JPH07165644A - Production of 1,4-butanediol and/or tetrahydrofuran - Google Patents

Abstract

PURPOSE:To produce 1,4-butanediol and/or tetrahydrofuran in high yield under relatively mild reaction condition by using a catalyst having high reaction activity. CONSTITUTION:1,4-Butanediol and/or tetrahydrofuran are produced by the catalytic hydrogenation reaction of maleic anhydride, maleic acid, succinic anhydride, succinic acid, gamma-butyrolactone or their mixture. The reaction is carried out by using a catalyst produced by supporting Ru, tin and at least one kind of element selected between Pt and Rh on a carrier.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention uses maleic anhydride, maleic acid, succinic anhydride, succinic acid, γ-butyrolactone or a mixture thereof as a raw material, and produces 1,4-butanediol and / or by a catalytic hydrogenation reaction. It relates to a method for producing tetrahydrofuran. 1,4-butanediol is
It is mainly used as a raw material for plastics such as polybutylene terephthalate and polyurethane, and is also used as a production intermediate for pyrrolidine and adipic acid. Tetrahydrofuran is used as a solvent because it has a low boiling point and an excellent dissolving power, and is also used as a raw material for polytetramethylene ether glycol, tetrahydrothiophene and the like.

[0002]

2. Description of the Related Art Heretofore, many methods have been reported for 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,
Since the carboxylic acid has to be once converted into an ester and then reduced, the manufacturing process becomes long. Also, with this method,
Generally, the reaction is carried out under a hydrogen pressure of 200 atm or more, which is an uneconomical method in terms of energy and equipment.

On the other hand, some catalysts which can directly reduce carboxylic acids such as maleic acid have been proposed. For example, JP-A-63-218636 and US Pat.
No. 686 describes a method for producing tetrahydrofuran or γ-butyrolactone from an aqueous maleic acid solution using a palladium-rhenium catalyst supported on activated carbon. However, the method described in JP-A-63-218636 has a low reaction substrate concentration, and the method described in US Pat. No. 4,659,686 requires a hydrogen pressure of 150 atm or higher when carrying out the reaction. There is a drawback that

US Pat. No. 4,827,001 proposes a method for directly reducing maleic acid using ruthenium-iron oxide as a catalyst. In this method, 1,4-butane is used. The selectivity of diol, tetrahydrofuran and γ-butyrolactone is not sufficient.

[0005]

As described above, in the conventional hydrogenation reaction of maleic acid or the like, the reaction is carried out under relatively high hydrogen pressure conditions or low substrate concentration conditions in order to enhance the reactivity. There was a need. Therefore, according to the present invention, a maleic acid or the like is hydrogenated using a catalyst having a high reaction activity to obtain 1,4
-To provide a method for producing butanediol and / or tetrahydrofuran.

[0006]

In the method of the present invention, maleic anhydride, maleic acid, succinic anhydride, succinic acid, γ-
When producing 1,4-butanediol and / or tetrahydrofuran by catalytic hydrogenation reaction using butyrolactone or a mixture thereof as a raw material, ruthenium (hereinafter,
A catalyst comprising at least one selected from “Ru”), platinum (hereinafter “Pt”) and rhodium (hereinafter “Rh”) and tin supported on a carrier. It is characterized by using.

The present invention will be described in detail below. In the method of the present invention, maleic anhydride, maleic acid, succinic anhydride, succinic acid, γ-butyrolactone or a mixture thereof is used as a reaction raw material. In the method of the present invention, in view of the estimated reaction mechanism and the analysis result of the reaction product, the (anhydrous) maleic acid is hydrogenated to become (anhydrous) succinic acid,
Then, it is supposed to be γ-butyrolactone and further produce 1,4-butanediol and / or tetrahydrofuran as a final product. Therefore, in the present invention, any of the above compounds can be used as a reaction raw material, and a mixture of two or more of these may be used.

In the method of the present invention, Ru, Pt and R
A catalyst in which at least one kind of h (hereinafter, Ru, Pt, and Rh are collectively referred to as "noble metal component") and tin are supported on a carrier is used. As the carrier, porous carriers such as activated carbon, diatomaceous earth, silica, alumina, titania and zirconia can be used alone or in combination of two or more kinds.

The method of preparing the catalyst is not particularly limited, but usually,
The immersion method is adopted. When the dipping method is used, for example, the compound of the precious metal component of the catalyst raw material compound and a tin compound can be dissolved in a solvent, for example, water to form a solution, and a separately prepared porous carrier is immersed in this solution, There is a method of supporting a precious metal component and a catalyst component composed of tin on a carrier.

The order of loading each catalyst component on the carrier is not particularly limited, and all the metal components may be loaded simultaneously at the same time, each component may be loaded individually one by one, or some of the components may be loaded. The effect of the present invention can be achieved even when the above are combined and carried a plurality of times. However, among them, especially, Ru and tin are first supported on a carrier, and then Pt and Rh are supported.
The effect of the present invention can be further enhanced by additionally supporting at least one selected from the group. The cause of the improvement of the reaction activity by supporting at least one selected from Pt and Rh after Ru and tin is not known in detail, but Pt having a high hydrogen activation ability or a high hydrogenation reaction activity. It is considered that the metal component on the catalyst is supported on the catalyst surface by supporting Rh or Rh later than the other components, and the metal component on the surface effectively functions in the hydrogenation reaction.

After the catalyst component solution is immersed and supported (when the immersion and supporting treatment is carried out a plurality of times, each time), it is dried. The drying is performed under reduced pressure, for example, 50 to 10
After the treatment under the temperature condition of 0 ° C., the treatment is conducted under the temperature condition of 100 to 150 ° C. under the flow of an inert gas such as argon gas. Then, if necessary, firing and reduction treatments are performed. When performing the firing treatment, usually 100 to
It is performed in the temperature range of 600 ° C. Further, when performing the reduction treatment, a known liquid-phase reduction method or vapor-phase reduction method is adopted, but in the case of the vapor-phase reduction method, it is usually in the temperature range of 100 to 500 ° C, preferably 200 to 350 ° C. Done in range. Regarding the structure of the catalyst after the reduction treatment, the details are unknown, but it is estimated that under the above-mentioned reducing conditions, substantially all of the noble metal component is reduced to metal, and tin is
It is presumed that a part remains divalent or tetravalent.

The amount of the noble metal component (the total amount of Ru and Pt or Rh) and tin supported is usually 0.5 to 50% by weight, preferably 1 to 20%, based on the carrier in terms of metal element.
% By weight. It is preferable that Pt and / or Rh coexist in an amount of 0.01 to 10 times by weight relative to Ru from the viewpoint of improving the activity. Tin is usually 0.1 with respect to the noble metal component.
It is preferable to coexist in an amount of up to 5 times by weight from the viewpoint of improving the selectivity of the product. Incidentally, as the raw material compound of the noble metal component and tin, nitric acid, sulfuric acid, mineral acid salts such as hydrochloric acid of these metals are generally used, but organic acid salts such as acetic acid, hydroxides,
Oxides or complex salts can also be used. As these raw material compounds, a solvent used for dipping and supporting on a carrier, for example, those soluble in water and the like are preferable, for example, ruthenium chloride, rhodium chloride, tin chloride, rhodium nitrate, tin acetate, hexachloroplatinic acid and the like. Can be mentioned.

To produce 1,4-butanediol and / or tetrahydrofuran by the method of the present invention, the temperature is usually 130 to 350 ° C., preferably 160 to 300.
C, hydrogen pressure 10-300 kg / cm ² , preferably 50
The condition of ~ 200 kg / cm ² is adopted. In the case of the batch reaction, the amount of the catalyst used is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the reaction raw material such as maleic anhydride, but various conditions such as reaction temperature or reaction pressure. Can be arbitrarily selected within a range in which a practical reaction rate can be obtained.

The reaction system may be either a liquid phase suspension reaction or a fixed bed reaction. The reaction may be carried out without a solvent, or if necessary, a solvent which does not adversely influence the reaction may be used. The solvent that can be used at this time is not particularly limited, but specifically, water; alcohols such as methanol, ethanol, octanol, and dodecanol; ethers such as tetrahydrofuran, dioxane, tetraethylene glycol dimethyl ether; and others, hexane, cyclohexane , And hydrocarbons such as decalin.

The 1,4-butanediol and / or tetrahydrofuran produced in the reaction is separated and purified by a known method such as distillation. In addition, the unreacted raw material remaining after the separation and purification or γ-butyrolactone as a reaction intermediate can be reused as a reaction raw material.

[0016]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited to the description of the following Examples unless it exceeds the gist thereof. In the following, “%” means “% by weight”. Example 1 A sample bottle having a volume of 30 ml was charged with RuCl ₃ .3H ₂ O in an amount of 0.
790 g, 0.228 g of H ₂ PtCl ₆ .6H ₂ O, S
0.476 g of nCl ₂ .2H ₂ O was weighed and put in each, and 1.8 ml of 5N-HCl aqueous solution was further put in to dissolve it.
4.36 g of SiO2 (Fuji Davison product, special grade 12, specific surface area of 679 m ² / g, pore volume of 0.37 ml / g) was added as a carrier and shaken well.
After that, the contents were transferred to a 100 ml eggplant-shaped flask, and the solvent water was removed at 60 ° C. and 25 mmHg in a rotary vacuum dryer, and the mixture was baked at 150 ° C. for 2 hours in a nitrogen atmosphere and then 300 ° C. in a hydrogen atmosphere. Reduced for 2 hours at 6.
The 1% Ru-1.7% Pt- 5% Sn / the SiO ₂ catalyst was prepared.

In a 200 ml autoclave, water 35
A solution prepared by dissolving 15 g of maleic anhydride in g was charged, and then 4 g of the catalyst prepared by the above method was charged, 20 kg / cm ² of hydrogen was injected under stirring at room temperature, and the temperature was raised to 240 ° C. While maintaining the internal temperature of the autoclave at 240 ° C,
Hydrogen was injected under pressure to increase the hydrogen pressure up to 100 kg / cm ^2, and the reaction was carried out at this pressure for 2 hours. After completion of the reaction, the reaction product was analyzed by gas chromatography. The results are shown in Table 1.

Example 2 0.680 g of RuCl ₃ .3H ₂ O, RhCl ₃ .3H ₂
0.245 g of O and 0.475 of SnCl ₂ .2H ₂ O
g, 1.8 ml of 5N-HCl aqueous solution, and S as a carrier
Preparation was carried out by the same procedure as in Example 1 using 4.40 g of iO _{2, and} was 5.3% Ru-1.8% Rh-5% S.
A catalyst of n / SiO ₂ was prepared.

Using this catalyst, hydrogenation reaction of maleic anhydride was carried out in the same procedure as in the example described in Example 1. The analysis results of the reaction product are shown in Table 1. Comparative Example 1 RuCl ₃ .3H ₂ O 0.906 g, SnCl ₂ .2H ₂
Using 0.475 g of O, 1.8 ml of a 5N-HCl aqueous solution, and 4.40 g of SiO ₂ as a carrier, the preparation was carried out in the same manner as in Example 1 to obtain 7% Ru-5% Sn.
A / SiO ₂ catalyst was prepared.

Using this catalyst, hydrogenation reaction of maleic anhydride was carried out in the same procedure as in the example described in Example 1. The analysis results of the reaction product are shown in Table 1.

[0021]

[Table 1] In Table 1, the abbreviations have the following meanings. CML: maleic anhydride THF: tetrahydrofuran GBL: γ-butyrolactone BDO: 1,4-butanediol

Example 3 A 50 ml sample bottle was charged with RuCl.₃・ 3H₂O to 1.
691g, H₂PtCl₆・ 6H₂0.226 g of O, S
nCl₂・ 2H₂Weigh 0.950 g of O and put it in
Then, 3.6 ml of 5N-HCl aqueous solution was further added and dissolved,
SiO as carrier ₂(Fuji Davison products, specialists
Grade 12, specific surface area 679m²/ G, pore volume
8.76 g of 0.37 ml / g) was added and shaken well.
Then, transfer the contents to a 100 ml eggplant-shaped flask,
In a vacuum dryer, add water as the solvent under the conditions of 60 ℃ and 25mmHg.
After removing, baking treatment is performed at 150 ° C. for 2 hours in a nitrogen gas atmosphere.
And then reduction treatment under hydrogen atmosphere at 300 ℃ for 2 hours
Then, 6.5% Ru-0.85% Pt-5% Sn / Si
O₂Was prepared.

In an autoclave having a capacity of 200 ml, water 35
A solution prepared by dissolving 15 g of maleic anhydride in g was charged, and then 4 g of the catalyst prepared by the above method was charged, 20 kg / cm ² of hydrogen was injected under stirring at room temperature, and the temperature was raised to 240 ° C. While maintaining this temperature, hydrogen was introduced under pressure to increase the hydrogen pressure to 70 kg / cm ² , and while maintaining this pressure, hydrogen gas was circulated while bubbling the reaction solution at about 25 liters / hour to remove volatile components from the system. The reaction was carried out for 2 hours while being removed to the outside. After the reaction was completed, the components remaining in the kettle and the volatile components removed outside the system were analyzed by gas chromatography. The results are shown in Table 2.

Example 4 RuCl ₃ .3H ₂ O was added to a sample bottle having a volume of 50 ml.
691 g, 0.950 g of SnCl ₂ .2H ₂ O are weighed and put, respectively, and 3.6 ml of 5N-HCl aqueous solution is further put in to dissolve, and SiO ₂ as a carrier (Fuji Devison product, special grade 12, specific surface area 679 m ² /
g, pore volume 0.37 ml / g) and added 8.76 g, and shaken well. After that, the contents were transferred to a 100 ml eggplant-shaped flask, and the solvent water was removed under the conditions of 60 ° C. and 25 mmHg in a rotary vacuum dryer, followed by baking treatment at 150 ° C. for 2 hours in a nitrogen gas atmosphere, and then in a hydrogen atmosphere. , At 300 ° C 2
After reduction treatment for time, Ru—Sn / SiO ₂ was obtained.

Next, in a sample bottle having a volume of 50 ml, H ₂ Pt was added.
Weigh out 0.226 g of Cl ₆ .6H ₂ O and add 5 more
After 3.6 ml of N-HCl aqueous solution was added and dissolved, the whole amount of Ru-Sn / SiO ₂ prepared above was added and shaken well.
After that, the contents were transferred to a 100 ml eggplant-shaped flask, and the solvent water was removed under the conditions of 60 ° C. and 25 mmHg in a rotary vacuum dryer, followed by baking treatment at 150 ° C. for 2 hours in a nitrogen gas atmosphere, and then in a hydrogen atmosphere. , Pt addition type catalyst (6.5% Ru-5% Sn) + after reduction treatment at 300 ° C. for 2 hours
0.85% Pt / SiO ₂ was prepared.

Using this catalyst, hydrogenation reaction of maleic anhydride was carried out in the same manner as in Example 3. The results are shown in Table 2. Example 5 The amount of SiO ₂ used was 8.506 g, H ₂ PtCl ₆ ·
A Pt-added type catalyst (6.5% Ru-5% S) was prepared in the same manner as in Example 4 except that 6H ₂ O was changed to 0.903 g.
n) + 3.4% Pt / SiO ₂ was prepared.

Using this catalyst, hydrogenation reaction of maleic anhydride was carried out in the same manner as in Example 3. The results are shown in Table 2.

[0028]

[Table 2] In Table 2, the abbreviations have the following meanings. CML: maleic anhydride THF: tetrahydrofuran GBL: γ-butyrolactone BDO: 1,4-butanediol

[0029]

According to the method of the present invention, maleic anhydride, maleic acid, succinic anhydride, succinic acid, γ-butyrolactone or a mixture thereof is used as a raw material, and the reaction is carried out under relatively mild reaction conditions by catalytic hydrogenation reaction. Thus, 1,4-butanediol and / or tetrahydrofuran can be produced in a high yield, and its industrial utility value is extremely large.

Claims (4)

[Claims] 1. When producing 1,4-butanediol and / or tetrahydrofuran by catalytic hydrogenation reaction using maleic anhydride, maleic acid, succinic anhydride, succinic acid, γ-butyrolactone, or a mixture thereof as a raw material. Using a catalyst in which at least one selected from ruthenium, platinum and rhodium and tin are supported on a carrier 1,
A method for producing 4-butanediol and / or tetrahydrofuran. 2. The catalyst according to claim 1, wherein the catalyst is such that ruthenium and tin are first supported on a carrier, and then at least one selected from platinum and rhodium is additionally supported on the carrier. A method for producing 1,4-butanediol and / or tetrahydrofuran. 3. The catalyst according to claim 1, wherein the catalyst prepared through a step of immersing a solution of a ruthenium compound, a compound of at least one metal selected from platinum and rhodium, and a tin compound in a carrier is used. A method for producing butanediol and / or tetrahydrofuran. 4. A catalyst prepared through a step of immersing a solution of a ruthenium compound and a tin compound in a carrier and a subsequent step of immersing a solution of at least one metal compound selected from platinum and rhodium in the carrier. The method for producing 1,4-butanediol and / or tetrahydrofuran according to claim 3.