JPS615036A - Production of alcohol - Google Patents

Abstract

PURPOSE:To obtain the titled compound in a remarkably high catalytic activity, in the direct hydrogenation of a carboxylic acid to produe the corresponding alcohol, by using a cobalt catalyst doubly activated with two kinds of different cocatalyst components each consisting of a specific metal. CONSTITUTION:An alcohol is produced in high catalytic activity, by contacting an organic carboxylic acid with hydrogen in the presence of a cobalt catalyst containing (A) one or more metals (the first cocatalyst component) selected from aluminum, zirconium, molybdenum and 3b-group element of the periodic table and (B) one or more metals (the second cocatalyst component) selected from copper and 8-group noble metal element of the periodic table. The atomic ratio of the first cocatalyst component to cobalt is 0.001-0.2, preferably 0.05-0.1, and that of the second cocatalyst component to cobalt is 1X10<-5>-0.005, preferably 5X10<-5>-0.002. Preferably, the second cocatalyst component is supplied in a form supported on cobalt containing the first cocatalyst component.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to the use of organic carboxylic acids having one or more carboxylic acid groups which are doubly activated with two different types of cocatalysts. This invention relates to a method for producing alcohol by hydrogenation using a cobalt catalyst.

[Conventional technology and problems]

Attempts to produce alcohols by direct hydrogenation of free carboxylic acids have been made for a long time, and numerous solid catalysts have been proposed. The main ones are copper-based catalysts including copper chromium, cobalt metal-based catalysts, iron-based catalysts, noble metal catalysts of ruthenium, rhodium and platinum, and rhenium catalysts. Among these catalysts, cobalt metal-based catalysts have been studied from an industrial perspective.

For example, Japanese Patent Publication No. 55-4090 discloses a catalyst in which rhenium and molybdenum are added to cobalt metal.
Publication No. 2056 proposes a catalyst in which a metal compound selected from iron, zinc, phosphorus, molybdenum, tungsten, and calcium is added to cobalt metal: The feature is that it improves the durability of the catalyst. However, methods using these catalysts are still not satisfactory in terms of catalytic activity.

[Means for solving problems]

Therefore, the present inventors conducted extensive research to find a highly active hydrogenation catalyst for directly hydrogenating carboxylic acids to produce the corresponding alcohols, and as a result, they completed their invention.

That is, the present invention uses aluminum and zirconium.

One or more metals selected from the group consisting of molybdenum and elements of group 3b of the periodic table (first promoter component), and one or more metals selected from the group consisting of copper and noble metal elements of group 8 of the periodic table ( The present invention provides a method for producing alcohol, which comprises bringing an organic carboxylic acid into contact with hydrogen in the presence of a cobalt catalyst containing a second promoter component.

The method for producing the catalyst composition according to the present invention is not particularly limited, and it can be prepared by a known method. For example, a precipitate obtained by drying and calcining a precipitate obtained by a coprecipitation method in which a precipitant is added to a mixed aqueous solution of metal lumps of cobalt, a metal serving as the first promoter component, and a metal serving as the second promoter component. Alternatively, it can be prepared by a method of uniformly mixing compounds such as respective oxides, hydroxides, carbonates, phosphates, nitrates, etc., and reducing the fired catalyst precursor with a reducing substance.

When adding the second promoter component here, as an alternative to the coprecipitation method or homogeneous mixing method described above, the metal compound of the second promoter component is precipitated or impregnated and supported on the cobalt compound containing the first promoter component. It is also possible to do this.

When preparing by coprecipitation method or by precipitating or impregnating and supporting the second cocatalyst component on a cobalt compound containing the first cocatalyst component, as long as the metal lump used is water-soluble. Any substance may be used, but generally it is a sulfur Wi salt, a nitrate, an ammonium complex salt, an acetate, or a chloride. In addition, ammonia, urea,
Alkaline aqueous solutions such as ammonium carbonate, sodium carbonate, sodium hydroxide, and potassium hydroxide are used.

In addition, such a catalyst composition may contain diatomaceous earth, alumina, silica gel, silica-alumina, magnesia, etc. to the extent that the activity or selectivity per unit volume is not significantly impaired.
There is no problem in using it after reducing it while supported on a known carrier such as zirconia or titania.

In the present invention, the first promoter component that can be added to the cobalt catalyst is at least one metal compound selected from the group consisting of aluminum, zirconium, molybdenum, and elements of group 5b of the periodic table, Particularly preferred are scandium, yttrium, lanthanide, and actinide.
It is a metal compound belonging to Group B. These metal compounds are oxygen-containing compounds such as oxygen oxides, phosphates or borates, and have an atomic ratio of 0.001 to cobalt.
-0.2, preferably 0.05-0.1.

The second promoter component that can be added to the nicobalt catalyst is copper,
At least one metal selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, and platinum.

Although it is possible to add these metals in a uniformly mixed state with cobalt and the first promoter component, it is particularly preferable to add them in a state in which they are supported on cobalt containing the first promoter component. , preferably 5x10 to 0.005 in atomic ratio to cobalt.
It is included at a rate of 0.002.

The cobalt catalyst doubly activated with the first and second cocatalyst components is obtained by reducing the catalyst precursor prepared by the method described above with a reducing substance. The reducing substances used here include hydrogen, carbon oxide, ammonia, hydrazine, formaldehyde, and methanol, but they may also be used alone or in a mixed state (and inert gases such as nitrogen or a small amount of May be used in the presence of water vapor.

When reducing the catalyst precursor, either a gas phase reduction method or a liquid phase reduction method performed in a solvent such as a hydrocarbon such as liquid paraffin, dioxane, an aliphatic alcohol, or an aliphatic ester may be used. For example, when reducing using hydrogen gas, the temperature is 150°C to 800°C, preferably 2°C.
It is preferable to carry out the treatment at a temperature of 00°C to 500°C until water generation is no longer observed or hydrogen absorption is no longer observed. In particular, when reducing in a solvent, the temperature is between 200°C and 3°C.
It is desirable to carry out the treatment at a temperature of 50° C. until no hydrogen absorption is observed.

The organic carboxylic acid used in the present invention may be a monocarboxylic acid or a polycarboxylic acid. Aliphatic carboxylic acids, aromatic carboxylic acids, araliphatic carboxylic acids, and alicyclic carboxylic acids are used as monocarboxylic acids, and aliphatic dicarboxylic acids and aromatic dicarboxylic acids are used as polycarboxylic acids. These carboxylic acids may be either free carboxylic acids or in the form of acid anhydrides.

It is also possible to use a solvent when hydrogenating the above carboxylic acids. Water, dioxane, alcohols, etc. can be used as a solvent, and a water solvent is particularly preferred. Furthermore, even in the case of hydrogenation without a solvent, a significant increase in catalytic activity is observed by adding a small amount of water. Here, the small amount of water is water in an amount of 1 to 3% by weight based on the raw material carboxylic acid, and this amount of water is sufficient to produce the effect.

The production method of the present invention can be carried out in any of the suspended bed reaction method, fluidized bed reaction method, or fixed bed reaction method, but in that case the catalyst shape is molded into a shape suitable for each reaction method. Ru.

For example, when the present invention is to be carried out using a suspended bed reaction method, the following reactions and conditions are selected.

The reaction temperature is preferably 150°C to 300°C, particularly preferably 180°C to 250°C. If the temperature is lower than 150°C, the catalytic activity decreases significantly, and if the temperature exceeds 300°C, a significant increase in by-products is observed, but in any case, the temperature is not impractical. Practical hydrogen pressure is preferably 150 ky/tan2 to 300 kg10n2.

The amount of the catalyst used is 0.5 to 50 weight percent, preferably 2 to 15 weight percent, based on the starting carboxylic acid.

〔Effect of the invention〕

The catalyst presented in the present invention exhibits very high activity in the direct hydrogenation of carboxylic acids to produce the corresponding alcohols, and lacks either the cobalt first cocatalyst component or the second cocatalyst component. However, the catalyst performance deteriorates significantly. Furthermore, it is surprising that a remarkable effect that was not initially expected was found by adding only a few tens of ppm of the second cocatalyst component relative to cobalt.

[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

In addition, in the reaction in the examples of the present invention, the acid value (AV) was 1.
Since hydrogen absorption occurs almost linearly with time until it drops to 0, the hydrogen absorption rate is used as a measure of activity. However, if a large amount of catalyst is used, the hydrogen absorption rate is too high, making it difficult to accurately determine the activity. Since this is not required, the amount of catalyst used is reduced to 4.
% or less and conduct activity measurements. In order to quickly complete the reaction in a short period of time, this can be achieved by raising the reaction temperature or increasing the amount of catalyst used. However, if the reaction temperature is raised, side reactions are more likely to occur, so the amount of catalyst used is increased. It is better to deal with it by In this case, the reaction can be completed in a short time by increasing the amount of catalyst used to about 5 to 7%.

Example 1 Catalyst Preparation A precipitate formed when a mixed aqueous solution of cobalt nitrate and yttrium nitrate with an atomic ratio of cobalt to yttrium of 1:0.01 and an aqueous ammonium carbonate solution were stirred and mixed at room temperature was sufficiently washed with water and then heated at 110°C. dry. After drying 6
Calcination is carried out at 00° C. for 4 hours to obtain the entire cobalt-yttrium oxide.

Next, the atomic ratio of cobalt to palladium is 1:o, o o
vI4 so that o a! The aqueous palladium nitrate solution and cobalt-yttrium oxide are thoroughly mixed and then dried at 110°C to obtain a palladium-supported cobalt-yttrium oxide.

Above, the oxide, lauryl alcohol,! :,! : After replacing the air charged in the autoclave with hydrogen at 4:50
The pressure was increased to 110R2, and the temperature was raised to 250t while stirring. After reduction until no hydrogen absorption was observed at 250°C, the resulting cake was used as a catalyst.

Cobalt-yttrium-palladium catalyst evaluated for catalytic activity 5.4.9
(as metallic cobalt) and 5 g of water using a rotating stirring method.
Pour into a 5 liter autoclave, hydrogen pressure 25 Q
The reaction was carried out at kl/m2, temperature of 225° C., and stirring speed of 80 rpm.

The reaction results are shown below.

Reaction time 29 minutes Hydrogen absorption rate 7 k110u12Win or more (at 2
25°C) Analysis value Hydroxyl value (OHV) = 184.
3.

8v=60.2, AV=5.0 Comparative Example 1 Catalyst Preparation A cobalt oxide is obtained according to the method described in Example 1 using an aqueous cobalt nitrate solution and an aqueous ammonium carbonate solution. The obtained cobalt oxide was reduced with hydrogen according to the method described in Example 1 to prepare a catalyst.

Catalyst Activity Evaluation According to the method described in Example 1, the activity of the catalyst prepared as described above was evaluated.

The reaction results are shown below.

Reaction time: 260 minutes Hydrogen absorption rate: 0, 71 kg/rat' 6 w
in (at 225℃) Analysis value 0) tV=141.4
1 = 79.9 AV = 0.07 Comparative Example 2 Catalyst Preparation The method described in Example 1 was applied to the cobalt oxide described in Comparative Example 1 so that the atomic ratio of cobalt to palladium was i: o, o o o a. A catalyst was prepared by impregnating and supporting palladium nitrate in accordance with the method described in Example 1, and reducing it with hydrogen by the method described in Example 1.

Catalyst Activity Evaluation According to the method described in Example 1, the activity of the catalyst prepared as described above was evaluated.

The reaction results are shown below.

Reaction time: 130 minutes Hydrogen absorption rate: 1,35 kl/7a2・min
(at 25℃) Analysis value 0HV=142.4 8V=7
8.5AV = 1.3 Comparative Example 3 Using the cobalt-yttrium oxide described in Catalyst Preparation Example 1, hydrogen reduction was performed according to the method described in Example 1 to prepare a solute medium.

Catalyst Activity Evaluation According to the method described in Example 1, the activity of the catalyst prepared as described above was evaluated.

The reaction results are shown below.

Reaction time: 300 minutes Hydrogen absorption rate: 0.99 units/i・win (at 225
℃ analysis value 0HV=208.9 SV=51.6
.

AV=8.8 As described above, it can be seen that the cobalt catalyst used in the present invention does not have the same performance even if any one of the co-catalyst components is missing.

Examples 2 to 4 Catalyst preparation Example 1 using cobalt nitrate and zirconyl nitrate so that the atomic ratio of cobalt to zirconium was 1:0.05.
A cobalt-zirconium oxide was obtained according to the method described in .

Using the above oxide, palladium nitrate, platinum nitrate, and copper nitrate were impregnated and supported according to the method described in Example 1, and then reduced with hydrogen according to the method described in Example 1 to prepare a catalyst.

Evaluation of Catalytic Activity The activity of the catalyst prepared as described above was evaluated in accordance with the method described in Example 1, except that a catalyst with a cobalt concentration of 5.19 was used.

The reaction results are shown in Table 1.

Comparative Example 4 Using the cobalt-zirconium oxides described in Melting Medium Preparation Examples 2 to 4, hydrogen reduction was performed according to the method described in Example 1 to prepare a catalyst.

Catalyst Activity Evaluation The activity of the catalysts prepared as described above was evaluated according to the method described in Examples 2 to 4.

The reaction results are shown in Table 1.

Examples 5 to 10 Catalyst Preparation Example 1 Using cerium nitrate, lanthanum nitrate, neodymium nitrate, scandium nitrate, ammonium molybdate, and aluminum nitrate so that the atomic ratio of cobalt to the first promoter component was 1:0.01. Each oxide was obtained according to the method described in .

Using the above oxide, the atomic ratio of cobalt to palladium is 1.
: Palladium nitrate was impregnated and supported according to the method described in Example 1 so as to have a concentration of 0.000 B, and hydrogen reduction was performed according to the method described in Example 1 to prepare a catalyst.

Catalyst Activity Evaluation According to the method described in Example 1, the activity of the catalyst prepared as described above was evaluated.

The reaction results are shown in Table 2.

Example 11 Using the catalyst described in Example 6, the activity of the catalyst was evaluated in accordance with the method described in Example 1, except that the reaction temperature was 200°C.

The reaction results are shown below.

Reaction time 65 minutes Hydrogen absorption rate 2.6 kfl/Cm2@min
(at 00℃) Analysis value 0) IV = 167.4 8
V=67.5A V=3.1 Examples 12 to 15 Catalyst Preparation Example 1 Using cobalt nitrate and zirconyl nitrate so that the atomic ratio of cobalt to zirconium was 1: o, ol.
A cobalt-zirconium oxide was obtained according to the method described in .

Using the above oxide, the atomic ratio of cobalt to palladium is 1: 0.00008, 1: 0,0004, 1:
Palladium nitrate was impregnated and supported according to the method described in Example 1 so that the ratio was 0.000B, 1:0,0015, and hydrogen reduction was performed according to the method described in Example 1 to prepare each catalyst.

Catalyst Activity Evaluation According to the method described in Example 1, the activity of the catalyst prepared as described above was evaluated.

The reaction results are shown in Table 3.

Comparative Example 5 Catalyst Preparation The cobalt-zirconium oxides described in Examples 12 to 15 were reduced with hydrogen according to the method described in Example 1 to prepare a catalyst.

Catalyst Activity Evaluation The activity of the catalyst prepared as described above was evaluated according to the method described in Example 1.

The reaction results are shown in Table 3.

Example 16 Adipic acid 150.9 (purity 98.15%) and Example 6
Catalyst 5.4.9 (as metal cobalt) and 3 g of water were placed in a rotary stirring 0.5 liter autoclave, hydrogen pressure 250 kg/ape2% temperature 250°C,
The reaction was carried out at a stirring speed of 800 rpm.

The reaction results are shown below.

Reaction time 180 minutes Hydrogen absorption rate 4.4 kg/s'・win (at 250°C) Ester dimerization condensate 1'-'% Adipic acid 6.8% Example 17 Olein wi! 1501 (AV=202J, 8V
-2rJ5.6IV=89.5) and the catalyst described in Example 1 5,4 Jil (as metallic cobalt) and water 1
The mixture was charged into a 5J'i rotary stirring type 0.5 liter autoclave, and the reaction was carried out at a hydrogen pressure of 250 kp/cm2, a temperature of 200° C., and a stirring speed of 800 rpm.

The reaction results are shown below.

Reaction time: 180 minutes

Claims (1)

[Scope of Claims] 1. One or more metals (first promoter component) selected from the group consisting of aluminum, zirconium, molybdenum, and elements of group 3b of the periodic table, and copper and noble metal elements of group 8 of the periodic table. A method for producing alcohol, which comprises bringing an organic carboxylic acid into contact with hydrogen in the presence of a cobalt catalyst containing one or more metals (second promoter component) selected from the group consisting of: 2. The first cocatalyst component has an atomic ratio of 0.00 to cobalt.
1 to 0.2, and the second promoter component is contained in an atomic ratio of 1 x 10^-^5 to 0.005 to cobalt. .