JPS6032610B2 - Method for producing primary alcohols - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing primary alcohols, and more specifically, hydrogenation reaction of 1,2-epoxy linear alkanes is carried out in the presence of a specific catalyst to produce linear aliphatic primary alcohols. Relating to a method of manufacturing.

Alcohols are important as intermediate raw materials for various industrial products, and since linear primary alcohols are particularly useful, various production methods have been proposed.

When alcohol is produced by hydrogenation reaction using 1,2-epoxy linear alkanes as raw materials, the alcohol obtained is usually a mixture of primary and secondary alcohols, and it is not possible to selectively produce primary alcohols. It was difficult.

To date, the only method for obtaining primary alcohols with relatively good selectivity is German Patent No. 113944 (1).
Only two examples have been disclosed: 961) and Special Publication No. 48-31083. The former uses metal catalysts such as cobalt, nickel, and iron supported on a carrier, or a mixture of these catalysts, while the latter uses metal borons such as nickel, cobalt, and iron produced using expensive sodium borohydride. This method uses a compound catalyst. The inventor is 1
, conducted extensive research on catalysts used in the hydrogenation reaction of 2-epoxy linear alkanes, and discovered a catalyst that is useful for selectively producing primary alcohols and can be prepared at low cost and easily. I was able to complete it.

In the present invention, primary alcohols are produced by hydrogenating a 1,2-epoxyalkane having 3 or more carbon atoms in the presence of a cobalt-phosphorus catalyst obtained by hydrogen reduction of cobalt phosphate. The present invention provides a method for manufacturing.

The method of the present invention can be expressed by the following equation.

The 1,2-epoxyalkane used in the method of the present invention has 3 or more carbon atoms, and in consideration of reactivity and product use, etc., 1,2-epoxyalkanes having 6 to 2 carbon atoms are preferred. As a catalyst, a cobalt/phosphorus catalyst obtained by hydrogen reduction of cobalt phosphate is used.

The cobalt-phosphorus catalyst is obtained by reducing cobalt phosphate in a hydrogen stream (preferably at normal pressure) at a temperature of 550 to 750 q○ for 1 to 1 incubation time. An example of preparation of this catalyst is as follows. Preparation example of catalyst 1 Co3(P04)2・Spot 20 (manufactured by Mitsuwa Kagaku ■, reagent 1
After drying at 11,000 for 5 hours in an electric muffle lamp, the sample was crushed in a mortar.

0.8 mm of the dried sample thus obtained was taken on a magnetic board and inserted into a quartz glass tube loaded into an electric tubular furnace.
3 at a given temperature while flowing at a flow rate of about 1 hydrogen/mjn.
Hydrogen reduction was carried out for hours.

The catalyst obtained by reduction at a temperature of 65,000°C was black in color, and the catalyst obtained by reduction at 750°C was gray-black in color.

Preparation example of catalyst 2 Alumina sol 200 (manufactured by Nissan Chemical Co., Ltd.) 10 minutes, Co3
(P04) 2. Crude 20 (manufactured by Mitsuwa Chemical ■, reagent grade 1) 1
．． 73 (20% by weight as Co/AI203) was mixed in a mortar.

The mixture was then dried in an electric muffle oven at a temperature of 11,000 °C for 5 hours. After drying, it was ground in a mortar. 1.0 mm of the dried sample thus obtained was placed on a porcelain board, inserted into a quartz glass tube equipped in an electric tubular furnace, and heated at a predetermined temperature for 3 hours while flowing hydrogen at a flow rate of 15 m/min. Hydrogen reduction was performed.

The catalyst obtained by reduction at temperatures of 400oo and 550qC is grayish-black-purple;
The catalyst obtained by reduction at a temperature of 10% was grayish-black in color.

Preparation Example 3 of Catalyst A pulverized dry sample was obtained in the same manner as in Preparation Example 2 above, and 1.0 minutes of this sample was air-calcined at a temperature of 550°C for 3 hours in an electric tubular furnace.

Next, reduction was carried out at a predetermined temperature while flowing hydrogen at a flow rate of about 15 birds/mjn. Conditions for carrying out the method of the present invention should be determined by taking into account the raw materials, the type of catalyst, etc.
Generally, it is carried out at a temperature of 100 to 200 q○ for 1 to 8 hours, preferably 120 to 160 q○ for 1 to 5 hours.

When the reaction temperature is low, the reaction rate decreases, so it is necessary to carry out the reaction for a long time. The amount of cobalt/phosphorus catalyst to be used is not limited; for example, when using a cobalt/phosphorus catalyst without a carrier, it is used in the range of 10 to 50, preferably about 40, per mole of 1,2-epoxyalkane as the raw material. That is appropriate. In the case of a liquid sample, the reaction of the present invention is carried out as it is or by dissolving it in a solvent, and in the case of a solid sample, it is carried out by dissolving it in a solvent. Solvents that can be used in the present invention include organic solvents such as alcohols and non-polar hydrocarbons, with methanol, ethanol, propanol, benzane, hexane, heptane, octane and the like being preferred. Note that when the catalyst is supported on alumina, a hydrocarbon solvent is preferable. According to the method of the present invention, a primary alcohol corresponding to the carbon number of the 1,2-epoxyalkane as a raw material can be selectively obtained.

Primary alcohols are used in the production of plasticizers, synthetic detergents, surfactants, pharmaceuticals, cosmetics, etc., and the method of the present invention advantageously produces relatively long-chain primary alcohols that are highly useful. be able to. Next, the present invention will be explained in detail with reference to examples.

Example 1 A predetermined amount of the cobalt/phosphorous catalyst produced by the method shown in Preparation Example 1 was used as a catalyst, and 1.0 mole (0.01 mole) of 1,2-epoxyhexane was used as a solvent and 5 moles of ethanol. A hydrogenation reaction was carried out.

The reaction was carried out at a temperature of 15°C under a hydrogen pressure of 40 kg'.
I did it for an hour. After the reaction was completed, the composition of the reaction product was analyzed using a gas chromatograph. The results are shown in Table 1. Table 1 Example 2 1,2-epoxy was prepared under the same conditions as in Example 1 except that the reaction temperature and reaction time were changed and the amount of catalyst was increased by 0.1 and was set to 0.49. A hydrogenation reaction of hexane was carried out.

The results are shown in Table 2. Table 2 A hydrogenation reaction of 1,2-epoxyhexane was carried out under the same conditions as in Example 1 except that the reaction temperature and reaction time were changed and the amount of catalyst was 0.4 hours.

The results are shown in Table 3. Table 3 Example 4 In Example 1, the reaction temperature was 15,000 and the reaction time was 3 hours, and the preparation conditions were different for each catalyst (without carrier).
A hydrogenation reaction of 1,2-epoxyhexane was carried out under the same conditions as in Example 1 except that 2 hours and 0.4 hours were used.

The results are shown in Table 4. Table 4 Example 5 The hydrogenation reaction of 1,2-epoxyhexane was carried out under the same conditions as in Example 1, except that 0.2 mm of the cobalt phosphorus catalyst produced by the method shown in Preparation Example 2 was used as the catalyst. I did it.

The results are shown in Table 5. Comparative Example A hydrogenation reaction of 1,2-epoxyhexane was carried out under the same conditions as in Example 1, except that Yama 2030.19 was used as a catalyst.

The results are shown in Table-5. Table 5 *Comparative Example - Example 6 Calcining Mountain 203 in Hydrogen 0.2% of the cobalt phosphorous catalyst produced by the method shown in Preparation Example 2 was used as the catalyst, and 5% of n-hexane was used as the solvent. A hydrogenation reaction of 1,2-epoxyoctane (1.3 nights, 0.01 mol) was carried out under the same conditions as those shown in Example 1, except for the following.

The results are shown in Table 6. Table 6 Example 7 A hydrogenation reaction of 1,2-epoxyoctane was carried out under the same conditions as in Example 6, except that 0.2 liters of catalyst with different preparation conditions were used.

The results are shown in Table 7. ±- 7 Example 8 As a catalyst, the hydrogen flow rate was adjusted to 15'/min according to Preparation Example 2 above.
min or 25 [/mjn as 65000 and 3
A hydrogenation reaction of 1,2-epoxyoctane was carried out under the same conditions as in Example 6 except that a cobalt/phosphorus catalyst obtained by time reduction treatment was used.

The results are shown in Table 8. Table-8*A: Hydrogen flow rate 15 [/m
Preparation B: Preparation at a hydrogen flow rate of 25/min Example 9 Using the cobalt-phosphorus catalyst prepared according to Preparation Example 1 (temperature 650°C) as a catalyst, 1,2-epoxytetradecane 2.1 min. 0.01 mol) and n-hexane were hydrogenated under the conditions of a temperature of 150 qo, a pressure of 40 k9/kg, and a time of 3 hours.

When the product was analyzed by gas chromatography, the total alcohol content was 60.2%, of which 90.5% was primary alcohol and 9.5% was secondary alcohol.

Claims (1)

[Claims] 1. Cobalt obtained by reducing cobalt phosphate with hydrogen.
A first method characterized by carrying out a hydrogenation reaction of a 1,2-epoxyalkane having 3 or more carbon atoms in the presence of a phosphorous catalyst.
A method for producing grade alcohols. 2. The method according to claim 1, wherein the 1,2-epoxyalkane has 6 to 20 carbon atoms. 3 The cobalt-phosphorus catalyst is Co_3(PO_4)_2.
The method according to claim 1, which is obtained by reducing 8H_2O in a hydrogen stream at a temperature of 500 to 750°C. 4. The method according to claim 1 or 3, wherein the cobalt-phosphorus catalyst is supported on alumina. 5. The method according to claim 1, wherein when the 1,2-epoxyalkane is a liquid, the hydrogenation reaction is carried out in the presence or absence of an organic solvent. 6. The method according to claim 1, wherein when the 1,2-epoxyalkane is solid, the hydrogenation reaction is carried out in the presence of an organic solvent. 7. The method according to claim 5 or 6, wherein the organic solvent is an alcohol or a nonpolar hydrocarbon. 8. The method according to claim 1, wherein the hydrogenation reaction is carried out at a temperature of 100 to 200°C. 9. The method according to claim 1, wherein the primary alcohol is a straight-chain aliphatic primary alcohol.