JPH0737410B2 - 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 has conventionally been 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 for directly producing MIBK from acetone and hydrogen in one step has been studied, and the following methods have been conventionally proposed.

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, palladium-chromium or the like.

[Problems to be solved by the invention]

However, the above method is problematic in terms of catalyst activity and catalyst life, and the above method is not practical in view of MIBK yield, catalyst activity and catalyst life.

[Means for solving problems]

In order to solve the above 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,
The inventors have found that the above problems can be solved by carrying out a reaction in a liquid phase using a catalyst in which an oxide or hydroxide of a specific metal element is combined with palladium as a new catalyst system, and arrived at the present invention.

That is, the gist of the present invention is to react at least one metal selected from the group consisting of titanium, zirconium and chromium in the one-step production of methyl isobutyl ketone by reacting acetone and hydrogen in the liquid phase in the presence of a catalyst. In the method for producing methyl isobutyl ketone, which comprises using a catalyst containing palladium or an oxide or hydroxide as an essential component.

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 which water is present, the produced product is usually a hydroxide or oxide containing a large amount of water. This product can be used for the purpose of the present invention as it is or after being dried, but a product obtained by baking at a suitable temperature and dehydration by heating can also be used for the present 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 unequivocally defined, and there are high activity in the water-containing state and high activity in the dehydrated state. As 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, although the form of the catalyst of the present invention is an oxide or a hydroxide, the oxide may be a hydrous oxide.

In order to produce MIBK from acetone according to the method of the present invention, an element that catalyzes the hydrogenation reaction is necessary. Generally, a white metal element is used, but palladium is particularly preferable,
This 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 palladium catalyst such as palladium-carbon or palladium-alumina is an oxide or hydroxide of the specific element. It can also be used as a mixture with.
The amount of palladium used is 0.001 to 10% by weight, preferably 0.01 to 5% by weight, relative to the oxide or hydroxide of the specific element.

MIBK is produced from acetone in the liquid phase. The reaction temperature 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 atmospheric pressure or 50 kg / cm 2.
^{Between 2} is often set under 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 Titanic acid obtained by hydrolysis of titanium tetrabutoxide
1.73 g and 0.52 g of 1% Pd / C (manufactured by Nippon Engelhard) that had been reduced with hydrogen at 400 ° C were used as catalysts, and 40 ml of acetone was supplied to a stainless steel autoclave with an internal volume of about 100 ml, and this autoclave was heated to 140 ° C. The mixture was heated, 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 solution was cooled and analyzed by gas chromatography. The results are shown in Table 1.

Example 2 2.38 g of catalyst in which the titanic acid used in Example 1 was impregnated in an aqueous palladium chloride solution to carry 0.3% by weight of palladium.
Was hydrogenated at 200 ° C., and then the reaction was carried out under the same reaction conditions as in Example 1. The results are shown in Table 1.

Example 3 The titanic acid obtained in Example 1 was calcined at 500 ° C. to form titanium oxide, and 1.60 g of this titanium oxide and 0.48 g of 1% Pd / C were used as a catalyst and used for the reaction under the same conditions as in Example 1. I was there. First result
Shown in the table.

Example 4 1.84 g of commercially available zirconium hydroxide (manufactured by Shin Nippon Metal Co., Ltd.),
0.55 g of 1% Pd / C was used as a catalyst and used in the reaction under the same conditions as in Example 1. The results are shown in Table 1.

Example 5 1.67 g of zirconium oxide obtained by calcining the zirconium hydroxide used in Example 4 at 500 ° C. and 0.5 g of 1% Pd / C were used as catalysts in the reaction under the same conditions as in Example 1. First result
Shown in the table.

Example 6 4N-ammonia water was added to an aqueous solution of chromium (II) nitrate,
The obtained precipitate was thoroughly washed with water and then dried at 100 ° C. (the product is temporarily referred to as Cr (OH) ₃ ). This Cr (OH) ₃ 2.77g
And 1% Pd / C 0.82 g were used as catalysts in the reaction under the same conditions as in Example 1. The results are shown in Table 1.

Example 7 Cr (OH) ₃ obtained in Example 6 was heated to 500 ° C. in a nitrogen atmosphere to obtain chromium oxide. This chromium oxide 1.07g and 1% P
Using d / C 0.32 g as a catalyst, the reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.

EFFECTS OF THE INVENTION By using a highly active and highly selective catalyst according to the method of the present invention, MI is economically advantageous from acetone and hydrogen.
BK can be manufactured.

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

Claims (1)

[Claims] 1. When at least one metal selected from the group consisting of titanium, zirconium and chromium is used in the step of producing methyl isobutyl ketone by reacting acetone and hydrogen in the liquid phase in the presence of a catalyst, the oxidation of at least one metal. A method for producing methyl isobutyl ketone, which comprises using a catalyst containing an oxide or a hydroxide and palladium as essential components.