JPH01143865A - Production of gamma-butyrolactone - Google Patents

Abstract

PURPOSE:To obtain gamma-butyrolactone in high selectivity by reacting maleic acid, succinic acid and/or their anhydride with hydrogen using a catalyst having excellent selectivity, catalytic activity, catalyst life, etc., and produced by adding Ca to Ni and Mo. CONSTITUTION:gamma-butyrolactone is produced by reacting maleic acid, succinic acid and/or their anhydride with hydrogen in the presence of a catalyst composed of nickel, molybdenum and calcium (especially preferably the atomic ratio of Mo to Ni is 0.001-0.1 and that of Ca to Ni is 0.005-0.09). The reaction sufficiently proceeds even under a low hydrogen pressure (i.e. about 70kg/cm<2>) by the use of the catalyst.

Description

Detailed description of the invention (a) Industrial application field The present invention is characterized by reacting maleic acid, succinic acid and/or their anhydrides with hydrogen in the presence of a catalyst consisting of nickel, molybdenum and calcium. The present invention relates to a method for producing T-butyrolactone.

(b) Prior Art Many proposals have been made regarding methods for producing T-butyrolactone by hydrogenating maleic acid, succinic acid and/or their anhydrides in a liquid phase.

Journal of the Chemical Society of Japan, No. 4, p. 646, 1974, describes the composition and activity of a binary catalyst consisting of nickel and molybdenum, and the atomic ratio of molybdenum to nickel is O.
The yield of T-butyrolactone is about 66% when the atomic ratio of molybdenum to nickel is 0.6.

It is therefore known to use binary catalysts consisting of nickel and molybdenum for the production of T-butyrolactone.

In addition, Special Publication No. 46-33008, Special Publication No. 49-
Binary catalysts consisting of nickel and molybdenum have also been proposed in Japanese Patent No. 5337 and British Patent No. 1587198.

Japanese Patent Publication No. 49-16423 discloses elemental nickel and one or more metal oxides selected from the group consisting of beryllium, magnesium, calcium, aluminum, titanium, vanadium, chromium, manganese, zinc, zirconium, molybdenum, tungsten, and thorium. There is a description of the catalyst used.

Japanese Patent Publication No. 54-41560 describes a catalyst in which nickel and molybdenum are combined with barium and/or thallium, and the atomic ratio of molybdenum to nickel is 0.01 to 0.
．． 20, the atomic ratio of barium or thallium to nickel is 0
．． A range of 0.05 to 0.15 is considered suitable.

(c) Problems to be solved by the invention Elemental nickel, beryllium, magnesium, calcium, aluminum, titanium,
vanadium, chromium, manganese, zinc, zirconium,
Catalysts using one or more metal oxides selected from the group consisting of molybdenum, tungsten, and thorium are merely described in the specification, and the claims and examples do not include elemental nickel, aluminum, titanium, This invention relates to a binary catalyst consisting of vanadium, molybdenum and manganese. Moreover, the reaction conditions require high pressure conditions of 300 atmospheres or more; for example, with a binary catalyst consisting of nickel and molybdenum, the selectivity of T-butyrolactone is only 1%, the selectivity of tetrahydrofuran is 92%, and - It cannot be said that it is a catalyst that selectively produces butyrolactone.

The catalyst disclosed in Japanese Patent Publication No. 54-41560 in which barium and/or thallium are added to nickel and molybdenum is more effective in hydrogenating maleic acid, succinic acid, and/or their anhydrides than the binary catalyst consisting of nickel and molybdenum. Although the activity has increased, additional tests by the present inventors show that in addition to γ-butyrolactone, tetrahydrofuran, 1,
Since 4-butanediol and polyester are produced, it cannot be said to be an industrially viable catalyst.

Therefore, in the hydrogenation reaction of maleic acid, succinic acid and/or their anhydrides, in the conventional catalyst system consisting of nickel and molybdenum, in addition to the target product γ-butyrolactone, propionic acid, butyric acid, tetrahydrofuran, etc.
The fact is that by-products such as 4-butanediol and polyester are unavoidable, and the separation and purification of these products requires considerable expense in order to obtain industrially highly pure γ-butyrolactone.

As mentioned above, although many proposals have been made regarding the hydrogenation reaction of maleic acid, succinic acid, and/or their anhydrides, there have been many proposals regarding the hydrogenation reaction of maleic acid, succinic acid, and/or their anhydrides. It was not at a satisfactory level.

(d) Means for Solving the Problems The inventors of the present invention have made extensive efforts to solve the above problems, and have found that by adding calcium to nickel and molybdenum, the catalytic activity and selectivity of T-butyrolactone can be improved. The present inventors have discovered that this can be greatly improved and have completed the present invention.

That is, the present invention relates to a method for producing T-butyrolactone, which is characterized by reacting maleic acid, succinic acid, and/or their anhydrides with hydrogen in the presence of a ternary catalyst consisting of nickel, molybdenum, and calcium. and
More specifically, the atomic ratio of molybdenum to nickel is 0.
．． The present invention relates to a method for producing T-butyrolactone characterized by using a ternary catalyst having an atomic ratio of calcium to nickel of 0.001 to 0.1 and 0.005 to 0.09.

The catalyst used in the present invention can be produced by impregnating a carrier with an aqueous solution of each of nickel, molybdenum and calcium compounds or a mixed solution thereof, or by first precipitating one or two of nickel, molybdenum and calcium compounds. (formation of a cake) and then impregnating the remaining components into the precipitate; and a method of adding a precipitant to an aqueous solution of nickel, molybdenum, and calcium compounds and co-precipitating, etc., but the most preferred manufacturing method is the coprecipitation method. It is.

Specifically describing the coprecipitation method, an aqueous solution of molybdenum and calcium compounds is mixed with a water-soluble nickel salt such as nickel acetate, and then a precipitant such as sodium carbonate is added to precipitate the nickel, molybdenum and calcium compounds ( In this method, a carrier is added, thoroughly mixed, and then dried.

In addition to this method, for example, a method can also be adopted in which molybdenum and calcium compounds are uniformly kneaded into a precipitate produced by adding a precipitant to an aqueous nickel compound solution in an aqueous solution, and then kneaded and attached to a carrier. can.

After thoroughly drying the mixture containing nickel, molybdenum, calcium and a carrier produced by the above method at 80 to 110'C, preferably at 300 to 500'C in a nitrogen stream.
The catalyst is then treated for several hours and further subjected to preliminary reduction treatment at 300 to 500°C for about 4 hours in a hydrogen stream to prepare a catalyst.

Nickel compounds include nickel nitrate, nickel carbonate,
Examples include nickel chloride, nickel sulfate, and nickel acetate.

Examples of molybdenum compounds include ammonium molybdate.

Examples of calcium compounds include calcium nitrate, calcium carbonate, calcium chloride, and calcium acetate.

Examples of the precipitant include ammonium carbonate, ammonium bicarbonate, sodium carbonate, and sodium hydroxide.

Examples of the carrier include silica, silica-alumina, and diatom, with diatomaceous earth being preferred.

The amount of the carrier used is 15 to 2 % based on the total amount of nickel compound, molybdenum compound, and calcium compound to be supported.
0% by weight is preferred.

The shape of the catalyst used in the present invention varies depending on the reaction mode,
When used in a suspended phase, it is preferable to use a powder of 1 to 50 microns, and when used in a fixed bed reactor, it is preferable to use it in a spherical or cylindrical form.

The atomic ratio of molybdenum to nickel in the ternary catalyst consisting of nickel, molybdenum and calcium used in the present invention is 0.001 to 0.1, preferably 0.005 to 0.
．． 1 is good.

Also, the atomic ratio of calcium to nickel is 0°005
-0.09, preferably 0.01-0.04.

Incidentally, as a result of X-ray analysis of the ternary catalyst consisting of nickel, molybdenum and calcium used in the present invention, it was confirmed that calcium molybdate was partially formed. In addition, a catalyst consisting of nickel, molybdenum and strontium to which strontium and magnesium in group Ⅰ of the periodic table are added in place of calcium, and a catalyst consisting of nickel, molybdenum and magnesium are not effective at all and therefore cannot be used in the present invention. It is thought that the ternary catalyst consisting of nickel, molybdenum and calcium is a completely new catalyst system different from the binary catalyst consisting of nickel and molybdenum.

The reaction conditions of maleic acid, succinic acid and/or their anhydrides with hydrogen are as follows.

The reaction temperature is 100-300°C, preferably 170-24°C.
0°C is good (and the hydrogen pressure is 50 to 200 kg/cd, preferably 70 to 150 kg/C11l).

When using maleic acid and/or maleic anhydride as a raw material, the reaction may be divided into two stages.

That is, a catalyst is added to maleic acid and/or maleic anhydride, and the reaction temperature is 50-100°C and the hydrogen pressure is 50-12°C.
After first hydrogenating the double bonds of maleic acid and/or maleic anhydride at 0 kg/cffl and a reaction time of 0.5 to 1 hour, the reaction temperature was further increased to 200 to 240°C, and the hydrogen pressure was increased to 1.
This is a method of increasing the reaction rate to 00 to 150 kg/cii.

In the present invention, the reaction proceeds satisfactorily even without a solvent, but maleic acid, succinic acid and/or their anhydrides can also be dissolved in a solvent for ease of handling.

Preferred solvents include γ-butyrolactone, tetrahydrofuran, and dioxane. At this time, the concentration of maleic acid, succinic acid and/or their anhydrides in the solvent is 2
0 to 70% by weight is preferred.

(e) Effects of the invention By adding calcium to nickel and molybdenum, the catalyst activity increased and the selectivity of T-butyrolactone improved to 90% or more.

The reaction proceeds satisfactorily even at a low hydrogen pressure of about 10 kg/c1a.

(f) Examples Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 293 g of nickel acetate tetrahydrate are dissolved in 1.51 l of water. Add 8.4 g of calcium nitrate tetrahydrate to this and 20 g of water.
0 ml of an aqueous solution and an aqueous solution of 12.6 g of ammonium molybdate dissolved in 300 n+ffi of water are mixed.

Add 30% sodium carbonate aqueous solution 600+++j! to this mixed solution as a precipitant. Add. At this time, the pH of the solution was 8.
It turned out to be 13.

46.1 g of diatomaceous earth was added to the resulting slurry, thoroughly mixed, and then filtered. After washing the precipitate with water and drying it at 110°C for 24 hours, the resulting powder was immersed in an air stream with a hydrogen to nitrogen ratio of 1=2.
After treatment at 00''C for 3 hours, reduction was performed at 450°C in a hydrogen stream for 3 hours.

The catalyst was cooled to room temperature and stored under nitrogen.

Next, 15 g of maleic anhydride and 60 g of tetrahydrofuran as a solvent were placed in a 100 IllN electromagnetic stirring autoclave.
-2, 2.25 g of the above catalyst was added.

Initially, the reaction was carried out for 1 hour at a reaction temperature of 100° C. and a hydrogen pressure of 100 kg/d, and absorption of about 3.421 hydrogen atoms was observed.

Next, the temperature is set to 240°C, and the hydrogen pressure is set to 120kg/c+.
Fi and the reaction was carried out for 4 hours.

After the reaction, γ-butyrolactone, propionic acid, butyric acid, tetrahydrofuran, and 1,4-butanediol in the reaction product were analyzed using gas chromatography using isobutyl benzoate as an internal standard, and maleic anhydride, succinic anhydride, succinic acid, etc. High performance liquid chromatography analysis was performed using methyl lactate as an internal standard. The results are shown in Table 1.

Example 2 The reaction was carried out in exactly the same manner as in Example 1, except that the amount of calcium nitrate added was changed to 9.4 g.

The results are shown in Table 1.

Example 3 Using the catalyst of Example 1, hydrogen pressure was 70 kg/cff
The reaction was carried out in exactly the same manner as in Example 1, except that 1 was changed. The results are shown in Table 1.

Example 4 Using the catalyst of Example 1, succinic anhydride 15 was used as the raw material.
g, reaction temperature 240℃, hydrogen pressure 120kg/cd
The reaction was carried out in exactly the same manner as in Example 1, except for the following. The results are shown in Table 1.゛Example 5.6.7 In the catalyst preparation of Example 1, the reduction temperature of the catalyst was set to 35
The reaction was carried out in exactly the same manner as in Example 1, except that the temperatures were 0°C, 400°C, and 425°C. The results are shown in Table 1.

Example 8 293 g of nickel acetate tetrahydrate are dissolved in 1.5 l of water. A solution of 940 g of sodium carbonate dissolved in 31 parts of water was added to this and left to stand for 1 hour. The pi of the slurry produced was 8.2.

Add ±280g of diatoms to the resulting slurry, mix thoroughly, age for 1 hour, filter, wash the precipitate three times with water, and heat at 110°C.
It was dried for 24 hours.

This dried product, 44 g of calcium nitrate tetrahydrate, and 7.46 g of ammonium molybdate were mixed in 300 ml of water! Thoroughly mix the aqueous solution dissolved in
It was dried at 10°C for 24 hours. After treating the obtained powder at 350 °C for 3 hours in an air stream with a hydrogen to nitrogen ratio of 1 = 2,
Reduction was performed at 450″C in a hydrogen stream for 3 hours.

Next, it was treated and reacted in exactly the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 A catalyst consisting of nickel and molybdenum prepared in exactly the same manner as in Example 1 was used except that calcium nitrate was not added, and the reaction was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 A catalyst consisting of nickel and calcium prepared in exactly the same manner as in Example 1 was used, except that ammonium molybdate was not added, and the reaction was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 A catalyst consisting of nickel, molybdenum, and barium was prepared in exactly the same manner as in Example 1, except that 9.27 g of barium nitrate was added instead of calcium nitrate, and the catalyst was treated in the same manner as in Example 1. , the reaction was carried out. The results are shown in Table 1.

Comparative Example 4 Strontium nitrate 5°31g instead of calcium nitrate
The reaction was carried out in the same manner as in Example 1, using a catalyst consisting of nickel, molybdenum and strontium, which was prepared in the same manner as in Example 1, except for the addition of . The results are shown in Table 1.

Comparative Example 5 A catalyst consisting of nickel, molybdenum, and magnesium was prepared in exactly the same manner as in Example 1, except that 3.04 g of magnesium nitrate was added instead of calcium nitrate, and the catalyst was treated in the same manner as in Example 1. , the reaction was carried out. The results are shown in Table 1.

Example 9 (Catalyst Deterioration Test) The pre-reduced catalyst of Example 1 was molded into 178 inch x 178 tablets and calcined at 300'C in a nitrogen stream.

After filling 200 ml of this tablet catalyst into a stainless steel reaction tube with an inner diameter of 32.9 mm and a length of 350 mm, 517H
Reduction was carried out at 420-430° C. in a hydrogen stream of r.

After that, the temperature of the catalyst layer was increased to 210°C, the hydrogen pressure was increased to 100°C.
kg/c4 and hydrogen is 104! /Hr.

In addition, maleic anhydride tetrahydrofuran 2 is used as a raw material.
A 0 wt % solution was fed at 200 yil/Hr.

Carbon monoxide, carbon dioxide, and hydrocarbons in the waste gas were extremely small.

The reaction products were continuously extracted from the reactor and subjected to gas chromatography analysis and high performance liquid chromatography analysis. The results are shown below.

Claims (1)

[Claims] 1) A method for producing γ-butyrolactone, which comprises reacting maleic acid, succinic acid and/or their anhydrides with hydrogen in the presence of a catalyst consisting of nickel, molybdenum and calcium. 2) The atomic ratio of molybdenum to nickel is 0.001
~0.1, the atomic ratio of calcium to nickel is 0.
The method for producing γ-butyrolactone according to claim 1, characterized in that a catalyst having a molecular weight of 0.005 to 0.09 is used.