JPH05301834A - Production of alpha,beta-unsaturated alcohol - Google Patents

Abstract

PURPOSE:To industrially produce an alpha,beta-unsaturated alcohol in high activity and in high selectivity by using an inexpensive metal having low toxicity. CONSTITUTION:In producing an alpha,beta-unsaturated alcohol by reacting an alpha,beta-unsaturated aldehyde with hydrogen in the presence of a catalyst, a catalyst which comprises one or more metals selected from indium, neodymium, magnesium, barium and lanthanum and silver and has the atomic ratio of the metal except silver and silver of 1:1-1:20 is used as the catalyst.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an α, β-unsaturated alcohol. The α, β-unsaturated alcohol is useful as an intermediate for synthetic resins, medicines, agricultural chemicals, perfumes, rubber drugs and the like.

[0002]

2. Description of the Related Art α, β-unsaturated alcohol is α, β-
The production method is generally carried out by reducing the unsaturated aldehyde, but while leaving the carbon-carbon double bond,
It is extremely difficult to selectively reduce only the formyl group, and many attempts have been made in the past.

For example, as a hydrogen reduction catalyst, a platinum group precious metal catalyst (WFTuley, R. Adams, J. Am. Chem. Soc. 47 3
061 (1925)), a copper-cadmium catalyst (US Pat. No. 276).
3696), Raney copper catalyst modified with cadmium (Japanese Patent Publication No. 39-610), osmium catalyst (US Pat. No. 3,655,777), silver-zinc catalyst (Japanese Patent Publication 4713010), silver -Cadmium catalyst (JP-A-53-18506, JP-A-1-1277041)
Japanese Patent Publication No. 4), a platinum catalyst modified with iron and silver (US Pat. No. 3,284,617), a catalyst in which rhodium is supported on Amberlyst (US Pat. No. 4,292,452), and the like have been proposed.

However, all of these catalysts have problems that they are expensive, the reaction rate and the selectivity of α, β-unsaturated alcohol are low, and that cadmium and osmium are highly toxic. As a reducing agent, there is a method of using a stoichiometric amount of sodium borohydride, metal hydride such as lithium aluminum hydride, or aluminum alkoxide such as aluminum ethoxide.
These methods require the use of large amounts of expensive reducing agents and are not industrially advantageous.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to use a metal which is inexpensive and has low toxicity and which is suitable for industrial production.
It is to provide a method for producing β-unsaturated alcohol.

[0006]

The present invention comprises reacting an α, β-unsaturated aldehyde with hydrogen in the presence of a catalyst,
In the method for producing α, β-unsaturated alcohol, as a catalyst, one or more metals selected from the group consisting of indium, neodymium, magnesium, barium, and lanthanum, and silver, and a metal other than silver. A method for producing an α, β-unsaturated alcohol, which comprises using a catalyst whose ratio to silver is 1: 1 to 1:20 in atomic ratio.

(Α, β-Unsaturated Aldehyde) The α, β-unsaturated aldehyde used in the present invention has 3 to 10 carbon atoms.
Are aliphatic α, β-unsaturated aldehydes and aromatic α, β-unsaturated aldehydes having 9 to 16 carbon atoms, and specifically,
Acrolein, methacrolein, crotonaldehyde,
Examples thereof include cinnamaldehyde.

(Catalyst) In the production method of the present invention, α, β-
Upon hydrogenation of the unsaturated aldehyde, one or more metals selected from the group consisting of indium, neodymium, magnesium, barium, and lanthanum, and silver, and the ratio of the metal other than silver and silver in atomic ratio. 1: 1 to 1: 2
A catalyst of 0, preferably 1: 1 to 1:15 is used. The ratio of silver to the metal other than silver is an atomic ratio,
When it is less than 1, the hydrogenation activity is lowered, and when it exceeds 20, the selectivity of unsaturated aldehyde is lowered, which is not preferable.

As a supply source of these elements, for example, a soluble metal compound which can be converted into a metal or a metal oxide by hydrolysis and subsequent calcination is used, and specifically, nitrates, sulfates, acetic acid are used. Salts, salts of inorganic and organic acids such as various halides; complex salts; chelate compounds;
Examples include metal-containing compounds such as alkoxide. The catalyst can also be supported on a suitable carrier such as silica or alumina, and the content of components other than the essential metals of the present catalyst such as the carrier is 97% or less, preferably 90% or less.

The catalyst may be produced by any method as long as the metal of the catalyst component is contained in an intimate mixed state. For example, the group consisting of silver, indium, neodymium, lanthanum, magnesium and barium. The above metal-containing compound of one or more metals selected from, respectively, to a metal or a metal oxide by firing subsequent to hydrolysis,
It can be produced by subjecting them to conventional methods such as an impregnation method, a precipitation method and a coprecipitation method. As the impregnation method, for example, it is selected from the group consisting of insoluble, silver, and indium, neodymium, lanthanum, magnesium, and barium in particles or fine powder of a porous carrier such as preformed aluminum oxide, silicon oxide, and titanium oxide. Impregnation, drying and firing of one or more metals.

The coprecipitation method includes indium, neodymium,
It is prepared by coprecipitation from a mixed solution of one or more metals selected from the group consisting of lanthanum, magnesium and barium, and silver. The precipitate of the formed metal mixture can be molded, calcined and used as a catalyst itself, or can be further used by supporting it on a suitable carrier such as silica or alumina. The form of the catalyst of the present invention is powder or molded, and the shape of the molded catalyst is columnar, tablet, spherical, granular, granular, plate-like or the like.

(Reaction Conditions) The reaction mode for carrying out the present invention may be either a liquid phase or a gas phase. Also,
At that time, the contact method between the raw material and the catalyst can be appropriately selected from conventionally known methods, for example, in a liquid phase reaction, a suspension bed method using a powder catalyst in a continuous or batch system, In the gas phase reaction, not only the usual fixed bed system, but also a fluidized bed system, a moving bed system or the like is possible.

The amount of hydrogen used is 1 to 1000 mol, preferably 2 to 200 mol, per 1 mol of the α, β-unsaturated aldehyde as the raw material. If the amount of hydrogen is too small, the catalyst tends to be deactivated due to carbon deposition, and if the amount of hydrogen is too large, it is economically unfavorable. The hydrogen to be used does not necessarily have to be of high purity, and a substance that does not inhibit this reaction, such as nitrogen or argon, may be mixed with hydrogen at an arbitrary ratio and used.

Although the optimum reaction temperature varies depending on the hydrogen pressure, it is generally 50 to 350 ° C., preferably 10
It is in the range of 0 to 250 ° C. If the temperature is lower than 50 ° C, the reaction rate of unsaturated aldehyde is low, which is not practical.
When the temperature exceeds 0 ° C, side reactions such as decomposition increase, and the selectivity of the target product decreases. The reaction pressure is not particularly limited,
In the case of a gas phase reaction, the sum of the partial pressures of α, β-unsaturated aldehyde and hydrogen is atmospheric pressure to 50 kg / cm ² , and in the case of a liquid phase reaction, 1
About 0 to 100 kg / cm ² is preferable.

[0015]

EFFECTS OF THE INVENTION According to the production method of the present invention, α,
A β-unsaturated alcohol can be produced, which is industrially beneficial.

[0016]

EXAMPLES Next, the present invention will be described more specifically by way of examples. <Example 1> Silver nitrate 1.70 g (10 mmol) and indium nitrate _{(In (NO 3) 3 ·} 3H 2 O) 0.35g
(1 mmol) was dissolved in 350 ml of distilled water, and the silicon oxide carrier (trade name: Carrier Act-50-) was dissolved therein.
9.6 g (manufactured by Fuji Devison Co., Ltd.) was added. This mixture
After stirring for 1 hour at room temperature in a rotary evaporator, the pressure was reduced, the temperature was raised to 80 ° C., and drying was performed for 2 hours. Next, after drying for 16 hours in a dryer at 120 ° C., it was baked for 3 hours in air in an electric furnace at 500 ° C.

By the above operation, a granular catalyst having a silver content of about 10% by weight and silver: indium = 10: 1 (atomic ratio) was obtained. A small reaction tube was filled with 10 ml of this catalyst, and acrolein and hydrogen were reacted under the following reaction conditions. The results are shown in Table 1. (Reaction conditions) Hydrogen / acrolein = 20.8 (molar ratio) Hydrogen flow rate = 151 / hr Reaction temperature = 200 ° C. Reaction pressure = 2.0 kg / cm ² SV = 1567 hr ⁻¹

Example 2 The reaction was carried out in the same manner as in Example 1 except that the catalyst prepared by changing the ratio of silver nitrate and indium nitrate was changed so that silver: indium = 5: 2. The results are shown in Table 1.

[0019]

[Table 1]

<Examples 3 to 6> Silver-indium catalyst prepared by the same method as in Example 1 was further added with various metals in Table 2 as the third component, Na ₂ CO ₃ and CsN, respectively.
_{O 3, Zr (NO 3)} 4 · 5H 2 O, Zn (NO 3) 2 · 6H 2
The reaction was performed in the same manner as in Example 1 except that a catalyst prepared by adding a predetermined amount in the form of O was used. The results are shown in Table 2.

[0021]

[Table 2]

<Examples 7 and 8> 7.08 g of silver nitrate (40
Mmol) and indium nitrate _{(In (NO 3) 3 ·} 3H
₂ O) (1.42 g, 4 mmol) was dissolved in 100 ml of distilled water, and a solution of 2.85 g of sodium carbonate in 100 ml of distilled water was added dropwise with stirring to form a precipitate. The solution containing this precipitate was stirred for 1 hour, and then the precipitate was filtered and thoroughly washed with distilled water. Next, this precipitate was added to a solution obtained by mixing 200 ml of distilled water and 200 g of colloidal silica (trade name: Snowtex: manufactured by Nissan Kagaku Co., Ltd.), stirred for 2 hours, sufficiently dispersed, and then filtered off the precipitate. Then
It was dried in a dryer at 120 ° C. for 16 hours. Then 5
Firing was performed in an electric furnace at 00 ° C. in air for 3 hours.

By the above operation, a granular catalyst having a silver content of about 10% by weight and silver: indium = 10: 1 (atomic ratio) was obtained. A small reaction tube was filled with 7.14 g of this catalyst, and S
V = 1572 hr ⁻¹ , and the reaction temperature was 200, respectively.
The reaction was carried out under the same reaction conditions as in Example 1 except that the temperature was 250 ° C and 250 ° C. The results are shown in Table 3.

[0024]

[Table 3]

[0025] <Example 9> Example 1, neodymium nitrate (Nd (NO ₃ instead of indium nitrate) ₃ · 3H
₂ O) 0.44 g (1 mmol) was used to prepare a catalyst, and the reaction was performed in the same manner as in Example 1 except that the SV value was changed to 1558 hr ⁻¹ . The results are shown in Table 4.

<Example 10> A reaction was carried out in the same manner as in Example 9 except that the SV value was changed to 34369 hr ^-1 . The results are shown in Table 4.

<Examples 11 and 12> In Example 9,
The reaction was performed in the same manner as in Example 9 except that silver: neodymium = 7: 3 and 1:10 (atomic ratio). The results are shown in Table 4.

[0028]

[Table 4]

<Example 13> In Example 1, nitric acid was added.
Magnesium nitrate (Mg (NO ₃)₂
・ 3H₂O) 0.20 g (1 mmol) was used to
Prepared and SV value is 1567hr^-1Example 1 except that
The reaction was performed in the same manner as in. The results are shown in Table 5.

<Embodiment 14> In the embodiment 13, the SV
The reaction was carried out in the same manner as in Example 12 except that the value was 3336 hr ^-1 . The results are shown in Table 5.

[0031] <Example 15> Example 1, barium nitrate in place of indium nitrate _{(Ba (NO 3) 2 ·} 3
A catalyst was prepared by using 0.261 g (1 mmol) of H ₂ O and the reaction was carried out in the same manner as in Example 1 except that the SV value was 3352 hr ⁻¹ . The results are shown in Table 5.

[0032] <Example 16> Example 1, lanthanum nitrate (Ln (NO ₃ instead of indium nitrate) _3.3
A catalyst was prepared by using 0.261 g (1 mmol) of H ₂ O and the reaction was carried out in the same manner as in Example 1 except that the SV value was 3352 hr ⁻¹ . The results are shown in Table 5.

[0033]

[Table 5]

Comparative Example 1 A catalyst was prepared by using cadmium nitrate (1 mmol) instead of indium nitrate in Example 1, and the reaction was carried out under the same reaction conditions as in Example 13. The results are shown in Table 6.

[0035]

[Table 6]

Claims (1)

[Claims] 1. A method for producing an α, β-unsaturated alcohol by reacting an α, β-unsaturated aldehyde with hydrogen in the presence of a catalyst, wherein indium, neodymium, magnesium, barium, and , A lanthanum, and at least one metal selected from the group consisting of lanthanum and silver, and the ratio of the metal other than silver and silver is 1: 1 to 1:20 in atomic ratio. A method for producing an α, β-unsaturated alcohol.