JPH0416237A - Catalyst and method for preparing gamma-butylolactone - Google Patents

Abstract

PURPOSE:To prepare a cyclic compound such as THF or the subject gamma-BL with high selectivity by using a solid catalyst prepared by supporting palladium and cobalt on a crystalline aluminosilicate carrier. CONSTITUTION:As a catalyst for preparing gamma-butylolactone by hydrogenating maleic or succinic anhydride, crystalline aluminosilicate such as zeolite or stabilized Y-type zeolite is used. Palladium and cobalt are supported on this crystalline aluminosilicate by ion exchange or dipping. The catalyst thus obtained prepares a cyclic compound such as THF or gamma-BL with high selectivity and high hydrogenating activity.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to the production of γ-butyrolactone by hydrogenating maleic acid or cono-conic acid anhydride (hereinafter, both are collectively abbreviated as C4 anhydride). The present invention relates to an improved catalyst for producing γ-butyrolactone and a method for producing γ-butyrolactone using the same.

[Conventional technology]

Conventionally, many proposals have been made regarding catalysts for producing γ-butyrolactone (hereinafter abbreviated as γ-BL) by hydrogenating C4 anhydride in a liquid phase, but these can be broadly classified into two types. For example, Ni-Re system (Special Publication No. 43-6947
Publication No.), Ni-No system (Japanese Patent Publication No. 49-5337), Ni-Re-Mo system (Japanese Patent Publication No. 48-37673)
There are two types of materials: those containing Ni as the main metal, such as in Japanese Patent Publication No. 5G-29142, and those containing Co as the main metal, such as Co--Pd (Japanese Patent Publication No. 5G-29142). However, Ni-based methods produce a large amount of tetrahydrofuran (hereinafter abbreviated as THF) and are likely to be accompanied by by-products such as butyric acid and propionic acid, so they have the disadvantage that they cannot selectively produce the desired γ-BL.

Moreover, due to the poor acid resistance, Ni is easily eluted into the reaction system, and although Re is added to improve the acid resistance, it is not sufficient.

On the other hand, the latter Co-Pd catalyst with Co as the main metal is
Compared to the former Ni-based material, it has a higher γ-BL selectivity and also has acid resistance, but its hydrogenation activity is slightly inferior. Sarani, γ
- Addition of chromium to improve BL selectivity (JP-A-61-1
No. 15079) or the carrier is diatomaceous
111974) or improved catalysts using niobium oxide as a carrier (Japanese Patent Application Laid-Open No. 111975/1982) have been proposed in order to suppress the elution of cobalt and palladium. In this way, when comparing both Ni-based and Co-based,
Co-based materials are characterized by a small amount of by-products produced and a high selectivity for γ-BL.

However, even in these Co-based known catalysts, by-products accompanied by ring cleavage such as succinic acid, maleic acid, propionic acid, butyric acid, and 1,4-butanediol are obtained in the hydrogenation of C4 anhydrides. Furthermore, the hydrogenation activity is also not sufficient.

[Problem to be solved by the invention] Therefore, by hydrogenating C4 anhydride in the presence of a catalyst, γ-B
In the reaction for obtaining L, there is a strong desire to develop a catalyst that has a high selectivity for cyclic compounds such as THF and γ-BL and has high hydrogenation activity.

[Means for Solving the Problems] In the process of studying catalyst carriers, the present inventors found that when crystalline aluminosilicate was used as a carrier, THF
Alternatively, it has been found that cyclic compounds such as γ-BL can be produced with high selectivity.

Among them, the inventors discovered an interesting new fact that stabilized Y-type zeolite specifically exhibits extremely high activity and has a high production ratio of cyclic compounds, leading to the completion of the present invention.

That is, the present invention is characterized in that a solid catalyst in which palladium and cobalt are supported on a crystalline aluminosilicate carrier is used in the reaction of hydrogenating C4 anhydride in the presence of a catalyst to obtain γ-BL. A method for manufacturing BL is provided.

The details will be explained below.

The support used in the catalyst of the present invention is a crystalline aluminosilicate. Specifically, Y type and L type.

These are so-called zeolites such as mordenite and ferrierite. These crystalline aluminosilicates may be used as they are, or stabilized zeolites in which the molar ratio of silica/alumina is increased by ordinary calcination treatment or various dealumination treatments such as steam calcination and acid treatment may be used.

The zeolite used as a catalyst carrier for the hydrogenation reaction preferably has a silica/alumina molar ratio of 5 or more.

Among them, the use of stabilized Y-type zeolite with a silica/alumina molar ratio of 5.8 or more obtained by acid treatment of Y-type zeolite as a carrier has extremely high activity compared to conventional catalysts, and it is possible to suppress the formation of cyclic compounds. It is extremely advantageous in terms of acquisition.

This crystalline aluminosilicate may be supported with an alkali metal or alkaline earth metal salt and subjected to a firing treatment. Y type, L type.

Mordenite, ferrierite, and stabilized zeolites obtained by dealuminizing them generally contain 0 to several percent of alkali metal or alkaline earth metal ions, but if a new alkali metal or alkaline earth metal ion is added to them, An alkaline earth metal ion source may also be added.

Alkali metals include sodium, potassium, and cesium; alkaline earth metals include calcium and magnesium.

For example, strontium can be used, and any of their halides, nitrates, sulfates, carbonates, and organic acid salts can be used as a raw material when preparing the catalyst. The supporting method may be any general ion exchange method or impregnation method.

By changing the content of these alkali metals and alkaline earth metals, the production of the desired γ-BL can be increased.

Its content varies slightly depending on the metal used and the type of stabilized zeolite, but the atomic ratio to cobalt is 0.
．． This effect can be achieved within the range of 0.05 to 1.0. If the atomic ratio is 0.1-0.4, the yield of γ-BL will be the highest.

There are no particular limitations on the method for producing the catalyst used in the present invention. For example, 1) zeolite is sequentially and simultaneously impregnated with thermally decomposable cobalt and palladium compounds, followed by normal drying, calcination,
2) A method of ion-exchanging palladium with zeolite, then impregnating it with a cobalt compound, and then firing and reducing it. 3) A method of physically mixing cobalt and palladium compounds with zeolite, then firing and reducing it. There are many methods, but any method can be used.

The cobalt compounds and palladium compounds used are:
There is no particular restriction as long as it can be thermally decomposed. Cobalt chloride is a cobalt compound.

Examples include cobalt nitrate, cobalt sulfate, and cobalt organic complexes, with cobalt nitrate being preferred.

On the other hand, examples of palladium compounds include palladium acetate, palladium ammonium chloride, palladium chloride, palladium nitrate, palladium sulfate, and tetraammine palladium chloride.

The ratio of the above-mentioned cobalt and palladium compounds is an important factor for the selectivity of γ-BL. That is, cobalt is 5 to 50% by weight and palladium is 0.5% by weight based on the total weight of the catalyst.
The content is preferably 5 to 6% by weight. If the content is less than that, the hydrogenation activity is poor and the selectivity of γ-BL is low. If cobalt and palladium are contained within the above range, activity 9
Although it is possible to achieve good results in terms of selectivity,
Since expensive palladium is used, the palladium content is preferably 0.2 to 2% by weight, and the cobalt content is preferably 5 to 30% by weight.

In the present invention, there are no restrictions on the shape of the catalyst, and it may be used as a powder or in the form of a mold, depending on the type of reaction. In the suspended bed, powder or granules are used, and in the fixed bed, tablet molded products, spherical or rod-shaped extrusion molded products, etc. are used.

In the present invention, the catalyst is activated by ordinary calcination and reduction, and then subjected to reaction.

The firing and reduction temperatures are not particularly limited as long as they are carried out in a stream of air, nitrogen or hydrogen within the range of 300 to 600°C.

In the method of the present invention, maleic acid or succinic anhydride is dissolved in a solvent and then subjected to the reaction.

As the solvent, dioxane or the like, which does not proceed with hydrogenation and does not react with the product, or γ-BL, which is a hydrogenation product that does not require solvent recovery, may be used.

The amount of catalyst to be used may be at least the amount necessary for hydrogenation to proceed at an appropriate reaction rate. However, since the amount used varies depending on the reaction type, it is difficult to limit it unconditionally, but in the case of a suspended bed, it is 1 to 3 by weight based on the C4 anhydride.
0%, preferably 2 to 15%.

In the present invention, the reaction is usually carried out under a hydrogen pressure of 150 to 30
carried out at 0°C, preferably in the range of 180 to 260°C,
The reaction pressure is selected to be in the range of 50 to 300 kg/cd G, preferably 50 to 200 kg/cJG. At temperatures and pressures lower than these, the reaction rate is extremely slow, and at temperatures and pressures higher than these, the product γ-BL decomposes and polymerizes, making it impractical.

In the present invention, the reaction can be carried out batchwise, semi-batchwise, in a suspended bed,
It can be carried out either in a continuous system or in a fixed bed flow system. Furthermore, γ
- Water generated from the reaction zone may be removed in order to improve the yield of BL.

[Effects of the Invention] The present invention provides a method in which cobalt and palladium are mainly supported on a crystalline aluminosilicate support in a reaction to obtain γ-BL by hydrogenating anhydride of maleic acid or succinic acid in a hydrogen gas atmosphere in the presence of a catalyst. By using this catalyst, cyclic products such as THF and γ-BL can be produced in higher yields than conventional catalysts.

Among them, when a stabilized Y-type zeolite carrier is used, the activity is so high that the reaction time can be halved, and furthermore, the desired product can be obtained with high selectivity at any time by adding an alkali metal or alkaline earth metal. The improved catalyst of the present invention is an industrially extremely useful catalyst for producing γ-BL which is superior in selectivity and activity to the various catalyst systems proposed so far.

[Examples] Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited only to these Examples.

(Preparation of Catalyst) An aqueous solution was prepared by dissolving 197 g of cobalt nitrate hexahydrate as a comparison catalyst in 250 ml of water, and after contacting and impregnating 200 g of commercially available silica gel, water was distilled off under reduced pressure. after that,
An aqueous solution of 4.2 g of palladium chloride dissolved in 200 ml of water was added, thoroughly mixed, and dried at 110° C. under reduced pressure for 10 hours to finely pulverize the material. Subsequently, the mixture was heated at 450° C. for 3 hours under a nitrogen stream (flow rate 25 II/h), and further activated for 3 hours under a hydrogen stream (flow rate 21/h) at the same temperature. The contents of cobalt and palladium in the obtained catalyst were 17% by weight and 1% by weight, respectively.

Catalyst preparation NaY using crystalline aluminosilicate as a carrier
(Silica/alumina molar ratio 5.6, TSZ manufactured by Tosoh Corporation)
-32ONAA), L-type C') f)/Fulmi f molar ratio 6.1, Tosoh TSZ-500KOA)
, %rudenite (silica/alumina molar ratio 10.5.
Toso Corporation TSZ60ONAA), 7 x 'J
:r-lite (silica/alumina molar ratio 16.8, Tosoh Corporation TSZ-720KOA) 20g of each 600°C air-fired product was loaded with metal as follows. Cobalt nitrate hexahydrate 2O, gg was Zeolite was added to a mixed solution of 0.54 g of radium nitrate dissolved in 25 ml of water to impregnate it, and water was distilled off in vacuo. Thereafter, it was dried at 110° C. for 10 hours and the catalyst was activated with nitrogen and hydrogen under the above conditions. The obtained catalyst (Ca
The contents of radium (radium, radium, and radium) in t, no., 1.2, and 3.4) were 17% by weight and 1% by weight, respectively.

Catalyst preparation using stabilized zeolite as a carrier (1) Silica/
Stabilized Y-type zeolite with alumina molar ratio of 14 and 40 (
Manufactured by Tosoh, H8Z-370HtlA.

600° C. air firing) Each 20 g was loaded with metal as follows. 20.8g of cobalt nitrate hexahydrate in 40ml of water
and 0.54 g of palladium nitrate in 25 g of water.
Zeolite was added to the mixed solution dissolved in m1 to impregnate it, and water was distilled off under reduced pressure. Thereafter, it was dried at 110° C. for 10 hours and the catalyst was activated with nitrogen and hydrogen under the above conditions. The contents of cobalt and palladium in the obtained catalyst (Cat, No. 5.6) were 17% by weight and 1% by weight, respectively.

(2) 20g of stabilized Y-type zeolite (silica/alumina ratio 40.600℃ air calcined) was suspended in 200ml of water, 024sol#! A predetermined amount of an aqueous solution of tetraamine palladium chloride was added and ion exchanged at 70°C for 3 hours. After filtration, washing, drying and air calcination, a stabilized zeolite containing 1% palladium was obtained. This was divided into two, and catalysts having different amounts of cobalt supported were prepared for each 10 g. Cobalt nitrate hexahydrate 8.7g, 12.3g
A 1% palladium-supported stabilized zeolite was added to an aqueous solution in which each of the above was dissolved in 50 ml of water to impregnate it. After distilling off the water in vacuo and drying, the catalyst was subsequently activated with nitrogen and hydrogen under the conditions described above. The cobalt and palladium contents of the obtained catalyst were as follows.

Cat, No, Co (wt%) Pd(tI
ffi%) 7 14.8 0.80 8 20 0.85 (3) 28.8g of cobalt nitrate hole hydrate in 40ml of water
A solution of 0.58 g of palladium nitrate in 20 m
A solution dissolved in 1 and 1. 10m of Og potassium chloride
20 g of stabilized Y-type zeolite with a silica/alumina molar ratio of 40 (6 each
00°C air firing) was added for impregnation, and water was distilled off in vacuo. The catalyst (Ca
The contents of cobalt, palladium, and potassium in No. t, No. 9) were 21% by weight, 1% by weight, and 2% by weight, respectively.

(4) 28.9g of cobalt nitrate hexahydrate in 40ml of water
A solution of 0.58 g of palladium nitrate in 20 m
A solution dissolved in 1 and 2.0 g of sodium chloride was added to 10
Silica/
20 g of stabilized Y-type ceolite (each fired in air at 600° C.) with an alumina molar ratio of 40 was added and impregnated, and water was distilled off in vacuo. The catalyst (C
The contents of cobalt, palladium, and sodium in at, No, IO) are 21% by weight, 1% by weight, and 3% by weight, respectively.
Met.

(5) Suspend 20 g of stabilized Y-type zeolite (silica/alumina molar ratio 40, air calcined at 600°C) in 200 ml of water, and add 1.5 liters of zeolite to alumina so that the molar ratio of potassium to alumina is 10 times the amount. i) and 3
, 0 mol#) of potassium chloride aqueous solution,
After ion exchange at 5°C for 13 hours, filtration, washing, and drying, air baking was performed at 450°C. The potassium content is 1.
They were 2% by weight and 1.4% by weight.

Next, this was suspended in 10 times the volume of water, 0.6% tetraamine palladium chloride aqueous solution was added, and the mixture was heated at 75°C.
Ion exchange was performed for 3 hours. After filtration, washing and drying, 40
Air firing was performed at 0°C. As a result, the aHk of palladium and potassium was 0.8% by weight, 0.7% by weight, 0.5% by weight, and 0.96% by weight, respectively. Further, stabilized zeolite supporting palladium and potassium was added to the cobalt nitrate aqueous solution so that the cobalt content was 1296 or 109δ, and impregnated. Water was distilled off in vacuo, and the catalyst was activated with nitrogen and hydrogen in the same manner as above. The content of each metal was as follows.

Cat, No, Co (wt%) Pd (wt%) K(
Weight%) 11 12 0.7 0.612
10 0.5 0.9 Examples 1-8. Comparative Example 1 A 300 ml stainless steel electromagnetic stirring autoclave was charged with 45 g of succinic anhydride, 75 g of dioxane, and 4.5 g of various catalysts shown in Table 1, and after the system was sufficiently replaced with hydrogen, the initial pressure was adjusted to 45 kg/cjG. Hydrogen was injected into the tank. The temperature was raised to 240°C while stirring, and after reaching a predetermined temperature, hydrogen adjusted to 100 kg/cj G was injected under pressure. Thereafter, the reaction was allowed to occur until the theoretical amount of hydrogen absorption was reached, and after completion of the reaction, the odocrape was cooled. After cooling to room temperature, hydrogen was purged, the liquid was taken out, the catalyst was filtered, and the filtrate was analyzed by gas chromatography. The results are shown in Table 1.

Examples 9 to 11, Comparative Example 2 60 g of maleic anhydride, 60 g of dioxane, and 6 g of the various catalysts shown in Table 2 were charged into a 300 ml stainless steel electromagnetic stirring autoclave, and after the system was sufficiently replaced with hydrogen, the mixture was first heated and stirred. 40℃, initial pressure 50kg/c
jG for 1 hour.

After that, the temperature was raised to 250℃, and after reaching the specified temperature, it was heated to 100℃.
Hydrogen adjusted to kg/cjG was injected under pressure. Example 1
The reaction was carried out in the same manner as above until the theoretical hydrogen absorption amount was reached, followed by post-treatment and analysis by gas chromatography. The results are shown in Table 2.

Examples 12 to 16, Comparative Example 3 45 g of succinic anhydride, 75 g of dioxane, and 4.5 g of the catalyst shown in Table 3 were placed in a 300 ml stainless steel electromagnetic stirring autoclave, and after the system was sufficiently replaced with hydrogen, the reaction time was The hydrogenation reaction was carried out in the same manner as in Example 1 for 3 hours, and then analyzed by gas chromatography. The results are shown in Table 3.

Claims (2)

[Claims] (1) A catalyst for producing γ-butyrolactone comprising a crystalline aluminosilicate carrier supporting cobalt and palladium. (2) A method for producing γ-butyrolactone, which comprises using the catalyst described in claim (1) as a catalyst in hydrogenating anhydride of maleic acid or succinic acid.