JPH0734866B2 - Catalyst for reducing carbonyl compound, method for producing the catalyst, and method for producing alcohol using the catalyst - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a catalyst for reducing a carbonyl compound having a copper-iron-aluminum atom as a main constituent and having high activity and high selectivity (excluding compounds having only an ester group). The present invention relates to a method for producing the same, and a method for producing alcohol using the catalyst.

[0002]

2. Description of the Related Art Alcohol is used as a fragrance, a solvent, a resin modifier, etc., and is generally produced by hydrogenating a carbonyl compound. Conventionally, the catalyst used for this hydrogen reduction is usually a copper-chromium oxide, and is usually called a copper-chromite catalyst. The manufacturing method is Industrial and Engineering Chemistry, No. 26.
Volume, page 878 (1936), has not made much progress to date. When manufacturing this catalyst,
It has the serious drawback that a large amount of hexavalent chromium ions are emitted. In order to prevent environmental pollution, these heavy metals are collected by a proper method, but the final treatment method of the heavy metal sludge generated here has not been established yet.

In order to solve this problem, copper-iron-aluminum type catalysts produced by various methods have been proposed (Japanese Patent Laid-Open Nos. 53-92395, 55-8820, and Japanese Examined Patent Publication). 58-50775). However, although these catalysts are superior in activity, selectivity and durability to conventional copper-chromite catalysts, the filtration rate is slow when the catalyst is separated from the catalyst-precipitated slurry during catalyst production, and large-scale filtration equipment is required. There is a drawback that requires (Japanese Patent Laid-Open No. 53-92395,
However, since urea is used as a precipitant, there is a problem in the manufacturing process such as a large load on the treatment of urea wastewater and ammonia wastewater due to this (Japanese Patent Publication No. 58-50775). Issue).

[0004]

In order to establish an industrial production method of a pollution-free catalyst which replaces a copper-chromite catalyst, which has a problem of environmental pollution, the inventors of the present invention have the problems of suppressing atomization of the catalyst and As a result of diligent study on rationalization of the catalyst production process, oxides and hydroxides of aluminum, silicon, titanium, zirconium, magnesium, iron,
Zeolite, and at least one selected from the group consisting of silica-alumina as a carrier, by using a hydroxide or carbonate of an alkali metal or alkaline earth metal instead of urea as a precipitant, the atomization of the catalyst The present invention was found to be a method for producing a copper-iron-aluminum-based catalyst in which a catalyst that can be suppressed, activity, selectivity, durability and filterability are significantly improved, and the catalyst production process is greatly simplified. It came to completion. That is, the present invention uses at least one selected from the group consisting of aluminum, silicon, titanium, zirconium, magnesium, iron oxides and hydroxides, zeolites, and silica-alumina as an atomic ratio (containing aluminum atoms. When the substance to be used is used as a carrier, the atomic ratio of the whole catalyst including the carrier is Cu / Fe / Al / (alkali metal and / or alkaline earth metal) /Zn=1/0.4 to 2.5 / 0.5 to 5.0 / 0-
0.4 / 0 to 1.0, wherein a carbonyl compound (excluding a compound having only an ester group) for reducing a catalyst and a method for producing the same, and a carbonyl compound (provided that The present invention provides a method for producing an alcohol, which comprises reducing hydrogen (excluding compounds having only an ester group).

The copper-iron-aluminum-based catalyst of the present invention is produced by the following method or. The manufacturing method which performs the following 1st process, 2nd process, 3rd process, and 4th process, or 1st process, 2nd process, and 3rd process in this order. (First step) At least one selected from the group consisting of aluminum, silicon, titanium, zirconium, magnesium, iron oxides and hydroxides, zeolite, and silica-alumina (hereinafter referred to as a carrier) is suspended in an aqueous medium. A step of making the solution turbid and causing the water-soluble copper salt and the water-soluble iron salt to react with an alkaline substance in the suspension to precipitate the copper compound and the iron compound on the surface of the carrier. (Second step) The surface of the solid particles present in the suspension obtained in the first step by reacting water-soluble aluminum with an alkaline substance in the suspension obtained in the first step Precipitating an aluminum compound on top. (Third step) A precipitate is obtained from the suspension obtained in the second step and washed with water to obtain a slurry or powder, or, if the fourth step is not carried out, then obtained. The process of drying and firing the slurry or powder. (Fourth step) (a) Consists of the slurry or powder obtained in the third step and (b) an alkali metal salt, an alkali metal hydroxide, an alkaline earth metal salt and an alkaline earth metal hydroxide A step of mixing with at least one selected from the group and drying and firing the obtained slurry or powder.

A manufacturing method in which the following first step, second step, third step and fourth step or first step, second step and third step are performed in this order. (First step) A carrier is suspended in an aqueous medium, and a water-soluble copper salt and a water-soluble iron salt are reacted with an alkaline substance in the suspension to precipitate a copper compound and an iron compound on the surface of the carrier. The process of making. (Second step) In the suspension obtained in the first step,
(I) by reacting a water-soluble aluminum salt with an alkaline substance, or (ii) by reacting a water-soluble aluminum salt and a water-soluble copper salt or a water-soluble zinc salt or a mixture thereof with an alkaline substance, On the surface of the solid particles present in the suspension obtained in the first step, the compound selected from the following (a) to (d) once or twice or more (in the case of two or more times, in no particular order) Precipitation step. (a) Aluminum compound. (b) Aluminum compounds and copper compounds. (c) Aluminum compounds and zinc compounds. (d) Aluminum compounds, copper compounds and zinc compounds. (Third step) A precipitate is obtained from the suspension obtained in the second step and washed with water to obtain a slurry or powder, or, if the fourth step is not carried out, then obtained. The process of drying and firing the slurry or powder. (Fourth step) (a) Consists of the slurry or powder obtained in the third step and (b) an alkali metal salt, an alkali metal hydroxide, an alkaline earth metal salt and an alkaline earth metal hydroxide A step of mixing with at least one selected from the group and drying and firing the obtained slurry or powder.

Each step of the method for producing a copper-iron-aluminum catalyst of the present invention will be described below. First Step The first step in the manufacturing method of the present invention is performed as follows. First, the water-soluble copper salt and the water-soluble iron salt are added in an atomic ratio of Cu / Fe.
= 1 / 0.4 to 2.5, and the carrier is added to this aqueous solution in an atomic ratio of Cu / carrier metal atom = 1 / 0.1 to 3.0
Suspend. The suspension is heated to 60 to 120 ° C. and an aqueous solution of an alkaline substance in an amount corresponding to the total equivalent number of copper and iron ions is added to precipitate the copper compound and the iron compound on the surface of the catalyst carrier. Examples of the water-soluble copper salt used in the present invention include cupric sulfate, cupric chloride, cupric nitrate and the like, and a mixture thereof may be used. Examples of the water-soluble iron salt used in the present invention include ferrous sulfate, ferrous chloride, ferrous nitrate and the like, and although a mixture thereof may be used, it is economical to use ferrous sulfate. It is the best from the aspect. It is also possible to use a ferric salt in combination, but care must be taken because if the ferric salt is added too much, the catalyst performance, especially the physical properties of the catalyst, will deteriorate.

Examples of the alkaline substance used in the present invention include hydroxides or carbonates of alkali metals or alkaline earth metals. The method of adding the alkaline substance to the suspension is not particularly limited, but in consideration of operability, these alkaline substances are usually added in an aqueous solution. When an alkali metal or alkaline earth metal hydroxide is used as the alkaline substance, it is desirable that the hydroxide be slowly added dropwise so as not to impair the filterability of the precipitation catalyst.
In the present invention, it is optimum to use an alkali metal carbonate. Although the concentrations of these alkaline substances can be arbitrarily selected, a high concentration of a precipitant can be used in view of the productivity of the catalyst. For example, in the case of sodium carbonate, 20-23%
An aqueous solution having a concentration of is suitable.

At least one selected from the group consisting of aluminum, silicon, titanium, zirconium, magnesium, iron oxides and hydroxides, zeolite, and silica-alumina as a carrier used in the first step is in a reaction tank. After being prepared in step (3), it may be used as it is, or may be prepared separately in advance. It is preferable to use those carriers having relatively uniform particle diameters. The average particle size of the carrier is 0.1 to 500 μm, preferably 0.4 to 50 μm. If the average particle size is below or above this range, both the catalytic activity and filterability cannot be simultaneously maintained at the levels desired by the present invention. As a method for preparing the carrier in the reaction vessel, the amount of ferric salt used as the carrier, for example, sulfate, nitrate, hydrochloride, etc. is dissolved in water, and then an amount of alkali equivalent to the number of equivalents of iron ion. There is a method in which a metal carbonate, for example, an aqueous sodium carbonate solution is added dropwise at a temperature of 60 ° C. or higher for neutralization. In the case of this method, the first step can be continuously performed by charging a copper salt and an iron salt into this slurry without purifying the formed precipitate. When a carrier having uniform physical properties is used, a catalyst with more stable performance can be produced. Therefore, it is more advantageous to use a carrier having uniform physical properties for production on an industrial scale.

Second Step The second step in the manufacturing method of the present invention is performed as follows.
That is, in the suspension obtained in the first step, (a) water-soluble aluminum salt (however, the amount of Al in this case is Cu / Al = atomic ratio to the water-soluble copper salt used in the first step). 1 / 0.1 ~ 5.0
, Preferably 1 / 0.5 to 3.0) and (b) an alkaline substance in an amount equivalent to the number of equivalents of the aluminum ion described in (a) above is added dropwise to adjust the temperature of the suspension. It is carried out by precipitating the aluminum compound while maintaining the temperature at 60 to 120 ° C. If the temperature of the suspension is out of this range, the desired activity and selectivity cannot be obtained in the obtained catalyst.

Examples of the water-soluble aluminum salt described in (a) above include aluminum sulfate, aluminum chloride, aluminum nitrate, and various types of alum, among which aluminum sulfate is most suitable. Moreover, you may use these mixtures. In order to further improve the activity and selectivity in the hydrogen reduction reaction in the aqueous solution described in (a) above, a water-soluble copper salt or a water-soluble zinc salt or a mixture thereof is used in the aqueous solution described in (a). Al / Cu / Zn = 1/0 to 1 in atomic ratio to aluminum salt
A copper compound or a zinc compound or a mixture thereof can be precipitated together with the aluminum compound by being present in an amount of / 0 to 0.5. Examples of the water-soluble copper salt described above include those described in the first step. Further, examples of the water-soluble zinc salt described above include zinc sulfate, zinc chloride, zinc nitrate, etc., but zinc sulfate is most preferable from the economical aspect.

An example of the alkaline substance described in (b) above is the alkaline substance used in the first step as well. The addition method is preferably an aqueous solution from the viewpoint of operability. The concentration is not particularly limited, but it is preferable to use an aqueous solution of about 20% by weight from the economical viewpoint. In order to prevent a sudden change in the pH of the suspension, the addition method of the alkaline substance is the aqueous solution described in (a) above and (b)
It is preferable to simultaneously add the alkaline substance described in 1 above or an aqueous solution thereof to the suspension. Further, when a water-soluble salt other than the water-soluble aluminum salt is used, the second step can be performed in one step or divided into two or more steps.

The example of the embodiment of the second step is as follows. Only the aluminum compound is precipitated. An aluminum compound and a copper compound are simultaneously precipitated. An aluminum compound and a zinc compound are simultaneously precipitated. The aluminum compound and the copper compound are simultaneously precipitated in the first step, and then the aluminum compound and the zinc compound are simultaneously precipitated in the second step. The aluminum compound and the copper compound are simultaneously precipitated in the first stage, and then the aluminum compound is precipitated in the second stage. The aluminum compound and the zinc compound are simultaneously precipitated in the first stage, and then the aluminum compound and the copper compound are simultaneously precipitated in the second stage. The aluminum compound and the zinc compound are simultaneously precipitated in the first stage, and then the aluminum compound is precipitated in the second stage. The aluminum compound, copper compound and zinc compound are simultaneously precipitated. The combination of these steps is repeated a plurality of times. The pH of the suspension obtained by the method described above is adjusted to 7.0 or higher, and then aging is performed for 0 to 8 hours.

Third step In the third step, the precipitate obtained in the second step is separated by a conventional method and washed with water to obtain a slurry or powder, or, if the fourth step is not carried out, then obtain it. The slurry or powder thus obtained is dried and calcined. Firing temperature is usually 100 ℃ or more 1
It is in the range of 200 ° C or lower, preferably 400 ° C or higher and 900 ° C or lower. The firing time is not particularly limited, but economically
10 hours or less is good. The product that has been calcined may be crushed, but may be used as a catalyst immediately without crushing.

Fourth Step In the manufacturing method of the present invention, the fourth step may or may not be performed. The fourth step is performed as follows. First, selected from the group consisting of (a) the slurry or powder obtained in the third step and (b) an alkali metal salt, an alkali metal hydroxide, an alkaline earth metal salt and an alkaline earth metal hydroxide. At least one (hereinafter,
Alkali metal / alkaline earth metal hydroxide, etc.) are mixed. In this case, the alkali metal / alkaline earth metal hydroxide or the like has an atomic ratio of Cu / (alkali metal and / or alkaline earth metal) = 1/0 to 0.4, preferably 1 / 0.001 to 0.4. To mix. The alkali metal / alkaline earth metal hydroxide or the like may be added in the form of powder or particles, but is preferably added as an aqueous solution. Examples of alkali metal / alkaline earth metal hydroxides include Ba (OH) ₂ , Ca (OH) ₂ , BaCO ₃ , and NaOH. The slurry or powder thus obtained is dried and calcined. The firing temperature is usually 100 ° C or higher and 120
It is in the range of 0 ° C or lower, preferably 400 ° C or higher and 900 ° C or lower. The firing time is not particularly limited, but economically
10 hours or less is good. The product that has been calcined may be crushed, but may be used as a catalyst immediately without crushing.

The catalyst of the present invention has excellent activities such as activity and selectivity due to the combination of the above-mentioned metals, but other metals such as noble metals may be added within the range not impairing the effects of the present invention. It is possible and does not preclude the combined use of any other metal.

In the present invention, a carbonyl compound (excluding compounds having only an ester group) is hydrogen-reduced in the presence of the above-mentioned catalyst for reduction to produce an alcohol. Examples of the carbonyl compound that can be used in the present invention include aliphatic compounds such as octyl aldehyde, decyl aldehyde, lauryl aldehyde, myristyl aldehyde, stearyl aldehyde, oleyl aldehyde, 2-ethylhexyl aldehyde, isostearyl aldehyde, undecylen aldehyde, citral and citronellal. Aldehydes or cyclohexanal, benzaldehyde, anisaldehyde, cumin aldehyde, phenylacetaldehyde, alicyclic or aromatic aldehydes such as furfural, nonyl methyl ketone, cyclohexanone, methyl cyclohexanone, methyl ethyl ketone, ketone compounds such as dibutyl ketone, and the like, When hydrogen reduction reaction is performed on these, the products corresponding to these are Lumpur is obtained.

In the method for producing alcohol of the present invention,
The reaction temperature for the hydrogen reduction reaction of carbonyl compounds is 100 to 30.
The temperature is preferably 0 ° C., and the hydrogen pressure is preferably about 5 to 400 kg / cm ² . Particularly, the hydrogen reduction reaction of aldehydes such as furfural, citronellal and benzaldehyde using the above-mentioned catalyst is carried out at a temperature of 110 to 250 ° C, preferably 130 to 18 ° C.
0 ℃, hydrogen pressure 10-300 kg / cm ² , preferably 20-150 kg
/ Is carried out in cm ^2. The amount of the above catalyst used is in the range of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the starting carbonyl compound.

[0019]

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

Example 1 A reactor having a reflux condenser was charged with water (300 g), CuSO ₄ .5H.
₂ O (48 g), FeSO ₄ .7H ₂ O (59 g) and aluminum hydroxide (Hijilite H-32 made by Showa Denko, 12.14 g) were added, and the temperature was raised to 96 ° C. with stirring. Temperature 95 ℃
The temperature was kept at ± 2 ° C for 1 hour. Then, while maintaining this temperature, a solution of Na ₂ CO ₃ (44.8 g) dissolved in water (150 g) was added dropwise over about 80 minutes. In the reaction, an initially blue-green precipitate gradually changed to brown and finally became black. The pH after the dropping was 8.95. Temperature is 95 ℃ ± 2 ℃
CuSO ₄ / 5H ₂ O (4.8g), Al ₂ (SO ₄ ) ₃ / 16H ₂ O
(46.8 g) dissolved in water (109.2 g) and Na ₂ CO ₃ (2
A solution of 7.6 g) dissolved in water (98.2 g) was added dropwise at the same time. 60 minutes for aqueous solution of metal salt,
It dripped over 30 minutes. PH after dropping alkaline solution in water
Was 8.71, and the pH after adding the metal salt aqueous solution was 8.11. A solution of Al ₂ (SO ₄ ) ₃ · 16H ₂ O (23.4 g) dissolved in water (53.5 g) was added dropwise to this over 30 minutes. The pH at this time was 4.12. Then, a solution of Na ₂ CO ₃ (14.3 g) dissolved in water (54.9 g) was added dropwise over 30 minutes. Further, 10% NaOH aqueous solution was added dropwise to adjust the pH to 10.5. Aging was performed for 1 hour while maintaining the pH at 10.5. After completion of the aging, the reaction product was filtered by suction.
Filtration was very easy and the filtrate was colorless. After washing the precipitate 3 times with 450 ml of water each time, Ba (OH) ₂ (4.21 g) was added to the water.
The solution dissolved in (320 g) was added, and the mixture was stirred for 30 minutes and evaporated to dryness. The dried product was lightly pulverized and calcined in air at 750 ° C. for 1 hour to obtain a desired catalyst. Cu / Fe / Al / Ba of this catalyst
The atomic ratio of / Zn was 1/1 / 1.81 / 0.063 / 0.

Using this catalyst, alcohol was produced by the following method. That is, in a 500 ml autoclave, 150 g of raw material citronellal (manufactured by Toyoda Fragrance) and 1.5 g of the above catalyst
After adding g to replace the system with hydrogen, the temperature is raised and the hydrogen pressure is 50 kg.
The reaction was carried out for 3 hours at a reaction temperature of 150 ° C./cm ² . During the reaction, sampling was performed at 30, 60, 90, 120, 150 minutes,
The composition was examined by gas chromatography analysis, the production amounts of citronellol and menthol as a by-product were plotted with the reaction time, and each production rate (zero-order reaction rate equation) was determined from the gradient,
When the selectivity is calculated from the ratio of the two, the production rate of citronellol (C): 200% / Hr (determined by GLC analysis. It means that the production rate is double that of 100% production in 1 hour. ) Menthol production rate (M): 0.8% / Hr (determined by GLC analysis. Meaning that it shows 0.8 / 100 production rate assuming 100% production in 1 hour) Selectivity M / C: 4.0 × The result was 10 ^-3 (the lower the number, the better the selectivity and the less by-products). After the reaction was completed, the reaction solution was cooled, the autoclave was opened to withdraw the reaction solution, 100 g of the extracted slurry was weighed, and a pressure filter with an internal heating temperature control of 3 cm inside diameter was used under constant conditions ( Filtration was carried out at a filtration pressure of 3 kg / cm ² and a filtration temperature of 50 ° C., and a filtration rate constant F (m ³ / m ² -Hr) per unit time was obtained to obtain a result of 6.0. The composition of the product is: citronellol 93.2%, citronellal 0.00
% And menthol 0.61%.

Example 2 In a 500 ml autoclave, 200 g of furfural (manufactured by Hanai Chemical), 0.8 g of Ca (OH) ₂ and 1.6 g of the catalyst of Example 1
Was added and the reaction was carried out at a hydrogen pressure of 120 kg / cm ² and a reaction temperature of 160 ° C. to produce furfuryl alcohol. In the reaction, hydrogen absorption was completed in 15 minutes. After the start of the reaction, the autoclave was cooled by cooling for 20 minutes, the contents were extracted and pressure filtered. Gas chromatographic analysis of the filtrate revealed that the composition of the product was 97.9% furfuryl alcohol and 0.16% unreacted furfural.

Example 3 To a 500 ml autoclave, 200 g of benzaldehyde (manufactured by Hanai Chemical Co., Ltd.) and 2 g of the catalyst of Example 1 were added and the hydrogen pressure was increased.
The reaction was carried out at 120 kg / cm ² and a reaction temperature of 180 ° C. to produce benzyl alcohol. In the reaction, hydrogen absorption was completed in 30 minutes. After 40 minutes from the start of the reaction, cooling was started, and after cooling, the autoclave was opened, the slurry was extracted, and pressure filtration was performed.
Gas chromatographic analysis of the filtrate revealed that the product composition was 97.3% benzyl alcohol and 0.25% unreacted benzaldehyde.

Examples 4 to 5 Catalysts were obtained in the same manner as in Example 1 except that the amount of barium hydroxide added was changed to the amount shown in Table 1. Using these catalysts, the same reaction as in Example 1 was carried out to obtain citronellol. Table 1 shows the production rate (C) of citronellol, the production rate (M) of menthol, the selectivity (M / C × 10 ⁻³ ), and the composition of the product.

Examples 6 to 8 Catalysts were obtained in the same manner as in Example 1 except that calcium hydroxide, sodium hydroxide and barium carbonate were used instead of barium hydroxide. Using these catalysts,
The same reaction as in Example 1 was performed to obtain citronellol.
Table 1 shows the production rate (C) of citronellol, the production rate (M) of menthol, the selectivity (M / C × 10 ⁻³ ), and the composition of the product.

Examples 9 to 14 Instead of aluminum hydroxide, titanium oxide, zirconium oxide, zeolite, silica-alumina, second oxide
A catalyst was obtained in the same manner as in Example 1 except that iron and magnesium oxide were used. Using these catalysts, the same reaction as in Example 1 was carried out to obtain citronellol. Table 2 shows the production rate (C) of citronellol, the production rate (M) of menthol, the selectivity (M / C × 10 ⁻³ ), and the composition of the product.

Examples 15 to 19 Cu / Fe / Al / (alkali metal / alkaline earth metal) / Zn
Example 1 except that the atomic ratio of was variously changed to the ratio shown in Table 2.
A catalyst was obtained in the same manner as in. Using these catalysts, the same reaction as in Example 1 was carried out to obtain citronellol. Table 2 shows the production rate (C) of citronellol, the production rate (M) of menthol, the selectivity (M / C × 10 ⁻³ ), and the composition of the product.

Comparative Examples 1 to 3 Catalysts were obtained in the same manner as in Example 1 except that the atomic ratio of Cu / Fe / Al / Ba / Zn was changed to the ratio shown in Table 3. Using these catalysts, the same reaction as in Example 1 was carried out to obtain citronellol. Table 3 shows the production rate (C) of citronellol, the production rate (M) of menthol, the selectivity (M / C × 10 ⁻³ ), and the composition of the product.

Comparative Example 4 Water (400 g), CuSO ₄ .5H was added to a reactor having a reflux condenser.
_{2 O (40.7g), FeSO 4} · 7H 2 O (45.5g) and Al ₂ (SO _{4) 3}
16H ₂ O (54.1 g) was added and the temperature was raised to 96 ° C. with stirring. The temperature was kept at 95 ° C ± 2 ° C and kept for 1 hour. Then, while maintaining this temperature, a solution of Na ₂ CO ₃ (64.5 g) dissolved in water (258 g) was added dropwise over about 80 minutes.
In the reaction, the initially blue-green precipitate gradually turns brown,
Eventually it turned black. Further, add 10% NaOH aqueous solution dropwise to adjust pH.
Was adjusted to 10.5. Aging was carried out for 1 hour while maintaining the pH at 10.5, and then the same operation as in Example 1 was carried out to obtain a catalyst. Using this catalyst, the same reaction as in Example 1 was carried out to obtain citronellol. Table 3 shows the production rate (C) of citronellol, the production rate (M) of menthol, the selectivity (M / C × 10 ⁻³ ), and the composition of the product.

Comparative Example 5 In a reactor having a reflux condenser, water (400 g), CuSO ₄ .5H
₂ O (40.7 g), FeSO ₄ / 7H ₂ O (45.5 g), Al ₂ (SO ₄ ) ₃
16H ₂ O (54.1 g) and aluminum hydroxide (Higelite H-32 manufactured by Showa Denko, 12.14 g) were added, and the temperature was raised to 96 ° C. with stirring. 1 while keeping the temperature at 95 ℃ ± 2 ℃
Held for hours. Then, while maintaining this temperature, Na ₂ CO ₃
A solution of (64.5 g) dissolved in water (258 g) was added dropwise over about 80 minutes. In the reaction, an initially blue-green precipitate gradually changed to brown and finally became black. Further, 10% NaOH aqueous solution was added dropwise to adjust the pH to 10.5. Aging was carried out for 1 hour while maintaining pH at 10.5, and after completion of the aging, suction filtration, washing with water, drying and calcination were carried out to obtain a catalyst. Using this catalyst, the same reaction as in Example 1 was carried out to obtain citronellol. Table 3 shows the production rate (C) of citronellol, the production rate (M) of menthol, the selectivity (M / C × 10 ⁻³ ), and the composition of the product.

Examples 20 to 23 Catalysts were obtained in the same manner as in Example 1 except that the calcination temperatures were 450 ° C, 600 ° C, 900 ° C and 1050 ° C. Using these catalysts, the same reaction as in Example 1 was carried out to obtain citronellol. Table 3 shows the production rate (C) of citronellol, the production rate (M) of menthol, the selectivity (M / C × 10 ⁻³ ), and the composition of the product.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

Industrial Applicability According to the present invention, a copper-iron-aluminum-based reduction catalyst having extremely high activity and high selectivity can be obtained, and by using such catalyst, very high-purity alcohol can be obtained in extremely high yield. Can be obtained at.

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Claims (6)

[Claims] 1. A carbonyl compound (provided that an ester group
Corresponding alcohols
A reduction catalyst for obtaining aluminum, silicon, titanium, zirconium, magnesium, iron oxides and hydroxides, zeolite, and at least one selected from the group consisting of silica-alumina as a carrier, the atomic ratio (When using a substance containing aluminum atoms as a carrier, the atomic ratio of the entire catalyst including the carrier) is Cu / Fe
/ Al / (alkali metal and / or alkaline earth metal) /
Zn = 1 / 0.4 to 2.5 / 0.5 to 5.0 / 0 to 0.4 / 0 to 1.0
A catalyst for reducing a carbonyl compound (excluding compounds having only an ester group). 2. In producing the reduction catalyst according to claim 1, the following first step, second step, third step and fourth step, or first step, second step and third step A method for producing a reduction catalyst, which is carried out in this order. (First step) At least one selected from the group consisting of aluminum, silicon, titanium, zirconium, magnesium, iron oxides and hydroxides, zeolite, and silica-alumina (hereinafter referred to as a carrier) is suspended in an aqueous medium. A step of making the solution turbid and causing the water-soluble copper salt and the water-soluble iron salt to react with an alkaline substance in the suspension to precipitate the copper compound and the iron compound on the surface of the carrier. (Second step) The surface of the solid particles present in the suspension obtained in the first step by reacting water-soluble aluminum with an alkaline substance in the suspension obtained in the first step Precipitating an aluminum compound on top. (Third step) A precipitate is obtained from the suspension obtained in the second step and washed with water to obtain a slurry or powder, or, if the fourth step is not carried out, then obtained. The process of drying and firing the slurry or powder. (Fourth step) (a) Consists of the slurry or powder obtained in the third step and (b) an alkali metal salt, an alkali metal hydroxide, an alkaline earth metal salt and an alkaline earth metal hydroxide A step of mixing with at least one selected from the group and drying and firing the obtained slurry or powder. 3. In producing the reduction catalyst according to claim 1, the following first step, second step, third step and fourth step, or first step, second step and third step A method for producing a reduction catalyst, which is carried out in this order. (First step) At least one selected from the group consisting of aluminum, silicon, titanium, zirconium, magnesium, iron oxides and hydroxides, zeolite, and silica-alumina (hereinafter referred to as a carrier) is suspended in an aqueous medium. A step of making the solution turbid and causing the water-soluble copper salt and the water-soluble iron salt to react with an alkaline substance in the suspension to precipitate the copper compound and the iron compound on the surface of the carrier. (Second step) In the suspension obtained in the first step,
(I) by reacting a water-soluble aluminum salt with an alkaline substance, or (ii) by reacting a water-soluble aluminum salt and a water-soluble copper salt or a water-soluble zinc salt or a mixture thereof with an alkaline substance, Compounds selected from the following (a) to (d) on the surface of the solid particles present in the suspension obtained in the first step, once or twice or more (in two or more times, in no particular order) Precipitation step. (a) Aluminum compound. (b) Aluminum compounds and copper compounds. (c) Aluminum compounds and zinc compounds. (d) Aluminum compounds, copper compounds and zinc compounds. (Third step) A precipitate is obtained from the suspension obtained in the second step and washed with water to obtain a slurry or powder, or, if the fourth step is not carried out, then obtained. The process of drying and firing the slurry or powder. (Fourth step) (a) Consists of the slurry or powder obtained in the third step and (b) an alkali metal salt, an alkali metal hydroxide, an alkaline earth metal salt and an alkaline earth metal hydroxide A step of mixing with at least one selected from the group and drying and firing the obtained slurry or powder. 4. The reaction temperature in the first step and the second step is 60 to
It is 120 degreeC, The manufacturing method of the catalyst for reduction of Claim 2 or 3. 5. The firing temperature in the third step or the fourth step is 100.
It is -1200 degreeC, The manufacturing method of the catalyst for reduction as described in any one of Claims 2-4. 6. In the presence of the reducing catalyst according to claim 1,
A process for producing an alcohol, which comprises reducing a carbonyl compound (excluding compounds having only an ester group) with hydrogen.