KR100338131B1 - Catalyst for the hydrogenation and method for preparing r-butyrolactone using the same catalyst - Google Patents

Abstract

The present invention relates to a hydrogenation catalyst represented by the following general formula (I)

Ni ₉ Pd _a Mo _b N _c Zr _d O _x . (Ⅰ)

In the formula, N is a metal element selected from Co, Cu, Zn, Ag, Pb, Ru, a is 0.001-0.5, b is 0.01-5, C is 0.001-1.0, d is 0.5-12.0, x is each component The stoichiometric value according to the valence and composition ratio of is shown.

A method for producing gamma-butyrolactone using this catalyst is provided.

The process of the present invention using the catalyst of the present invention has the effect of producing gamma-butyrolactone from maleic anhydride or succinic anhydride with high selectivity and high yield under mild reaction conditions.

Description

Catalytic reaction for the hydrogenation and method for preparing r-butyrolactone using the same catalyst

The present invention relates to a catalyst useful for producing gamma-butyrolactone from maleic anhydride or succinic anhydride with high selectivity and high yield and to a method for producing gamma-butyrolactone from maleic anhydride or succinic anhydride using this catalyst. will be.

Specifically, in the preparation of gamma-butyrolactone by hydrogenation of maleic anhydride or succinic anhydride, a catalyst useful for hydrogenation and anhydrous using this catalyst The present invention relates to a method for producing gamma-butyrolactone by hydrogenating maleic acid or succinic anhydride in a liquid-gas flow reaction under mild reaction conditions at low temperature and low pressure.

Gamma-butyrolactone is a substance having a high boiling point (B · P 204 ° C.) and is used only as an intermediate for synthesizing pyrrolidone, N-methylpyrrolidone, N-vinylpyrrolidone, polyvinylpyrrolidone, etc. In addition, it is one of the important raw materials used in various fields of pesticides, medicine, dyes and pigments, fragrances, cosmetics, petrochemicals and electronics.

Conventional methods for preparing gamma-butyrolactone include dehydrogenation of 1,4-butanediol, carbonylation of 1,4-butanediol or allyl alcohol, and hydrogenation of maleic anhydride or succinic anhydride. Production methods are known, but the production of gamma-butyrolactone using 1,4-butanediol or allyl alcohol as raw materials is more economical than the direct hydrogenation of maleic anhydride because the raw materials are expensive and the reaction proceeds in multiple stages. Can not do it.

As a process for producing gamma-butyrolactone from maleic anhydride or succinic anhydride, a method of hydrogenating a liquid phase under a homogeneous or heterogeneous catalyst and a method of hydrogenating in a gas phase have been developed, and a catalyst suitable for each process is known. . The well-known heterogeneous liquid hydrogenation catalyst and its process (JP 87-111975, USP 5,118,821, JP 92-16237, EP 543340) proceed under high temperature and high pressure, and have a disadvantage in that the process yield is not satisfactory. In view of the process of catalyst separation, solvent separation and recovery, and loss of solvent due to hydrocracking reaction, etc., there are many disadvantages in commercialization. On the other hand, gas phase hydrogenation processes include Cu-Zn (GBP 1,168,220), Cu-Cr (USP 3,065,243), Cu-Zn-Cr (USP 5,698,713), Cu-Zn-Cr-Al (EP 332,140A), Cu-Zn-Al- M (M is at least one element selected from IIA.IIIA, VA, VIIIA, Ag, Au, III-VIIB, lanthanum series and actinium series; CN 1034541A) and dissolve maleic anhydride or succinic anhydride in a solvent. Or as it is injected into a fixed bed reactor to produce gamma-butyrolactone, despite the simplicity of the process has the following problems.

In general, the gas phase hydrogenation reaction proceeds at a relatively high temperature of 220 to 400 ° C., so that succinic anhydride as a hydrogenation reaction intermediate and gamma-butyrolactone as an object of the present invention are subjected to hydrogen peroxide decomposition and carbonyl group leaving reaction. By side reaction, it is easy to produce by-products, such as 1, 4- butanediol, tetrahydrofuran, butanol, a propanol, propanoic acid, butanoic acid. In the described open to reduce the side reactions such as the hydrogenation capacity it is relatively weak because of the Cu based alloy it is at a low space velocity of the hydrogenation activity of the majority, or Cu using a catalyst 0.003~1.0hr ^-1, preferably 0.01~0.1hr ^- Illustrated as being operated at ¹ , the productivity of gamma-butyrolactone is low. In addition, a high boiling point impurity contained in the raw material or the raw material is carbonized, or a part of maleic anhydride is hydro-isomerized by water remaining in the reaction product to produce an extremely high fumaric acid (mp: 287 ° C.) or a polymer. High purity of the reactants is required because this causes problems in operation and promotes deactivation of the catalyst. In addition, it is necessary to activate the catalyst periodically for the continuous reaction (e.g. USP 5,347,021), and in order to alleviate the deactivation of the catalyst, the amount of hydrogen used must be operated in a range of 50 molar ratios, preferably 100 to 300 molar ratios. I suggest things. As a method to supplement the disadvantages of the gas phase hydrogenation process on the Cu-based catalyst, USP 5,637,735 proposes a method of simultaneously supplying alcohol to the reaction raw material on the Cu-Zn-Cr-Zr catalyst using 1 to 4 molar ratios of maleic anhydride. However, this method is similar in principle to the method of using an esterified product of maleic anhydride or succinic anhydride. Rather, it is not a good method for the process because an excess alcohol must be used.

In summary, the conventional process for preparing a gamma-butyrolactone catalyst has its own characteristics, but the reaction conditions are harsh, or the space velocity of the reactants is too low, resulting in poor productivity, or low yield of gamma-butyrolactone. In addition, there is a problem that the deactivation rate of the catalyst is fast, the catalyst life is short, the hydrogen consumption is high, and the method of adding alcohol requires a recovery process of alcohol.

It is an object of the present invention to produce gamma-butyrolactone from maleic anhydride or succinic anhydride, which is a novel liquid and gaseous hydrogen reduction which maintains high activity and high selectivity even under conditions in which a large amount of raw materials are continuously supplied. It is another object of the present invention to provide a method for preparing gamma-butyrolactone under mild and low temperature conditions at low temperature using the catalyst.

The inventors of the present invention conducted a study to solve the carbonization of the reactants and the shortening of catalyst life, which are almost inevitable in the direct gas phase hydrogenation process of maleic anhydride, while mitigating the purity restriction conditions of maleic anhydride and smooth process operation. In order to make it possible for a long time, it is confirmed that the above problems can be solved by supplying maleic anhydride with a high boiling point solvent and maintaining a liquid state in a catalyst layer of a part of a reactant and a product including an organic solvent during the reaction. It was completed.

The method of the present invention is similar to the liquid phase reaction in that the liquid phase is maintained by using a solvent, but the conventional liquid phase reaction technology is a liquid slurry reaction type of high temperature and high pressure (over 50 atm), but the present invention is low temperature and low pressure ( In the reaction conditions of 50 atm or less), gamma-butyrolactone is produced in a fluid reaction type that allows reactants and hydrogen gas to pass simultaneously through the catalyst bed under the same direction of flow. Similar to the trickle bed reaction, but in the trickle bed reaction, very low reactant feed rates, reactants, are used to maintain the liquid phase of the reactants and products and to maintain the reaction liquid flow in the standing bed as a standing still. The low hydrogen ratio (molar ratio of 1-5), low temperature and high pressure are required, resulting in very low catalytic reaction productivity. The longer is the fruit digestion reaction proceeds increases the generated by-products, such as tetrahydrofuran followed by the problems such as the need to strictly control the operating conditions. On the other hand, the liquid-gas catalyst process of the present invention does not operate under the restriction that all reactants, products, and solvents must maintain a steady flow of liquid in the catalyst bed, and can operate under an appropriate residence time, thereby suppressing the superhydrogenation reaction. It is a process that combines the advantages of liquid and gas phase processes in that it can ensure operational stability. In this case, as the reaction temperature is lowered, the control range of other reaction conditions such as reaction pressure and flow rate of hydrogen can be widened, so that a high activity catalyst having excellent productivity even under mild reaction conditions is required. The following general formula (I) shows the catalyst system of the present invention showing excellent activity and selectivity.

Ni ₉ Pd _a Mo _b N _c Zr _d O _x . (Ⅰ)

In formula (1), Ni, Pd, Mo, Zr and O represent nickel, palladium, molybdenum, zirconium and oxygen, respectively, N represents cobalt (Co), copper (Cu), zinc (Zn), silver (Ag), It is a metal element selected from lead (Pb) and ruthenium (Ru), and a, b, c, d, and x represent atomic ratios of palladium, molybdenum, N, zirconium, and oxygen. When nickel is 9, a is 0.001 to 5 , Preferably has a value in the range of 0.05 to 2, b has a value in the range of 0.01 to 5, preferably 0.1 to 2, c has a value in the range of 0.001 to 1.0 and d is 0.5 to 12.0, preferably It has a value in the range of 1 to 5. x has a stoichiometric number according to the valence and composition ratio of each component when the component is in the oxide state in the process of preparing the catalyst, but the nickel and palladium components in the metal state when activated as a hydrogenation catalyst As it is reduced, the molybdenum, N and zirconium have different values depending on the degree of reduction of each component and the b, c, d values.

That is, the general formula (I) may be represented as follows.

Ni ₉ Pd _a Mo _b N _c Zr _d O _x . (Ⅰ)

In the formula, N is a metal element selected from Co, Cu, Zn, Ag, Pb, Ru, a is 0.001-0.5, b is 0.01-5, C is 0.001-1.0, d is 0.5-12.0, x is each component The stoichiometric value according to the valence and composition ratio of is shown.

Known catalysts based on nickel which are used to prepare gamma-butyrolactone from maleic anhydride or succinic anhydride include Ni-Mo-Ba (Tl) (USP 3,890,361) and Ni-Mo-Ba-Re (published in Japan). Patent Publication No. 88-88045), Ni-Mo-Ba-Re / SiO ₂ (or Al ₂ O ₃ ) (Japanese Patent Publication No. 88-88044), Ni-Mo-Ca / Diatomaceous Earth (Japanese Patent Publication No. 89-143865) Ni-Mo-Ca (Japanese Patent Laid-Open No. 87-299550), Ni-Pd / SiO ₂ (USP 5,118,821), Ni-Pd-Co / Al ₂ O ₃ or Al ₂ O ₃ -SiO ₂ (USP 4,814,464), Ni-Co / SiO ₂ (USP 5,086,030), but these are catalysts designed for high-temperature, high-pressure liquid phase slurry reactions, and have low activity and selectivity at low and low pressures. The present inventors show excellent activity and reaction stability when nickel is combined with zirconia, which itself has a reducing ability, as a reducing carrier in a constant component ratio, and when palladium and molybdenum components are added thereto, the activity and selectivity are clearly improved. And to complete the present invention.

The catalyst of the general formula (I) may be prepared by a conventional catalyst production method, but it is suitable to dissolve the water-soluble salts of the respective element elements in water and then prepare by the coprecipitation method. Nickel, N and zirconium components use water-soluble salts such as nitrates or hydrochlorides. In the preparation method, the component salt is dissolved in water to form a mixed solution, and then coprecipitated with sodium hydroxide, sodium carbonate, ammonia, ammonium carbonate, or a suitable alkali solution. After aging, the coprecipitation solution is filtered to obtain a cake and washed with water. The cake is dispersed in water, and then ammonium molybdate and palladium salt solutions are added sequentially and evaporated to dryness. The N component may be added during coprecipitation or addition of a palladium component. In particular, the palladium component may be coated on a catalyst powder which is dried or calcined at 400 ° C or below. The evaporated dried cake is dried at 120 ° C. and calcined at 300 ° C. to 600 ° C., preferably 350 to 500 ° C. The calcined oxide catalyst is reduced in a H ₂ / N ₂ gas stream after charging to the reactor. The reduction temperature is reduced at 300 ° C to 600 ° C, preferably at 350 ° C to 450 ° C. The reduction time depends on the amount of H ₂ / N ₂ gas and the catalyst usage, but it is carried out for about 10 hours. Since it generates heat during the reduction process, the hydrogen concentration, gas flow rate, temperature increase rate, etc. are adjusted to prevent the catalyst from deteriorating due to a rapid temperature rise.

The reaction proceeds under a flow of hydrogen or hydrogen or an inert mixed gas, and the ratio of hydrogen to maleic anhydride must be increased in order to maintain some of the solvent or reactant and product in the liquid phase in the catalyst bed when excess hydrogen is used, with selectivity Since the energy cost of reducing and recovering excess hydrogen is increased, the appropriate molar ratio is carried out in the range of 5 to 70: 1, more preferably 10 to 40: 1. The reaction temperature is controlled in the range of 150 ° C to 240 ° C, preferably 160 ° C to 220 ° C, because it is advantageous to operate within the boiling point (204 ° C) of gamma-butyrolactone as the present reaction product to achieve the object of the present invention. do. The reaction pressure is adjusted in the range of 1 to 50 atm, preferably 1 to 30 atm. Maleic anhydride or succinic anhydride is used after being dissolved in a high boiling point solvent. Since the solvent plays a decisive role in maintaining the liquid state of the catalyst layer during operation, the higher the boiling point, the better. As the high boiling point solvent, polyethers such as triethyleneglycoldimethylether, tetraethyleneglycol dimethylether (hereinafter referred to as TEGDME), and 18-crown-6 and gamma-butyrolactone are used. When using the product gamma-butyrolactone as a solvent, despite the advantages of the process of separation and purification, high pressure conditions are required because of the relatively low boiling point, so that it can be combined with saturated hydrocarbon oils having a boiling point of more than 280 ℃ and specific gravity of 0.9 or less. When used, the advantages of the catalytic process of the present invention can be exhibited to the maximum. The hydrogenation reaction product is simply separated by phase separation with the solvent, and the reaction product dissolved in the solvent can be ignored, so that the solvent can be recovered and reused as it is without purification. Hydrocarbon-based oils, however, contain sulfur, which may affect the catalyst. Therefore, hydrogenated reformate with hydrogen removed should be used. The concentration of maleic anhydride or succinic anhydride relative to the solvent is supplied by making 10wt% to 80wt%, preferably 20wt% to 70wt% solution. When using a high boiling point hydrocarbon oil solvent together, the oil solvent has a weight hourly space velocity (WHSV) of 0.01. To 2.0hr^-One, Preferably 0.01 To 0.2hr^-OneFeed at speed. The feed of reactant was 0.05 hrs when the WHSV was calculated from fatty acid anhydride alone.^-OneTo 1.0hr^-One, Preferably 0.07hr^-OneTo 0.5hr^-OneFeed at speed. At this time, the weight of the catalyst is defined as a value based on the weight of the catalyst in the oxide state before reduction for convenience. For reference, the conditions for maintaining the liquid phase in the catalyst bed in consideration of the physical properties of the reactants or products, the solvent used, the reaction temperature, the flow rate of hydrogen gas, and the reaction pressure are specified in EP 379323A2.

The following examples illustrate the invention in more detail and are not intended to limit the scope of the invention. In the examples, the conversion rate was expressed based on succinic anhydride, which is the primary hydrogenation product of maleic anhydride, to indicate the degree of hydrogenation in the sequential reaction, and the conversion rate of maleic anhydride itself was almost 100% under the reaction conditions of each example.

Example 1

Catalyst manufacturing

30.0 g of nickel nitrate (Ni (NO ₃ ) ₂ 6H ₂ O), 8.45 g of zirconium oxychloride (ZrOCl _2. 8H ₂ O) and 0.133 g of ruthenium chloride (Ru 43.6%) were dissolved in 200 g of distilled water, followed by sodium hydroxide and Aqueous solution of sodium carbonate is added for coprecipitation. The coprecipitation solution is aged at 70-80 ° C. for 4 hours and then washed with distilled water until the sodium content is sufficiently removed. To this was added a solution of 2.02 g of ammonium molybdate ((NH ₄ ) Mo ₇ O ₂₄ 4H ₂ O) and 0.61 g of palladium nitrate (Pd (NO ₃ ) _2. nH ₂ O, n = 1.9), and then uniformly Mix, evaporate and dry. After drying at 120 ℃ for more than 12 hours and fractionated to a size of 20 to 30 mesh and then fired at 400 ℃ for 4 hours. The metal element composition ratio except oxygen of this catalyst (1) is as follows.

Catalyst (1): Ni ₉ Mo _1.0 Pd _0.2 Ru _0.05 Zr _2.3

Thereafter, oxygen is excluded when describing the metal element composition ratio of the catalysts.

Catalytic reduction

Into a 1/2 inch diameter reactor, 4.0 g of catalyst was charged, gradually raising the temperature while flowing a 5% H ₂ / N ₂ mixed gas, and reduced at 420 ° C. for 9 hours.

Hydrogenation of Maleic Anhydride

The reaction conditions were set at 200 ° C. and 3 atm, and a solution of maleic anhydride (MAn) dissolved in TEGDME (MAn: TEGDME = 20: 80 w / w) was injected from the top of the reactor and reacted. At this time, the reactant and hydrogen gas flow in the same direction, and the molar ratio of WHSV (catalytic oxide basis) to 0.24 hr ⁻¹ and H ₂ / MAn to maleic anhydride is reacted at 25 conditions.

The reaction result was 99.8% conversion and the selectivity of gamma-butyrolactone was 90.2%.

Example 2)

Catalyst (2): Ni ₉ Mo _1.0 Pd _0.1 Ru _0.05 Zr _2.3

The catalyst component except for the palladium component in the catalyst (1) of Example 1) was prepared in the same manner, dried at 120, and then ground to 100 mesh or less. After carrying out a solution of 0.305 g of palladium nitrate dissolved therein, it was reacted after firing under the same conditions. The reaction was conducted at a reaction temperature of 195 ° C, reaction pressure of 3 atmospheres, WHSV = 0.24hr, and H2 / MAn = 25, and the conversion rate was 99.5%, and the selectivity of gamma-butyrolactone was 92.6%.

Comparative Example 1)

Comparative Catalyst (1): Ni ₉ Zr _2.3

Comparative catalyst (1) consisting only of nickel and zirconium components was prepared by co-precipitation method as in Example 1) and reacted under the conditions of WHSV of 0.09hr ^-1 , reaction temperature of 200 ° C, reaction pressure of 3 atmospheres, and H ₂ / MAn = 25. I was. At this time, a solution of maleic anhydride dissolved in 20 wt% TEGDME was supplied. The reaction result was a conversion rate of 99.5%, the selectivity of gamma-butyrolactone was 83.9%. In particular, the selectivity to propanoic acid in the byproduct was 13.9%.

Comparative Examples 2-4)

Comparative Catalyst (2): Ni ₉ Mo _0.5 Zr _2.3

Comparative Catalyst (3): Ni ₉ Mo _0.5 (70 wt%) / SiO ₂ (30 wt%)

Comparative Catalyst (4): Ni ₉ Mo _0.5 (70 wt%) / Al ₂ O ₃ (30 wt%)

In order to investigate the carrier effect in the nickel-based catalyst, the catalyst (1) of Example 1) was prepared in the same manner except for the palladium component. Silica was prepared by a coprecipitation method using SiO ₂ powder (Aerosil Ox-50) and aluminum as aluminum nitrate. The WHSV was reacted under the conditions of 0.09hr ⁻¹ , reaction temperature 200 ° C., reaction pressure 3 atm, and H ₂ / MAn = 25, as shown in Table 1 below.

Comparative Example catalyst % Conversion % Selectivity 234 Ni ₉ Mo _0.5 Zr _2.3 Ni ₉ Mo _0.5 (70wt%) / SiO ₂ (30wt%) Ni ₉ Mo _0.5 (70wt%) / Al ₂ O ₃ (30wt%) 97.895.495.3 92.385.779.5

Example 3

Catalyst (3): Ni ₉ Mo _1.0 Pd _0.2 Co _0.5 Zr _2.3

A catalyst was prepared in the same manner as in the catalyst (1) of Example 1) except that the cobalt component was added. Under the same reaction conditions as in Example 1), the reaction result was 99.9% conversion, 90.8% gamma-butyrolactone selectivity, and 91.2% conversion 98.5% selectivity.

Examples 4-7)

In the catalyst (3) of Example 3), instead of cobalt, copper, zinc, silver, and lead were prepared in the same composition as in Table 2. The catalyst (4) and catalyst (5) added with copper and zinc components were prepared in the same manner as in Example 1), and the catalysts (6) and catalyst (7) with silver and lead added were precursor compounds of the above components. (Silver silver nitrate and lead nitrate) were prepared by dissolving in palladium nitrate and supplying water, evaporating and drying. The results of the reaction under the same conditions as in Example 1) are shown in Table 2 below.

Example catalyst % Conversion % Selectivity 4567 Ni ₉ Mo _1.0 Pd _0.2 Cu _0.2 Zr _2.3 Ni ₉ Mo _1.0 Pd _0.2 Zn _0.2 Zr _2.3 Ni ₉ Mo _1.0 Pd _0.2 Ag _0.1 Zr _2.3 Ni ₉ Mo _1.0 Pd _0.2 Pb _0.02 Zr _2.3 99.399.299.799.5 91.291.089.292.1

Example 8

A solution obtained by dissolving maleic anhydride in gamma-butyrolactone at a weight ratio of 60 to 40 was dissolved in the catalyst (3) of Example 3 at a reaction temperature of 195 ° C. and a reaction pressure of 5 atm so that the WHSV of maleic anhydride was 0.24 hr ⁻¹ . A hydrocarbon-based hydrogenated reformate having an average boiling point of 350 ° C. was supplied at 0.1 hr ⁻¹ of WHSV, and reacted under a condition of H ₂ / MAn = 25. The conversion rate was 98.5% and the gamma-butyrolactone selectivity was 92.0%.

Example 9

The solution (3) of Example 3) was used and the solution of succinic anhydride dissolved in TEGDME under the same reaction conditions (10 wt%) was reacted by supplying 0.24hr ⁻¹ of WHSV to succinic anhydride. The reaction result was 99.7% conversion and the selectivity of gamma-butyrolactone was 83.0%.

Example 10)

A stainless reactor having an internal diameter of 1 inch and a length of 1.2 m was charged with 180 ml of a catalyst obtained by extruding the catalyst (1) of Example 1 by extrusion molding (extrusion diameter = 4 mm), and hydrogen reduction was carried out in the same manner as in Example 1). To activate the catalyst. First, a hydrocarbon oil having an average boiling point of 350 ° C. is supplied from the top of the reactor at a rate of 0.10 ml / min, and the catalyst layer is wetted with a solvent. The catalyst layer was wetted with a solvent, and a solution of maleic anhydride dissolved in gamma-butyrolactone at the top of the reactor (MAn / GBL = 6/4 weight ratio) was supplied at a rate of WHSV = 0.20hr ⁻¹ (based on maleic anhydride), and the reaction temperature was 200. The reaction was carried out under the conditions of C, a reaction pressure of 7 atm, and H ₂ / MAn = 25. The conversion was 94.9% and gamma-butyrolactone selectivity 91.2% at 500 hours.

Example 11

In order to confirm the effect of the high boiling point solvent, maleic anhydride (MAn / GBL = 6/4 weight ratio) was fed at a rate of WHSV = 0.12hr ⁻¹ using the molding catalyst of Example 10), and the same as in Example 10). The reaction was carried out by the method, and the supply of the high boiling point solvent was stopped after a certain reaction time. The reaction temperature, reaction pressure and reaction results are shown in Table 3. The conversion rate was 89.9% and the gamma-butyrolactone selectivity was 96.7% at 340 hours. After that, the solvent supply was stopped, and the conversion rate began to decrease, and the conversion rate was 78.1% and the gamma-butyrolactone selectivity was 98.1% at a reaction time of 460 hours (120 hours after the hydrocarbon oil supply was stopped).

Response time (hr) Reaction temperature / reaction pressure (℃ / atm) Maleic anhydride conversion (%) Gamma-Butyrolactone Selectivity (%) High boiling hydrocarbon oil 48340 185/6190/6 88.889.9 95.796.7 OO 410460 190/6190/6 82.978.1 99.298.1 XX

The process of the invention using the catalyst of the invention has the effect of producing gamma-butyrolactone from high selectivity and high yield under mild reaction conditions.

Claims (5)

Hydrogenation reaction catalyst represented by the following general formula (I) Ni ₉ Pd _a Mo _b N _c Zr _d O _x . (Ⅰ) In the formula, N is a metal element selected from Co, Cu, Zn, Ag, Pb, Ru, a is 0.001-0.5, b is 0.01-5, C is 0.001-1.0, d is 0.5-12.0, x is each component The stoichiometric value according to the valence and composition ratio of is shown. In the method for producing gamma-butyrolactone by hydrogenation of maleic anhydride or succinic anhydride, maleic anhydride or succinic anhydride dissolved in a high boiling point solvent is supplied in a liquid phase to the catalyst layer represented by the following general formula (I). Process for producing gamma-butyrolactone by hydrogenation with hydrogen or hydrogen-containing gas. Ni ₉ Pd _a Mo _b N _c Zr _d O _x . (Ⅰ) In the formula, N is a metal element selected from Co, Cu, Zn, Ag, Pb, Ru, a is 0.001-0.5, b is 0.01-5, C is 0.001-1.0, d is 0.5-12.0, x is each component The stoichiometric value according to the valence and composition ratio of is shown. The method for producing gamma-butyrolactone according to claim 2, wherein the molar ratio of hydrogen to maleic anhydride or succinic anhydride is 10 to 50: 1 at a reaction pressure of normal pressure to 30 atmospheres and a reaction temperature of 160 to 220 ° C. The solvent according to claim 2, wherein the high boiling point solvent is selected from gamma-butyrolactone, triethylene glycol dimethyl ether, or tetraethylene glycol dimethyl ether and is a liquid in which 10 to 80% by weight of maleic anhydride or succinic anhydride is dissolved in a high boiling point solvent. A method for producing gamma-butyrolactone which is fed to a catalyst layer and subjected to a hydrogenation reaction. The high boiling point solvent is a hydrocarbon oil having a boiling point of 280 ℃ or more, specific gravity of 0.9 or less, alone or in combination with gamma-butyrolactone, and the solvent is separated from the reaction product and reused after the reaction Method for preparing gamma-butyrolactone.