JP3206183B2 - Method for producing 1,4-butanediol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention, maleic anhydride, maleic acid, succinic acid anhydride, by the catalytic hydrogenation of the oxygenated C ₄ hydrocarbon selected from succinic acid or γ- butyrolactone 1,4-butanediol And a method for producing the same. 1,4-butanediol is mainly used as a raw material for plastics such as polybutylene terephthalate and polyurethane, and is also used as an intermediate for producing pyrrolidine and adipic acid.

[0002]

2. Description of the Related Art Hitherto, many methods have been reported for producing 1,4-butanediol by hydrogenating oxygen-containing C ₄ hydrocarbons such as maleic anhydride. For example, the best known method is to use a copper-based catalyst. However, in this method, an organic carboxylic acid such as maleic acid cannot be directly reduced, and the carboxylic acid must be once converted into an ester and then reduced, which increases the production process. Further, in this method, the reaction is generally performed under a hydrogen pressure of 200 atm or more, which is uneconomical in terms of energy and equipment.

[0003] On the other hand, some catalysts capable of directly reducing a carboxylic acid such as maleic acid have been proposed. For example, JP-A-63-218636 or U.S. Pat.
No. 686 describes a method for producing tetrahydrofuran or γ-butyrolactone from an aqueous solution of maleic acid using a palladium-rhenium catalyst supported on activated carbon. In this method, the selectivity for 1,4-butanediol is very low.

Further, US Pat. No. 4,827,001 proposes a method for directly reducing maleic acid using a ruthenium-iron oxide as a catalyst.
Insufficient selectivity for 4-butanediol.

[0005]

As described above, conventionally, in the method of hydrogenating maleic acid or the like, it is necessary to carry out the reaction under relatively high hydrogen pressure conditions in order to increase the reactivity. Was. In addition, since various reaction products are produced by hydrogenation, it is difficult to obtain 1,4-butanediol with a high selectivity, and the by-product of tetrahydrofuran has been inevitable.

[0006]

The present inventors have conducted intensive studies in view of the above problems, and as a result, when performing catalytic hydrogenation reaction of maleic acid or the like in the presence of a catalyst, ruthenium is used as a catalyst.
It has been found that when a reaction is carried out in the presence of a specific substance using a supported catalyst of uranium and tin, the production of 1,4-butanediol is dramatically increased, and the present invention has been reached. .

That is, the gist of the present invention is to provide maleic anhydride,
In a method for producing 1,4-butanediol by catalytic hydrogenation of maleic acid, succinic anhydride, succinic acid or γ-butyrolactone, the catalytic hydrogenation is carried out by (1) supporting ruthenium and tin on a carrier. And (2) a method for producing 1,4-butanediol, which is carried out in the presence of an alkali metal compound, an alkaline earth metal compound or a nitrogen base compound; and maleic anhydride, maleic acid, A method for producing 1,4-butanediol by catalytically hydrogenating succinic anhydride, succinic acid or γ-butyrolactone, wherein the catalytic hydrogenation is carried out by (1) ruthenium and tin,
And (2) a method for producing 1,4-butanediol, which is carried out in the presence of a supported catalyst in which an alkali metal compound or an alkaline earth metal compound is supported on a carrier.

Hereinafter, the present invention will be described in detail. The reaction raw material of the present invention is maleic anhydride, maleic acid, succinic anhydride, succinic acid, γ-butyrolactone or a mixture thereof. In the hydrogenation reaction of the present invention, (anhydrous) maleic acid is hydrogenated into (anhydride) succinic acid from the viewpoint of the reaction mechanism or the analysis result of the reaction product,
Subsequently, it is considered that γ-butyrolactone is formed, and that 1,4-butanediol is further generated. Therefore, in the present invention, any of the above compounds can be used as a reaction raw material, or a mixture of two or more compounds may be used.

[0009] In the present invention, the metal constituting the catalyst and
It is essential to use ruthenium and tin. These metal components are used as a supported catalyst which is carried on a carrier.

Activated carbon, diatomaceous earth, silica, alumina, titania, zirconia and the like can be used alone or in combination of two or more as a carrier for supporting the noble metal and tin. The method of contacting the raw material compounds of the noble metal component and the tin component with these carriers is not particularly limited, but an immersion method is usually employed. That is, for example, the raw material compound is dissolved in a solvent capable of dissolving, for example, water to form a solution, and the porous carrier is immersed in the solution to be impregnated and supported. After the support, it is dried, and if necessary, calcined and reduced. Firing is usually 10
Performed at 0-600 ° C. As the reduction treatment, known liquid-phase reduction and gas-phase reduction are used. In the case of gas-phase reduction,
Usually, it is carried out at 100 to 500 ° C, preferably 200 to 350 ° C.

The loading amounts of ruthenium and tin are generally 0.5 to 50% by weight, preferably 1 to 50% by weight, based on the carrier.
20% by weight. In addition, it is preferable that the amount of supported tin is usually 0.1 to 5% by weight based on ruthenium , from the viewpoint of improving the selectivity of the product. As the raw material compounds of ruthenium and tin, mineral salts of these metals such as nitric acid, sulfuric acid and hydrochloric acid are generally used, but organic acid salts such as acetic acid, hydroxides, oxides or complex salts are also used. You can also.

The above catalysts can be used as described above even when used alone.
Although it has sufficient hydrogenation activity of the reaction material, 1,4
-To obtain butanediol with high selectivity, alkali
Metal compounds, alkaline earth metal compounds or nitrogen basification
The compound must be present in the reaction system. Alkali metallization
Compounds and alkaline earth metal compounds are
Is a mineral acid salt with alkaline earth metal nitric acid, hydrochloric acid, sulfuric acid, etc.
Organic acid salts such as acetic acid and oxalic acid, hydroxides, oxides, etc.
LiNO_Three, LiCl, LiOAc, NaOAc,
KOAc, CsOAc, Mg (OAc)_Two, Ca (OA
c)_Two, Sr (OAc) _Two, Ba (OAc)_Two, LiO
H and the like.

The nitrogen-base compound is ammonia,
Organic amines and salts thereof, or pyrrole, pyrrolidine, pyridine, piperidine, indole, nitrogen-containing heterocyclic compounds such as quinoline and salts thereof, ammonium acetate, triethylamine, pyridine, pyrroline,
N-methylpyrrolidine and the like. The method for causing the alkali metal compound, alkaline earth metal compound or nitrogen-base compound to be present in the reaction system is not particularly limited, and these compounds may be directly added to the reaction system. The addition amount is usually 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the catalyst.

As for the alkali metal compound and the alkaline earth metal compound, in addition to the method of directly adding them to the above-mentioned reaction system, a method of supporting them as a metal component together with a catalyst component on a carrier is also possible. As in the method for supporting the catalyst component on the carrier, a method for impregnating the carrier with an aqueous solution of an alkali metal compound or the like is usually adopted, as in the method for supporting the catalyst component. After the support, the support is dried and, if necessary, is fired and reduced. The amount of the alkali metal or alkaline earth metal carried is usually 0.1 to 100 parts by weight per 100 parts by weight of the catalyst.
Parts by weight, preferably 1 to 50 parts by weight.

The catalytic hydrogenation reaction in the present invention is usually performed at a temperature of 130 to 350 ° C., preferably 160 to 300 ° C., a hydrogen pressure of 10 to 300 kg / cm ² , preferably 50 to 200 kg.
It is performed in the range of kg / cm ² . The amount of the catalyst used in the reaction is desirably 0.1 to 100 parts by weight based on 100 parts by weight of the reaction raw material such as maleic anhydride. However, depending on various conditions such as a reaction temperature or a reaction pressure, a practical amount may be used. It can be arbitrarily selected within a range where the reaction rate can be obtained.

As a reaction system, either a liquid phase suspension reaction or a fixed bed reaction can be employed. The reaction may be carried out without a solvent, or a solvent may be used if necessary.
When a solvent is used, the solvent is not particularly limited as long as it does not adversely affect the reaction, and specific examples thereof include water; alcohols such as methanol, ethanol, octanol, and dodecanol; tetrahydrofuran, dioxane, and tetraoxane. Ethers such as ethylene glycol dimethyl ether; and hydrocarbons such as hexane, cyclohexane, and decalin.

The 1,4-butanediol produced by the reaction is separated and purified by a known method such as distillation. The reaction raw material remaining after the separation or γ-butyrolactone as a reaction intermediate can be recycled to the reaction system as a reaction raw material and used again.

[0018]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist of the invention. “%” Indicates “% by weight”.

Examples 1 to 8 Ruthenium (III) chloride and tin (II) chloride were combined with 5N HCl.
It is dissolved in an aqueous solution and ethanol (1/1 volume ratio), and SiO ₂ (manufactured by Fuji Devison, specific surface area 609 m ² ) is used as a carrier.
/ G, pore volume of 0.37 ml / g), and after removing the solvent with a rotary vacuum dryer, baking at 150 ° C. for 2 hours under a nitrogen atmosphere, and then reducing at 300 ° C. for 2 hours under a hydrogen atmosphere, It was obtained 7% Ru-5% Sn / SiO 2 catalyst. 0.5 g of maleic anhydride was dissolved in 9.5 g of water, and 0.2 g of the catalyst prepared by the above method was added to 0.3 mm of the additive shown in Table 1.
The mixture was charged into a 70 ml spinner-stirring autoclave together with 100 l of hydrogen, and 100 kg / cm ² of hydrogen was injected at room temperature.
The reaction was carried out at a temperature of 3 ° C. for 3 hours. The results obtained by analyzing the reaction product by gas chromatography are shown in Table 1.

Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that no additive was added using the catalyst of Example 1 and the results are shown in Table 1.

[0021]

[Table 1] CML: maleic anhydride THF: tetrahydrofuran GBL: γ-butyrolactone BDO: 1,4-butanediol

Example 9 LiOAc was dissolved in water.
% Ru-5% Sn / SiO _2, and after removing the solvent by a rotary vacuum dryer, baking at 150 ° C. for 2 hours under a nitrogen atmosphere, and then reducing at 300 ° C. for 2 hours under a hydrogen atmosphere,
It was obtained 7% Ru-5% Sn- 0.3% Li / SiO 2 catalyst. 15 g of maleic anhydride was dissolved in 35 g of water, charged in a 200 ml autoclave together with 4 g of the catalyst prepared by the above method, and 20 kg / cm ² of hydrogen was injected under pressure at room temperature.
The temperature was raised to 40 ° C. Next, at 240 ° C.,
g / cm ² and reacted for 2 hours. Table 2 shows the results.
Shown in

Comparative Example 2 Using the catalyst of Example 1, the reaction was carried out in the same manner as in Example 9 without adding any additives. Table 2 shows the results.

[0024]

[Table 2] CML: maleic anhydride THF: tetrahydrofuran GBL: γ-butyrolactone BDO: 1,4-butanediol

[0025]

According to the method of the present invention, tetrahydrofuran is obtained under a relatively mild reaction condition by a catalytic hydrogenation reaction using maleic anhydride, maleic acid, succinic anhydride, succinic acid or γ-butyrolactone as a raw material. By-products such as 1,4-butanediol can be produced with high selectivity and high yield.

Continuation of front page (56) References JP-A-1-168346 (JP, A) JP-A-64-15136 (JP, A) JP-A-58-216131 (JP, A) JP-A-61-56139 (JP, A) , A) JP-A-61-243033 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 31/20 C07C 29/149 C07B 61/00 300

Claims (2)

(57) [Claims] 1. A method for producing 1,4-butanediol by catalytically hydrogenating maleic anhydride, maleic acid, succinic anhydride, succinic acid or γ-butyrolactone,
The catalytic hydrogenation is carried out in the presence of (1) a supported catalyst comprising ruthenium and tin supported on a carrier and (2) an alkali metal compound, an alkaline earth metal compound or a nitrogen base compound. -A method for producing butanediol. 2. A method for producing 1,4-butanediol by catalytic hydrogenation of maleic anhydride, maleic acid, succinic anhydride, succinic acid or γ-butyrolactone,
The catalytic hydrogenation is carried out by (1) ruthenium and tin, and (2)
A method for producing 1,4-butanediol, which is carried out in the presence of a supported catalyst comprising an alkali metal compound or an alkaline earth metal compound supported on a carrier.