene and 2,5-dimethyl-1,5-hexadiene, 4-methyl-2-pentene, 5
-(2-propenyl)-2-norbornene and other compounds that have a double bond other than the terminal and can be isomerized to a more stable position can be mentioned.

If necessary, the reaction can be carried out by diluting it with an inert medium such as a hydrocarbon solvent such as pentane, hexane, cyclohexane, heptane, dodecane, etc., but even just separating the catalyst after the reaction can achieve the desired high-grade isomerization. Since the obtained olefin can be obtained, either no medium or a solvent to be used in the next step may be selected.

The isomerization reaction can be carried out by either the hatch method or the continuous method, and it is also effective to pre-treat the raw material with a desiccant such as alumina in advance. 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 easily separated from the catalyst by filtration, decantation, or the like.

In this way, an isomerized olefin is obtained, but if the solid base catalyst of the present invention is used, the activity is extremely high even without an auxiliary agent such as ammonia or hydrazine, so the isomerization reaction can be completed extremely efficiently even with a small amount of catalyst. Can be done.

Moreover, the target product is selectively produced with almost no by-products such as polymers, and a high-quality target product can be obtained simply by separating the catalyst.

<Effects of the Invention> The solid base of the present invention exhibits extremely high activity even on its own, and has advantages such as not only being able to efficiently carry out the desired reaction but also being able to be handled safely.

Furthermore, since an alkali metal hydride that is easy to handle and obtain can be used as a raw material, the present invention is advantageous in this respect as well.

<Examples> The present invention will be explained in more detail by Examples below.
The present invention is not limited only to the examples.

Reference example 1 23.5 liters of sodium aluminate in a 300 ml flask
g and 200 ml of water were added to dissolve the sodium aluminate. Next, 109 g of γ-alumina was added to this,
While heating to 6°C and stirring, water was distilled off under reduced pressure.
33.3g of powder was obtained.

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

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 with stirring in a nitrogen stream, and then allowed to cool.

Next, add 1 g of sodium hydride (a commercially available product was washed with hexane under a nitrogen atmosphere, filtered, dried to remove 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 a solid base.

Table 1 Examples 2 to 7, Comparative Examples 1 to 4 The solid bases shown in Table 1 were obtained in the same manner as in Example 1 except as 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 m1 flask, and 5-vinyl 2
- Add 76.0 g of norbornene (purity 99.9%),
Stirred at 15-20°C for 10 hours.

After the reaction, the reaction solution was analyzed by gas chromatography and found to be 5-vinyl-2-norbornene (hereinafter referred to as VN
5-ethylidene-2-norbornene (hereinafter referred to as ENB) 99.4%. The catalyst was filtered off to obtain 15.4 g of a product.

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

Reference Example 14 0.9% of the solid base prepared in Example 1 was placed in a glass tube with an outer jacket having an inner diameter of 5 mmΦ and a length of 100 mm under a nitrogen atmosphere.
6g was filled.

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

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

Time (hr) VNB (%) ENB (%
)15 0.3 99.525
0,3 99.535 0.3
99.545 0.3 99
．． 5 Total flow rate 151.7g, ENB average purity 99.5
%Met.

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

After the reaction, the reaction solution was analyzed by gas chromatography, and it was found that 4-methyl-1-pentene was 0.4%, 4-methyl-2-pentene was 8.9%, and 2-methyl-2-pentene was 90.5%. there were.

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, and 4-methyl 1-
36.2 g of pentene was added and stirred at 15 to 20°C for 8 hours.

When the reaction solution was analyzed in the same manner as in Reference Example 15, it was found that 0.4% of 4-methyl-1-pentene and 9% of 4-methyl-2-pentene.
．． 4%, 2-methyl-2-pentene 90.2%.

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

After the reaction, analysis in the same manner as in Reference Example 15 revealed that 4-methyl-1-pentene was 90.7%, 4-methyl-2-pentene was 5.8%, and 2-methyl-2-pentene was 3.3%. Ta.

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

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

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

After the reaction, analysis in the same manner as in Reference Example 15 revealed that 4-methyl-1-pentene was 0.4%, 4-methyl-2-pentene was 8.8%, and 2-methyl-2-pentene was 90.6%. Ta.

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, and 4-methyl 1-
6 g of pentene was added and stirred at 15-20°C for 48 hours.

When the reaction solution was analyzed in the same manner as in Reference Example 15, it was found that 4-methyl-1-pentene was 89.3%, 4-methyl-2-pentene was 6.7%, and 2-methyl-2-pentene was 3.8%. Ta.

17 (complete)

Claims (1)

[Claims] A method for producing a solid base, which comprises heating alumina pretreated with an alkali metal salt of carbonic acid or aluminate with an alkali metal hydride at a temperature of 200 to 450°C in an inert gas atmosphere.