JP3194811B2 - Method for producing lactones - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing lactones, and more particularly to a method for producing γ-butyrolactone. γ-butyrolactone is a compound useful as a solvent for organic electroconductive solutions and as a raw material for synthesis such as pyrrolidones.

[0002]

2. Description of the Related Art Conventionally, many proposals have been made regarding a method for producing a lactone by hydrogenating a saturated and / or unsaturated dicarboxylic acid derivative in a liquid phase.

For example, a method using a cobalt-palladium catalyst supported on silica as a catalyst (for example, Japanese Patent Publication No.
8-29142) is known. The method using a cobalt-palladium-based catalyst has the advantage that the cost of the catalyst is relatively low, but the reaction conditions are 250 ° C., 1
Since it is severe at 50 kg / cm ² G, the equipment cost is high, which is not preferable in view of industrial operation.

Further, Japanese Patent Publication No. 45-32061 discloses that
Production examples of lactones using a nickel-rhenium-based catalyst supported on diatomaceous earth have been reported. However, also in this publication, the reaction conditions are 250 ° C., 120 kg / cm ²
There is a problem that it is severe with G, and side reactions such as formation of cyclic ether and decarboxylation proceed, and the selectivity of lactones is not satisfactory.

In Japanese Patent Application Laid-Open No. 2-9873, lactones are synthesized with high selectivity by using a catalyst in which nickel and palladium are supported on silica having a high specific surface area of 50 m ² / g or more. ing. This publication cannot be said to be a preferable method because the reaction conditions are as severe as 235 ° C. and 95 kg / cm ² G, but it shows that the type of the support and the specific surface area are very important. That is, the silica carrier having a specific surface area of at least 50 m ² / g of the present publication is compared with conventionally known carriers such as silica, silica alumina, alumina, and diatomaceous earth.
It has been shown to be a preferred carrier that provides high activity and selectivity. In particular, a catalyst supported on diatomaceous earth comprising the same catalyst components of nickel and palladium (Japanese Patent Publication No.
The results of the reaction of the present publication are remarkably improved as compared with that of JP-A No. 33030), which indicates that the selection of the carrier is very important.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high yield under a milder condition than a conventionally known catalyst even when a saturated or unsaturated dicarboxylic acid derivative is used as a raw material. An object of the present invention is to provide a method for producing lactones, particularly γ-butyrolactone.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, zirconia was used as a carrier, and nickel and one or more VIIs were used.
The present inventors have found that when a hydrogenation reaction is carried out using a catalyst supporting a Group I noble metal, a saturated and / or unsaturated dicarboxylic acid derivative of a raw material can be converted into a lactone at a high yield under mild conditions. It was completed. That is, the present invention is characterized in that, when hydrogenating a saturated and / or unsaturated dicarboxylic acid derivative, a catalyst is used in which zirconia having a specific surface area of 50 m ² / g or more carries nickel and one or more noble metals of Group VIII. And a method for producing lactones.

Hereinafter, the present invention will be described in detail.

The raw material used in the present invention is a saturated and / or unsaturated dicarboxylic acid derivative. Specifically, anhydrides of saturated and / or unsaturated dicarboxylic acids such as maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, methylsuccinic anhydride, glutaric anhydride, maleic acid, succinic acid, fumaric acid , Itaconic acid, citraconic acid,
Saturated and / or unsaturated dicarboxylic acids such as mesaconic acid, methylsuccinic acid, glutaric acid and the like can be mentioned. In particular, when γ-butyrolactone is intended, maleic anhydride, maleic acid, succinic anhydride, succinic acid, and fumaric acid can be mentioned as raw materials.

[0010] These raw materials of the saturated or unsaturated dicarboxylic acid derivatives may be mixed in any ratio as long as the hydrogenation products are the same.

In the method of the present invention, the saturated and / or unsaturated dicarboxylic acid derivative is preferably dissolved in a solvent and then subjected to the reaction. The solvent is not particularly limited as long as it is inert to the hydrogenation reaction and does not react with the product lactones.Examples include ethers such as diethyl ether, dimethoxyethane, diglyme, triglyme, tetrahydrofuran, and dioxane. , Methyl acetate, ethyl acetate, methyl benzoate, esters such as ethyl benzoate, methanol, ethanol, n-butanol, iso-butanol, tert-butanol, 1,
Alcohols such as 4-butanediol, n-hexane,
Examples thereof include aliphatic hydrocarbons such as cyclohexane, acidic solvents such as acetic acid, lactones such as γ-butyrolactone, and acid amides such as 2-pyrrolidone and N-methylpyrrolidone.

The amount of these solvents used is not particularly limited as long as the raw materials are dissolved at the reaction temperature. The solvent does not need to be dried before use, and conversely, water may be present if it is about 1 molar equivalent to the raw material.

In the present invention, zirconia is used as a carrier, and a carrier having a specific surface area of 50 m ² / g or more is used.
Preferably it is at least 70 m ² / g. 50
When zirconia having a specific surface area smaller than m ² / g is used,
The activity of the catalyst may be insufficient. In addition, these zirconia can be obtained in various crystal structures depending on the raw material at the time of preparation and the heat treatment conditions at the time of preparation.In the present invention, the crystal structure of zirconia is metastable tetragonal, monoclinic,
It may be either tetragonal or cubic, and may be amorphous.

The method of preparing zirconia is not particularly limited, and a method prepared by hydrolyzing a zirconium compound or the like may be used. The zirconium compound is not particularly limited, and various inorganic and organic zirconium compounds can be used. Examples of the inorganic zirconium compound include zirconium nitrate, zirconium oxide chloride, zirconium oxide nitrate, zirconium oxide perchlorate, zirconium sulfate, and the like. Examples of the organic zirconium compound include zirconium tetrapropoxide and zirconium-2,4-pentadionate.

[0015] The specific surface area of zirconia is greatly affected by the heat treatment method at the time of preparing zirconia, in particular, the heat treatment temperature. However, since the obtained zirconia crystal form differs depending on the raw material of zirconia and the preparation method,
It is difficult to determine the range of the heat treatment method. Therefore, the specific surface area of zirconia finally obtained is 50 m ²
/ G or more, it is important to appropriately adjust the heat treatment temperature. If you decide on the temperature range, 10
Heat treatment up to 00 ° C. is preferred.

The shape of zirconia is not particularly limited, and it can be used as it is or in the form of powder according to the type of reaction. For the suspension bed, powder or granules are used, and for the fixed bed, tablet compression moldings, spherical or columnar extrusion moldings, and the like are used.

In the present invention, a catalyst is used in which nickel and one or more noble metals of Group VIII are supported on zirconia. The nickel compound that can be used in preparing the catalyst is not particularly limited as long as it can be converted to metallic nickel during or before the hydrogenation reaction. Specifically, various inorganics such as nickel carbonate, nickel chloride, nickel hydroxide, nickel nitrate, nickel oxide, nickel sulfate, nickel acetate, nickel oxalate,
Organic nickel compounds can be used.

The raw material of the Group VIII noble metal coexisting with nickel is not particularly limited as long as the raw material can be converted to a zero-valent metal during the hydrogenation reaction or before use in the reaction. Then, hexachloropalladium ammonium, ammonium tetrachloropalladate, dinitrodiamine palladium, chlorocarbonyl palladium, palladium chloride, palladium nitrate, palladium oxide, palladium sulfate, palladium acetate, palladium acetylacetonate, potassium dinitrosulfite palladium, Potassium hexachloropalladate, sodium tetrachloropalladate, tetraamminepalladium chloride, tetraamminepalladium nitrate, dichlorodiaminepalladium, dichloro (ethylenediamine) palladium Arm, palladium compounds such as potassium tetracyano palladium acids and the like.

Also, ammonium hexachlororhodate, ammonium pentachloroaquarhodate, potassium pentachloroaquarhodate, rhodium chloride, rhodium hydroxide, rhodium nitrate, rhodium oxide, sodium hexachlororhodate, mer-trichlorotriamminerhodium, chloropentane Ammine rhodium chloride,
Dichlorobis (ethylenediamine) rhodium nitrate, tris (ethylenediamine) rhodium chloride, trans
-Rhodium compounds such as dichlorotetrapyridine rhodium chloride, dodecacarbonyltetrarhodium, hexadecacarbonylhexarhodium and the like.

Further, ammonium oxydecachlorodiruthenate, ammonium pentachloroaquaruthenate, ammonium chloride ruthenate, potassium oxydecachlorodiruthenate, potassium pentachloroaquaruthenate, potassium perruthenate, ruthenium chloride, nitrosylruthenium nitrate , Ruthenium oxide, hexaammineruthenium chloride, pentaamminechlororuthenium chloride, dodecacarbonyltriruthenium,
Ruthenium compounds such as hexacarbonyltetrachlorodiruthenium and cesium tricarbonyltrichlororuthenate are exemplified.

Further, ammonium hexabromoiridate, ammonium hexachloroiridate, hexachloroiridic acid, iridium chloride, iridium oxide,
Potassium hexachloroiridate, sodium hexachloroiridate, chloropentaammineiridium chloride, dichlorobis (ethylenediamine) iridium chloride, dodecacarbonyl tetriiridium, tran
An iridium compound such as s-octacarbonyloctachlorotetriiridic acid is exemplified.

Further, ammonium hexabromoplatinate,
Ammonium tetrachloroplatinate, dinitrodiamineplatinum, dinitrosulfiteplatinic acid, hexachloroplatinic acid, hexahydroxyplatinic acid, platinum chloride, platinum oxide, potassium hexachloroplatinate, potassium hexahydroxoplatinate, potassium tetrachloroplatinate, hexachloroplatinum Platinum compounds such as sodium platinate, tetraammineplatinum chloride, tetraammineplatinum hydroxide, and sodium tetracyanoplatinate are exemplified.

Among these, a palladium compound is preferred.

The amount of nickel supported on the catalyst used in the present invention is 0.1 to 60% by weight, preferably 1 to 50% by weight, as nickel metal, based on the total weight of the catalyst including the support. The amount of the noble group VIII metal supported on nickel depends on the atomic ratio (for example, Pd or Ru / N
(i atomic ratio) is preferably 0.3 or less.
If the atomic ratio exceeds 0.3, the properties of the Group VIII noble metal become strong, and a side reaction such as a decarbonylation reaction may occur.

The method for preparing the catalyst comprising nickel and a noble metal of Group VIII used in the present invention is not particularly limited, and a catalyst prepared by a known method can be used. For example, it can be prepared by a precipitation method, a kneading method, an impregnation method, a deposition method, or the like. At this time, all the elements may be supported simultaneously or sequentially. For example, when preparing by an impregnation method, a nickel compound and a group VIII element, for example, a compound such as palladium or ruthenium, are dissolved in a suitable solvent, a carrier is added thereto, and if necessary, left for a predetermined time. After that, it is dried.

Reduction may be performed directly after drying, or in some cases, reduction may be performed after firing. Of course, reduction may be performed in the reaction system. The reduction method is not particularly limited as long as metallic nickel and one or more kinds of noble metals of Group VIII can be obtained. For example, reduction in a gas phase using hydrogen or the like or reduction in a liquid phase using hydrazine or the like is possible. It does not matter. The reduction temperature is not particularly limited as long as the nickel compound and at least one group VIII noble metal compound used as the raw materials are reduced to a metal, but a temperature up to 600 ° C. may be used.

Further, in the case of preparing by a deposition method, a nickel compound and a noble metal element of the group VIII, for example, a compound such as palladium and ruthenium are dissolved in a suitable solvent, for example, water, and a carrier is added. The agent is added slowly or all at once to deposit the nickel, palladium or ruthenium component, and the resulting mixture is dried, and thereafter can be used as a catalyst in the same manner as in the impregnation method.

Further, the catalyst used in the present invention preferably has a chlorine content of 0.9% by weight or less. Such a catalyst can be prepared by using a raw material containing no chlorine, or by washing with, for example, aqueous ammonia at any stage of the preparation. If the chlorine content is more than 0.9% by weight, sufficient catalytic activity may not be obtained.

In the present invention, the reaction can be carried out batchwise, semi-batchwise, continuously with a suspension bed or in a fixed bed flow system.

The reaction according to the method of the present invention is carried out under heating and under hydrogen pressure. The reaction temperature is 100 to 240 ° C, preferably 120 to 240 ° C, more preferably 120 to 240 ° C.
230 ° C is chosen. If it is higher than this, only the progress of the side reaction increases, and if it is lower, the reaction speed is disadvantageous. The pressure of hydrogen is 10 to 140 kg / cm.
² G, preferably 15 to 120 kg / cm ² G is selected. In the process of the present invention, the desired reaction proceeds sufficiently within this range, so that higher pressures beyond this are unnecessary, and lower pressures are disadvantageous in terms of reaction rate.

The reaction time varies depending on the setting method of the temperature, pressure, amount of catalyst, etc. or the reaction method, so that it is difficult to determine the range in a straightforward manner.
In the semi-batch mode, 0.5 hours or more is required, and preferably 1 to 20 hours. It may be longer, but
Since the reaction is completed within this range, it is meaningless. If it is shorter than this, a high conversion may not be obtained. In a continuous reaction using a suspension bed or a fixed bed flow reaction, the residence time may be 0.1 to 10 hours.

The amount of the catalyst used is not particularly limited, but is preferably 0.5 to 200% by weight, more preferably 1 to 150% by weight, based on the raw material.

[0033]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to only these Examples.

Catalyst Preparation Example 1 10% Ni-1.8% Pd / ZrO ₂ (90 m ² / g) 7.43 g of nickel nitrate (Ni (NO ₃ ) ₂ .6H ₂ O)
And palladium nitrate aqueous solution (Pd; 4.4 wt%) 6.1
4 g were added to 50 ml of water. Zirconia having a specific surface area of 90 m ² / g (manufactured by Norton; Sample Number 921) crushed to 200 mesh or less in this solution.
6337) 13.23 g was added.

After standing for a predetermined time, water was removed under reduced pressure using a rotary evaporator, and the obtained paste was dried at 40 ° C. for 1 hour under reduced pressure, and further dried at 120 ° C. for 2 hours to obtain a powder. .

The above-mentioned powder is put into a gas flow reduction device,
Using a gas mixed with 135 ml / min of nitrogen and 15 ml / min of hydrogen, reduction was performed at 400 ° C. for 15 hours, and 10%
A Ni-1.8% Pd / ZrO ₂ (90 m ² / g) catalyst was obtained. The atomic ratio between Pd and Ni was 0.1. As a result of measurement with a fluorescent X-ray analyzer, the chlorine content was 0.05%.
% By weight or less.

Catalyst Preparation Example 2 10% Ni-1.8% Pd / SiO ₂ (180 m ² / g) Silica (CARiACT, manufactured by Fuji Devison) as a carrier
-15; 180 m ² / g), a catalyst was prepared in the same manner as in Catalyst Preparation Example 1, and 10% Ni-1.8%
A Pd / SiO ₂ (180 m ² / g) catalyst was obtained. As a result of measurement with a fluorescent X-ray analyzer, the chlorine content was 0.05% by weight.
It was below.

Catalyst Preparation Example 3 10% Ni-1.8% Pd / SiO ₂ (300 m ² / g) Silica (CARACT, manufactured by Fuji Devison Co., Ltd.) as a carrier
-10; 300 m ² / g), a catalyst was prepared in the same manner as in Catalyst Preparation Example 1, and 10% Ni-1.8%
A Pd / SiO ₂ (300 m ² / g) catalyst was obtained. As a result of measurement with a fluorescent X-ray analyzer, the chlorine content was 0.05% by weight.
It was below.

Catalyst Preparation Example 4 10% Ni-1.8% Pd / diatomaceous earth (35 m ² /
g) A catalyst was prepared in the same manner as in Catalyst Preparation Example 1 except that diatomaceous earth (HSC; 35 m ² / g) manufactured by Johns-Manville was used as a carrier, and 10% Ni-1.8 was prepared.
% Pd / diatomaceous earth (35 m ² / g) catalyst was obtained. As a result of measurement with a fluorescent X-ray analyzer, the chlorine content was 0.05% by weight or less.

Catalyst Preparation Example 5 10% Ni-1.8% Pd / ZrO ₂ (12 m ² / g) Zirconia (Sample N, manufactured by Norton) as a carrier
umber 9016433; 12m ² / g) except for using the catalyst prepared in a similar manner to Catalyst Preparation Example 1, 1
0% Ni-1.8% Pd / ZrO 2 (12m 2 / g) to obtain a catalyst. As a result of measurement with a fluorescent X-ray analyzer, the chlorine content was 0.05% by weight or less.

Catalyst Preparation Example 6 10% Ni-0.3% Pd / ZrO ₂ (90 m ² / g) An aqueous solution of palladium nitrate (Pd; 4.4 wt%) was added to 1.0%
A catalyst was prepared in the same manner as in Catalyst Preparation Example 1, except that 2 g and 13.46 g of zirconia were used.
3% Pd / ZrO ₂ (90 m ² / g) was obtained. The atomic ratio of Pd to Ni in the obtained catalyst was 0.017.

Catalyst Preparation Example 7 10% Ni-3.6% Pd / ZrO ₂ (90 m ² / g) palladium nitrate aqueous solution (Pd; 4.4 wt%)
A catalyst was prepared in the same manner as in Catalyst Preparation Example 1 except that 27 g and zirconia were 12.96 g, and 10% Ni-
A 3.6% Pd / ZrO ₂ (90 m ² / g) catalyst was obtained. The atomic ratio of Pd to Ni in the obtained catalyst was 0.2.
Further, as a result of measurement with a fluorescent X-ray analyzer, the chlorine content was 0.05% by weight or less.

[0043] Catalyst Preparation Example 8 20% Ni-0.6% Pd / ZrO 2 a (98m ² / g) nickel nitrate _{(Ni (NO 3) 2 ·} 6H 2 O) 14.8
6 g, 2.05 g of an aqueous solution of palladium nitrate (Pd; 4.4 wt%), and 98 m ² / g of zirconia (Norton; Sample Number 9116293)
A catalyst was prepared in the same manner as in Catalyst Preparation Example 1 except that 11.91 g was used, and 20% Ni-0.6% Pd / ZrO
₂ (98 m ² / g) catalyst was obtained. Pd and N of the obtained catalyst
The atomic ratio of i was 0.017. Further, as a result of measurement with a fluorescent X-ray analyzer, the chlorine content was 0.05% by weight or less.

Catalyst Preparation Example 9 10% Ni-0.9% Pd / ZrO ₂ (53 m ² / g) An aqueous solution of palladium nitrate (Pd; 4.4 wt%) was 3.0
7 g, and 53 m ² / g to zirconia (Norton;
Sample Number 9116296) 13.
A catalyst was prepared in the same manner as in Catalyst Preparation Example 1 except that 37 g was used, and 10% Ni-0.9% Pd / ZrO ₂ (5
3 m ² / g) catalyst was obtained. The atomic ratio of Pd to Ni in the obtained catalyst was 0.05. Further, as a result of measurement with a fluorescent X-ray analyzer, the chlorine content was 0.05% by weight or less.

Catalyst Preparation Example 10 10% Ni / ZrO ₂ (90 m ² / g) Nickel nitrate (Ni (NO ₃ ) ₂ .6H ₂ O) 7.43 g
Was dissolved in 50 ml of water. This solution was mixed with Norton zirconia (Sample Number 921633).
7; 90 m ^{2 /} g) 13.50 g was pulverized to 200 mesh or less and added.

After standing for a predetermined time, water was removed under reduced pressure using a rotary evaporator, and the obtained paste was dried at 40 ° C. for 1 hour under reduced pressure, and further dried at 120 ° C. for 2 hours to obtain a powder. .

The above-mentioned powder is put into a gas flow type reduction device,
Using a gas mixed with 135 ml / min of nitrogen and 15 ml / min of hydrogen, reduction was performed at 400 ° C. for 15 hours, and 10%
A Ni / ZrO ₂ (90 m ² / g) catalyst was obtained.

Catalyst Preparation Example 11 2.0% Pd / ZrO ₂ (90 m ² / g) An aqueous solution of palladium nitrate (Pd; 4.4 wt%) was used instead of nickel nitrate (Ni (NO ₃ ) ₂ .6H ₂ O). 6.8
A catalyst was prepared in the same manner as in Catalyst Preparation Example 10, except that 2 g was used, and zirconia was changed to 14.70 g,
A 2.0% Pd / ZrO ₂ (90 m ² / g) catalyst was obtained.

Example 1 In a 200 ml stainless steel autoclave, 1.96 g (20 mmol) of maleic anhydride, 10% Ni-1.8% Pd / ZrO ₂ prepared in Catalyst Preparation Example 1 (90 m ² /
g) After 420 mg of THF and 20 ml of THF were charged and the inside of the system was sufficiently replaced with hydrogen, hydrogen was injected under pressure to 50 kg / cm ² G. While heating and stirring, the temperature was raised to 150 ° C and 3
The hydrogenation reaction was performed for hours.

After the completion of the reaction, the autoclave was cooled to room temperature, then purged with hydrogen and the reaction solution was taken out. After filtering off the catalyst and the like, the filtrate was analyzed by gas chromatography, and as a result, the yield of γ-butyrolactone was 96.5 mol% with respect to the starting material maleic anhydride.

Example 2 In a 200 ml stainless steel autoclave, 10.0 g (100 mmol) of succinic anhydride, 10% Ni-1.8% Pd / ZrO ₂ (90 m ² /
g) 2.0 g and 20 ml of THF were charged, and the inside of the system was sufficiently replaced with hydrogen, and then hydrogen was injected under pressure to 50 kg / cm ² G. The temperature was raised to 180 ° C. while heating and stirring, and a hydrogenation reaction was carried out for 4 hours while keeping the hydrogen pressure constant.

After the completion of the reaction, the autoclave was cooled to room temperature, then purged with hydrogen and the reaction solution was taken out. After filtering off the catalyst and the like, the filtrate was analyzed by gas chromatography. As a result, the yield of γ-butyrolactone was 78.0 mol% with respect to the raw material succinic anhydride.

Example 3 In a 200 ml stainless steel autoclave, 30.0 g (300 mmol) of succinic anhydride, 10% Ni-0.3% Pd / ZrO ₂ (90 m ² /
g) 3.0 g and 45 ml of THF were charged and the inside of the system was sufficiently replaced with hydrogen, and then hydrogen was injected under pressure to 50 kg / cm ² G. The temperature was raised to 200 ° C. with heating and stirring, and a hydrogenation reaction was performed for 3 hours while keeping the hydrogen pressure constant.

After the completion of the reaction, the autoclave was cooled to room temperature, then purged with hydrogen and the reaction solution was taken out. After filtering off the catalyst and the like, the filtrate was analyzed by gas chromatography, and as a result, the yield of γ-butyrolactone was 74.5 mol% based on the raw material succinic anhydride.

Example 4 17.71 g (15 parts) of succinic acid was used instead of succinic anhydride.
0 mmol), and the catalyst was 10% Ni-1.8% Pd / ZrO ₂ (90 m ² /
The reaction was carried out in the same manner as in Example 3 except that g) was used. Table 1 shows the results.

Example 5 The catalyst was 10% Ni-3.6% P prepared in Catalyst Preparation Example 7.
The reaction was carried out in the same manner as in Example 3 except that d / ZrO ₂ (90 m ² / g) was used. Table 1 shows the results.

Example 6 The catalyst was 20% Ni-0.6% P prepared in Catalyst Preparation Example 8.
The reaction was carried out in the same manner as in Example 3 except that d / ZrO ₂ (98 m ² / g) was used. Table 1 shows the results.

Example 7 The catalyst was 10% Ni-0.9% P prepared in Catalyst Preparation Example 9.
The reaction was carried out in the same manner as in Example 3 except that d / ZrO ₂ (53 m ² / g) was used. Table 1 shows the results.

Comparative Example 1 A 10% Ni / ZrO ₂ catalyst prepared in Catalyst Preparation Example 10 was used.
(90 m ² / g) except that the reaction was carried out in the same manner as in Example 3. Table 1 shows the results.

Comparative Example 2 A 2.0% Pd / ZrO catalyst prepared in Catalyst Preparation Example 11 was used.
_The reaction was carried out in the same manner as in Example 3 except that the reaction volume was changed to ₂ (90 m ² / g). Table 1 shows the results.

Comparative Example 3 The catalyst was 10% Ni-1.8% P prepared in Catalyst Preparation Example 2.
The reaction was carried out in the same manner as in Example 1 except that d / SiO ₂ (180 m ² / g) and the reaction temperature were 180 ° C. Table 1 shows the results.

Comparative Example 4 The catalyst was 10% Ni-1.8% P prepared in Catalyst Preparation Example 2.
Example 2 except that d / SiO ₂ (180 m ² / g) was used.
The reaction was carried out in the same manner as described above. Table 1 shows the results.

Comparative Example 5 The catalyst was 10% Ni-1.8% P prepared in Catalyst Preparation Example 3.
Example 3 except that d / SiO ₂ (300 m ² / g) was used.
The reaction was carried out in the same manner as described above. Table 1 shows the results.

Comparative Example 6 The catalyst was 10% Ni-1.8% P prepared in Catalyst Preparation Example 4.
The reaction was carried out in the same manner as in Example 3 except that d / diatomaceous earth (35 m ² / g) was used. Table 1 shows the results.

Comparative Example 7 The catalyst was 10% Ni-1.8% P prepared in Catalyst Preparation Example 5.
The reaction was carried out in the same manner as in Example 3 except that d / ZrO ₂ (12 m ² / g) was used. Table 1 shows the results.

[0066]

[Table 1]

The abbreviations in the table represent the following.

THF: tetrahydrofuran MAN: maleic anhydride SAN: succinic anhydride SAC: succinic acid

[0069]

According to the present invention, in the hydrogenation of a saturated and / or unsaturated dicarboxylic acid derivative, a hydrogenation reaction is carried out using zirconia with a catalyst supporting nickel and at least one noble metal of Group VIII. By performing the above, lactones can be produced in a higher yield under mild conditions as compared with a heterogeneous catalyst supported on a conventionally known carrier.

[0070]

Continuation of the front page (56) References JP-A-1-143865 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 307/33 B01J 23/89 C07B 61/00 300 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A hydrogenation method for a saturated and / or unsaturated dicarboxylic acid derivative, characterized in that a catalyst comprising nickel and at least one noble metal of Group VIII supported on zirconia having a specific surface area of 50 m ² / g or more. For producing lactones. 2. The method according to claim 1, wherein the Group VIII noble metal is palladium. 3. The method according to claim 1, wherein the atomic ratio of the Group VIII noble metal and nickel supported on zirconia is 0.3 or less. 4. The process according to claim 1, wherein the chlorine content of the catalyst is 0.9% by weight or less.