JPH0737411B2 - Method for producing methyl isobutyl ketone - Google Patents

Description

TECHNICAL FIELD The present invention relates to an improved method for producing methyl isobutyl ketone (hereinafter abbreviated as MIBK), which is highly useful as an organic solvent.

[Conventional technology]

MIBK is conventionally produced by a so-called three-step method using acetone and hydrogen as raw materials and passing through diacetone alcohol and mesityl oxide. However, this method is long in all steps, and since the first diacetone alcohol production step is an equilibrium reaction, the raw material conversion cannot be increased and the efficiency is low.

Therefore, a method of directly producing MIBK from acetone and hydrogen in one step has also been studied, and conventionally, the following proposals have been made.

A method of reacting in a liquid phase using palladium-ion exchange resin, palladium-zirconium phosphate, palladium-alumina or the like as a catalyst.

White metal element as a catalyst-zirconia, palladium-
A method of reacting in a gas phase using titania, palladium-magnesia-titania or the like.

[Problems to be solved by the invention]

However, the above method has problems in terms of catalyst activity and catalyst life. The above method is also not practical in view of MIBK yield, catalyst activity, catalyst life, etc.

[Means for solving problems]

In order to solve such problems, the present inventors have made diligent efforts to develop a novel highly active and highly selective catalyst capable of directly producing MIBK from acetone and hydrogen in one step, and as a result, The present invention has been achieved by finding that the above problems can be solved by using an oxide or hydroxide of a metal species and palladium as essential components and a catalyst system.

That is, the gist of the present invention is to react at least one metal oxide selected from the group consisting of cerium, hafnium and tantalum in the one-step production of methyl isobutyl ketone by reacting acetone and hydrogen in the presence of a catalyst. Or a method for producing methyl isobutyl ketone, which comprises using a catalyst containing hydroxide and palladium as essential components.

The method of the present invention will be described in detail below.

The oxide or hydroxide of the specific metal element used in the method of the present invention is produced by various known methods. That is, the action of alkali on the soluble salt solution, the hydrolysis of alkoxide, the thermal decomposition of unstable compounds, and the oxidation of metals.

Of these production methods, when produced in a system in the presence of water, the produced product is usually a hydroxide or oxide containing a considerable amount of water. This product can be used as it is or after drying, for the purpose of the present invention.
Those baked at a suitable temperature and dehydrated by heating can also be used for this purpose. Regarding the condensation activity of acetone, depending on the element or the manufacturing method, the size of the water-containing product and the heat-dehydrated product cannot be generally stated. However, compared with various known catalysts, the catalyst of the present invention produces MIBK with high activity and high selectivity regardless of the presence or absence of a water content. Therefore, the form of the catalyst of the present invention is an oxide or a hydroxide, but the oxide may be a hydrous oxide.

The production of MIBK from acetone according to the method of the present invention requires an element which catalyzes the hydrogenation reaction. Generally, a white metal element is used, but palladium is particularly preferable, and palladium is used in the method of the present invention. As a method of using palladium, it can be used by supporting it on an oxide or hydroxide of the above-mentioned specific metal element, but a catalyst such as palladium-carbon, palladium-alumina or the like is used as an oxide or hydroxide of the specific metal element. It can also be used as a mixture with a substance. The amount of palladium used is based on the oxide or hydroxide of a specific metal element.
The weight ratio is usually 0.001 to 10%, preferably 0.01 to 5%.

MIBK can be produced from acetone in either the gas phase or the liquid phase, but is preferably in the liquid phase. . The reaction temperature in the liquid phase is preferably below the critical temperature of acetone (235 ° C). Since catalytic activity cannot be obtained at too low a temperature, it is preferably between 30 ° C and 200 ° C. The reaction pressure is not less than the spontaneous pressure of acetone and not more than 150 kg / cm ² , more preferably between normal pressure and 50 kg / cm ² , and it is set in a hydrogen atmosphere. The catalyst may be used in the form of either a suspension bed or a fixed bed. The conversion of acetone is preferably suppressed to 50% or less.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded.

Example 1 1.7 g of ceric hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 400 ° C. in advance
Hydrogen reduced with 1% Pd / C (manufactured by Nippon Engelhard) 0.
51 g and 40 ml of acetone were supplied to a stainless steel micro autoclave with an internal volume of about 100 ml.
The mixture was heated to 0 ° C., hydrogen was added so that the reaction pressure became a gauge pressure of 10 kg / cm ^2, and the reaction was carried out with stirring. Hydrogen was continuously supplied so that a constant pressure was always maintained during the reaction.
After the reaction, the reaction was cooled and analyzed by gas chromatography. The results are shown in Table 1.

Example 2 What baked the ceric hydroxide of Example 1 at 500 degreeC.
Using 1.07 g and 0.32 g of 1% Pd / C as a catalyst, the reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.

Example 3 Using the oxide of 1.83 g of cerium hydroxide of Example 1 calcined at 650 ° C. and 0.55 g of 1% Pd / C as a catalyst, 90 ° C., 7 kg / cm ²
The same procedure as in Example 1 was carried out except that the reaction was carried out at G. The results are shown in Table 1.

Example 4 25 g of hafnium oxychloride was dissolved in water of 1 and 5N-ammonia water was added to form a precipitate. The precipitate was thoroughly washed with water until chlorine ions were eliminated, and then dried at 100 ° C. 2.10 g and 1% Pd / C 0.63 g were used as catalysts under the same conditions as in Example 1. The results are shown in Table 1.

Example 5 The hafnium hydroxide obtained in Example 4 is calcined at 500 ° C. to give hafnium oxide, which is reacted at 180 ° C. and 16.5 kg / cm ² G using 2.03 g of oxide and 0.68 g of 1% Pd / C as a catalyst. Was done. The results are shown in Table 1.

Example 6 After dissolving 5 g of tantalum pentachloride in 50 ml of ethanol to form an ethoxide, an ethanol solution of potassium hydroxide (92 g /
) Was added to form a precipitate. After aging this precipitate,
After being washed twice with 1N-hydrochloric acid aqueous solution by boiling, it was washed with boiling deionized water three times and dried at 120 ° C. to give hydrous tantalum oxide (tantalic acid). 1.47 g of this tantalic acid and 1% Pd /
The reaction was carried out under the same conditions as in Example 1 using 0.44 g of C as a catalyst. The results are shown in Table 1.

[Effects of the Invention] According to the method of the present invention, MIBK is produced in one step from acetone and hydrogen.
In the production of MIBK, MIBK can be produced economically and advantageously by using a highly active and highly selective catalyst containing palladium as an essential component and an oxide or hydroxide of a specific metal element.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C07C 45/73 // C07B 61/00 300

Claims (1)

[Claims] 1. When producing methyl isobutyl ketone in a single step by reacting acetone and hydrogen in the presence of a catalyst,
A method for producing methyl isobutyl ketone, which comprises using a catalyst containing palladium and at least one metal oxide or hydroxide selected from the group consisting of cerium, hafnium and tantalum as essential components.