Production methods of catalyst for hydrogenation and diol

Abstract

The invention relates to a novel catalyst for hydrogenation for hydrogenating at least one of dicarboxylic acid or its acid anhydride. The catalyst for hydrogenation according to a first embodiment is obtained by supporting at least one of palladium or platinum, and cobalt on a carrier, and subjecting the resulting carrier to a reduction treatment at 400 K or higher. The catalyst for hydrogenation according to a second embodiment is obtained by supporting at least one of palladium or platinum, and molybdenum on a carrier, and subjecting the resulting carrier to a reduction treatment at 500 K or higher.

Claims

1. A production method of a catalyst for hydrogenation for hydrogenating at least one of dicarboxylic acid or its acid anhydride, comprising: supporting at least one of palladium or platinum, and cobalt, as a metal component, on a carrier, and subjecting the resulting carrier to a reduction treatment at 400 K or higher, wherein a whole part of the metal component consists of: (i) the at least one of palladium or platinum and/or a compound of the at least one of palladium or platinum and (ii) the cobalt and/or a compound of the cobalt.

2. The production method of a catalyst for hydrogenation according to claim 1, wherein the reduction treatment is a reduction treatment in a gas phase.

3. The production method of a catalyst for hydrogenation according to claim 1, wherein the catalyst contains the at least one of palladium or platinum in a form of a simple substance, and the cobalt in a form of a simple substance and/or an oxide.

4. A production method of a catalyst for hydrogenation for hydrogenating at least one of dicarboxylic acid or its acid anhydride, comprising: supporting at least one of palladium or platinum, and molybdenum, as a metal component, on a carrier, and subjecting the resulting carrier to a reduction treatment at 1000K or higher, wherein a whole part of the metal component consists of: (i) the at least one of palladium or platinum and/or a compound of the at least one of palladium or platinum and (ii) the molybdenum and/or a compound of the molybdenum.

5. The production method of a catalyst for hydrogenation according to claim 4, wherein the reduction treatment is a reduction treatment in a gas phase.

6. The production method of a catalyst for hydrogenation according to claim 4, wherein the catalyst contains the at least one of palladium or platinum in a form of a simple substance, and the molybdenum in a form of a simple substance and/or an oxide.

7. A production method of a diol, comprising: subjecting a carrier having supported thereon at least one of palladium or platinum, and cobalt, as a metal component, to a reduction treatment at 400 K or higher, wherein a whole part of the metal component consists of: (i) the at least one of palladium or platinum and/or a compound of the at least one of palladium or platinum; and (ii) the cobalt and/or a compound of the cobalt, and hydrogenating at least one of dicarboxylic acid or its acid anhydride in the presence of the reduced carrier as a catalyst, thereby producing a diol.

8. The production method of a diol according to claim 7, wherein the reduction treatment is a reduction treatment in a gas phase.

9. The production method of a diol according to claim 7, wherein the catalyst contains the at least one of palladium or platinum in a form of a simple substance, and the cobalt in a form of a simple substance and/or an oxide.

10. A production method of a diol, comprising: subjecting a carrier having supported thereon at least one of palladium or platinum, and molybdenum, as a metal component, to a reduction treatment at 1000K or higher, wherein a whole part of the metal component consists of: (i) the at least one of palladium or platinum and/or a compound of the at least one of palladium or platinum; and (ii) the molybdenum and/or a compound of the molybdenum, and hydrogenating at least one of dicarboxylic acid or its acid anhydride in the presence of the reduced carrier as a catalyst, thereby producing a diol.

11. The production method of a diol according to claim 10, wherein the reduction treatment is a reduction treatment in a gas phase.

12. The production method of a diol according to claim 10, wherein the catalyst contains the at least one of palladium or platinum in a form of a simple substance, and the molybdenum in a form of a simple substance and/or an oxide.

13. A catalyst for hydrogenation for hydrogenating at least one of dicarboxylic acid or its acid anhydride, which comprises a carrier, at least one of palladium or platinum supported on the carrier, and cobalt supported on the carrier, and is obtained by subjecting the resulting carrier to a reduction treatment at 400 K or higher, wherein a whole part of a metal component supported on the carrier consists of: (i) the at least one of palladium or platinum and/or a compound of the at least one of palladium or platinum; and (ii) the cobalt and/or a compound of the cobalt.

14. The catalyst for hydrogenation according to claim 13, wherein the at least one of palladium or platinum is contained in a form of a simple substance, and the cobalt is contained in a form of a simple substance and/or an oxide.

15. A catalyst for hydrogenation for hydrogenating at least one of dicarboxylic acid or its acid anhydride, which comprises a carrier, at least one of palladium or platinum supported on the carrier, and molybdenum supported on the carrier, and is obtained by subjecting the resulting carrier to a reduction treatment at 1000K or higher, wherein a whole part of a metal component supported on the carrier consists of: (i) the at least one of palladium or platinum and/or a compound of the at least one of palladium or platinum and (ii) the molybdenum and/or a compound of the molybdenum.

16. The catalyst for hydrogenation according to claim 15, wherein the at least one of palladium or platinum is contained in a form of a simple substance, and the molybdenum is contained in a form of a simple substance and/or an oxide.

Description

EXAMPLES

(1) Examples are described below, but the present invention is not construed as being limited to those examples.

Production Example 1 Preparation of Mo—Pd Catalyst (MoO.SUB.x.—Pd/SiO.SUB.a.)

(2) Silica (SiO.sub.2) (manufactured by Fuji Silysia Chemical Ltd., product name “CARiACT G-6”, specific surface area: 485 m.sup.2/g, pore volume: 0.74 mL/g, packing density: 0.49 g/mL, water content: 0.2% by mass, average particle diameter: 75 to 150 μm, pretreatment: 973 K, 1 hour) was used as a carrier.

(3) 0.43 g of a palladium nitrate (Pd(NO.sub.3).sub.2) solution (manufactured by Wako Pure Chemical Industries Ltd., 10% by mass Pd (NO.sub.3).sub.2) was put in a 5 mL sample bottle, and diluted with distilled water to obtain 5 g of a solution. 1.6 g of the silica was put in a 100 mL beaker, 5 g of the diluted palladium nitrate solution was added to the beaker little by little while heating to 353 to 363 K with a hot stirrer, and Pd was supported on the silica based on an incipient-wetness method while sufficiently mixing. After vaporizing water on the stirrer, the silica having palladium supported thereon was dried in an oven at 383 K overnight.

(4) 0.664 g of hexaammonium heptamolybdate tetrahydrate ((NH.sub.4).sub.6Mo.sub.7O.sub.24.4H.sub.2O, manufactured by Wako Pure Chemical industries Ltd., 99.0%) was put in a small bottle, and distilled water was added to the small bottle to prepare 5 g of an aqueous solution. 5 g of the hexaammonium heptamolybdate tetrahydrate solution prepared was added to the beaker containing therein the silica having palladium supported thereon little by little while heating the beaker to 353 to 363 K by a hot stirrer, and the supporting based on an incipient-wetness method was repeatedly conducted until a molar ratio of molybdenum to palladium became Mo/Pd=20. After vaporizing water on the stirrer, the silica having palladium and molybdenum supported thereon was dried in an oven at 383 K overnight. Thereafter, the carrier obtained was placed in a muffle furnace, heated to 673 K in a temperature rising rate of 10 K/min, and then baked at 673 K for 3 hours (temperature rising rate: 10 K/min). Thus, Mo—Pd catalyst (MoO.sub.x—Pd/SiO.sub.2) was obtained (the amount of palladium supported is 1.0% by mass in terms of metal, based on the mass of the entire catalyst. Mo/Pd=20/1 (molar ratio)). MoO.sub.x may contain a compound of x=0 (that is, a simple substance of the oxidation number of 0).

Production Example 2 Preparation of Co—Pd Catalyst (CoO.SUB.x.—Pd/SiO.SUB.2.)

(5) 0.43 g of a palladium nitrate (Pd(NO.sub.3).sub.2) solution (manufactured by Wako Pure Chemical Industries Ltd., 10% by mass Pd (NO.sub.3).sub.2) was put in a 5 mL sample bottle, and diluted with distilled water to obtain 5 g of a solution. 1.7 g of silica (SiO.sub.2) (manufactured by Fuji Silysia Chemical Ltd., product, name “CARiACT G-6”) was put in a 100 mL beaker, 5 g of the diluted palladium nitrate solution was added to the beaker little by little while heating to 353 to 363 K with a hot stirrer, and Pd was supported on the silica based on an incipient-wetness method while sufficiently mixing. After vaporizing water on the stirrer, the silica having palladium supported thereon vas dried in an oven at 383 K overnight.

(6) 1.09 g of cobalt nitrate ((Co(NO.sub.3).sub.2.6H.sub.2O, manufactured by Wako Pure Chemical Industries Ltd., 98.0%) was put in a small bottle, and distilled water was added to the small bottle to prepare 5 g of an aqueous solution. 5 g of the hexaammonium heptamolybdate tetrahydrate solution prepared was added to the beaker containing therein the silica having palladium supported thereon little by little while heating the beaker to 353 to 363 K by a hot stirrer, and the supporting based on an incipient-wetness method was repeatedly conducted until a molar ratio of cobalt to palladium became Co/Pd=20. After vaporizing water on the stirrer, the silica having palladium and cobalt supported thereon was dried in an oven at 383 K overnight. Thereafter, the carrier obtained was placed in a muffle furnace, heated to 673 K in a temperature rising rate of 10 K/min, and then baked at 673 K for 3 hours. Thus, Co—Pd catalyst (CoO.sub.x—Pd/SiO.sub.2) was obtained (the amount of palladium supported is 1.0% by mass in terms of metal, based on the mass of the entire catalyst. Co/Pd=20/1 (molar ratio)). CoO.sub.x may contain a compound of x=0 (that is, a simple substance of the oxidation number of 0).

Production Example 3 Preparation of Mo Catalyst (MoO.SUB.x./SiO.SUB.2.)

(7) 0.66 g of hexaammonium heptamolybdate tetrahydrate ((NH.sub.4).sub.6Mo.sub.7O.sub.24. 4H.sub.2O, manufactured by Wako Pure Chemical Industries Ltd., 99.0%) was put in a 5 mL sample bottle, and distilled water was added to the small bottle to prepare 5 g of an aqueous solution. 1.64 g of silica (SiO.sub.2) (manufactured by Fuji Silysia Chemical Ltd., product name “CARiACT G-6”) was put in a 100 mL beaker, 5 g of the hexaammonium heptamolybdate tetrahydrate solution was added to the beaker little by little while heating to 353 to 363 K with a hot stirrer, and the supporting was conducted based on an incipient-wetness method while sufficiently mixing. After vaporizing water on the stirrer, the silica having molybdenum supported thereon was dried in an oven at 383 K overnight. Thereafter, the carrier obtained was placed in a muffle furnace, heated to 673K in a temperature rising rate of 10 K/min, and then baked at 673 K for 3 hours. Thus, Mo catalyst (MoO.sub.x/SiO.sub.2) was obtained (the amount of molybdenum supported is 18% by mass in terms of metal, based on the mass of the entire catalyst).

Production Example 4 Preparation of Pd Catalyst (Pd/SiO.SUB.2.)

(8) 0.43 g of palladium nitrate (Pd(NO.sub.3).sub.2) solution (manufactured by Wako Pure Chemical Industries Ltd., 10% by mass Pd(NO.sub.3).sub.2) was put in a 5 mL sample bottle, and diluted with distilled water to obtain 5 g of a solution. 1.98 g of silica (SiO.sub.2) (manufactured by Fuji Silysia Chemical Ltd., product name “CARiACT G-6”) was put in a 100 mL beaker, 5 g of the diluted palladium nitrate solution was added to the beaker little by little while heating to 353 to 363 K by a hot stirrer, and the supporting was conducted based or an incipient-wetness method while sufficiently stirring. After vaporizing water on the stirrer, the carrier obtained was dried in an oven at 383 K overnight. Thereafter, the carrier obtained was placed in a muffle furnace, heated to 673 K in a temperature rising rate of 10 K/min, and then baked at 673 K for 3 hours. Thus, Pd catalyst (Pd/SiO.sub.2) was obtained (the amount of palladium supported is 1.0% by mass in terms of metal, based on the mass of the entire catalyst).

Production Example 5 Preparation of Co—Pd Catalyst (CoO.SUB.x.—Pd/SiO.SUB.2.)

(9) Four Co—Pd catalysts (CoO.sub.x—Pd/SiO.sub.2) having different molar ratio were obtained in the same manner as Production Example 2, except for changing the molar ratio of cobalt to palladium to Co/Pd=8, 12, 16 and 32 (the amount of palladium supported is 1.0% by mass in terms of metal, based on the mass of the entire catalyst. Co/Pd=8, 12, 16 and 32 (molar ratio)).

Example 1

(10) 0.2 g of the Mo—Pd catalyst (MoO.sub.x—Pd/SiO.sub.2) obtained in Production Example 1 was placed in a quartz glass reaction tube (inner diameter 4 mm, outer diameter 6 mm, length 35 cm), and the reaction tube was set to a reduction apparatus. After nitrogen substitution, the reaction tube was heated to 673 K in a temperature rising rate of 10 K/min, and gas phase reduction was performed under the conditions of reduction temperature: 673 K and reduction time: 1 hour under hydrogen flowing, followed by cooling.

(11) In a nitrogen-substituted glove box, 0.10 g of the Mo—Pd catalyst after reduction vas put in an autoclave (high pressure batch type reaction apparatus, volume: 190 mL) containing 1.0 g of succinic acid (manufactured by Wako Pure Chemical Industries Ltd., 99.5%) and 19 g of 1,4-dioxane (manufactured by Wako Pure Chemical Industries Ltd., 99.5%) as a solvent, and the autoclave was sealed. Hydrogen of 1 MPa was introduced in the autoclave, and the autoclave was heated to 473 K by a reactor. After the temperature rising, hydrogen of 8 MPa was introduced in the autoclave, and hydrogenation reaction was conducted in a stirring speed of 500 rpm for 4 hours. After completion of the reaction, the autoclave was cooled with a water bath, and a liquid phase and a gas phase were recovered. Regarding the recovered materials, the product was analyzed by the analysis method described hereinafter.

Examples 2 to 5 and Comparative Example 1

(12) The gas phase reduction and hydrogenation reaction were conducted in the same manners as in Example 1, except that the reduction temperature in the gas phase reduction was changed to 873 K in Example 2, 1073 K in Example 3, 1173 K in Example 4, 1273 K in Example 5 and 473 K in Comparative Example 1, as shown in Table 1 below, and the products obtained were analyzed.

Example 6

(13) 0.2 g of the Co—Pd catalyst (CoO.sub.x—Pd/SiO.sub.2) obtained in Production Example 2 was placed in a quartz glass reaction tube (inner diameter 4 mm, outer diameter 6 mm, length 35 cm), and the reaction tube was set to a reduction apparatus. After nitrogen substitution, the reaction tube was heated to 473 k in a temperature rising rate of 10 K/min, and gas phase reduction was performed under the conditions of reduction temperature: 473 K and reduction time: 1 hour under hydrogen flowing, followed by cooling.

(14) In a nitrogen-substituted glove box, 0.10 g of the Co—Pd catalyst after reduction vas put in an autoclave (high pressure batch type reaction apparatus, volume: 190 mL) containing 1.0 g of succinic acid (manufactured by Wako Pure Chemical Industries Ltd., 99.5%) and 19 g of 1,4-dioxane (manufactured by Wako Pure Chemical Industries Ltd., 99.5%) as a solvent, and the autoclave was sealed. Hydrogen of 1 MPa was introduced in the autoclave, and the autoclave was heated to 473 K by a reactor. After the temperature rising, hydrogen of 8 MPa was introduced in the autoclave, and hydrogenation reaction was conducted in a stirring speed of 500 rpm for 4 hours. After completion of the reaction, the autoclave was cooled with a water bath, and a liquid phase and a gas phase were recovered. Regarding the recovered materials, the product was analyzed in the same manner as in Example 1.

Examples 7 to 10

(15) The gas phase reduction and the hydrogenation reaction were conducted in the same manner as in Example 6, except that the reduction temperature in the gas phase reduction was changed to 573 in Example 7, 673K in Example 8, 873 K in Example 9 and 1173 K in Example 10, as shown in Table 1 below. Products obtained were analyzed.

Comparative Example 2

(16) 0.2 g of the Mo catalyst (MoO.sub.x/SiO.sub.2) obtained in Production Example 3 was placed in a Quartz glass reaction tube (inner diameter 4 mm, outer diameter 6 mm, length 35 cm), and the reaction tube was set to a reduction apparatus. After nitrogen substitution, the reaction tube was heated to 1173 K in a temperature rising rate of 10 K/min, and gas phase reduction was performed under the conditions of reduction temperature: 1173 K and reduction time: 1 hour under hydrogen flowing, followed by cooling, using 0.10 of Mo catalyst after the reduction, the hydrogenation reaction of succinic acid was conducted in the same manner as in Example 1, and the product was analyzed.

Comparative Example 3

(17) 0.2 g of the Pd catalyst (Pd/SiO.sub.2) obtained in Production Example 4 was placed in a quartz glass reaction tube (inner diameter 4 mm, outer diameter 6 mm, length 35 cm), and the reaction tube was set to a reduction apparatus. After nitrogen substitution, the reaction tube was heated to 1173 K in a temperature rising rate of 10 K/min, and gas phase reduction was performed under the conditions of reduction temperature: 1173 K and reduction time: 1 hour under hydrogen flowing, followed by cooling. Using 0.10 of Pd catalyst; after the reduction, the hydrogenation reaction of succinic acid was conducted in the same manner as in Example 1, and the product was analyzed.

(18) The analytical conditions of the product are as follows. Using a gas chromatograph (GC) apparatus (“GC-2014” manufactured by Shimadzu Corporation), the liquid component was measured by “GC-FID”, and the gas component was measured by “GC-FID with metanator”. However, succinic acid has high boiling point, and is difficult to be measured with GC. Therefore, succinic acid was measured with HPLC (“LC-20AD” manufactured by Shimadzu Corporation).

(19) Internal standard material: 2-Methoxyethanol 1.5 mL

(20) [GC-FID (GC-2014)]

(21) Column: HF-FFAP

(22) Total analysis time: 30.00 min, inlet pressure: 87.6 kPa, column flow rate: 1.11 mL/min, linear velocity: 28.6 cm/s, split ratio: 25.0, total flow rate: 31.3 mL/min, injection mode: SPLIT, control mode: pressure, carrier gas: N.sub.2, vaporization chamber temperature: 533 K, detector temperature: 533 K, filter signal time constant: 200 ms, number of sample cleaning: 5 times, number of sample injection: 2 times, sample injection amount: 0.5 μL, number of solvent cleaning: 3 times (both before and after), waiting time after sample inhalation: 0.2 s, waiting time after sample injection: 0.0 s, AOC power supply: on, column length: 30 m, column inner diameter: 0.250 mm column membrane thickness: 0.25 μm

(23) Temperature rising program of column: (initial) temperature 333 K, time 0.00 min, (one stage) rate: 10.00 K/rain, temperature 503 K, hold time 13.00 min

(24) [GC-FID with Metanator (GC-2014)]

(25) Column: Porapak-T

(26) Time: 4.00 min, vaporization chamber temperature: 353 K, detector temperature: 353 K, frame: on, filter signal time constant: 200 ms, control mode: single L, detector signal input: CH1, background save: non, background correction: non, detector signal subtraction: non, signal attenuation: ×2.sup.−4, kind of analog signal: wide, metanator temperature: 673 K

(27) The temperature of the column is constant as 333 K.

(28) [(HPLC-RID (LC-20AD)]

(29) Flow rate: 0.9000 mL/min, pressure: 6.0 MPa, column temperature: 323 K

(30) Regarding Examples 1 to 10 and Comparative Examples 1 to 3, conversion rate, selectivity and mass balance were calculated from the following formulae.
Conversion rate (%)=[Total carbon atoms (mol) of product/(Total carbon atoms (mol) of residual substrate+total carbon atoms (mol) of product)]×100
Selectivity (%) of each material=[Total carbon atoms (mol) of each material/Total carbon atoms (mol) of product]×100
Mass balance (%)=[(Total carbon atoms (mol) of residual substrate+total carbon atoms (mol) of product)/Total carbon atoms of substrate supplied]×100

(31) TABLE-US-00001 TABLE 1 Reduction Conversion Mass Temperature rate Selectivity (%) Balance Catalyst (K) (%) BDO GBL THF BuA BuOH PrA CO CO.sub.2 CH.sub.4 C.sub.2H.sub.6 (%) Com. Ex. 1 MoO.sub.x—Pd/SiO.sub.2 473 6.4 0.0 82 18 0.0 0.0 0.0 0.2 0.0 0.0 0.0 103 Ex. 1 MoO.sub.x—Pd/SiO.sub.2 673 22 0.0 98 1.4 0.0 0.0 0.0 0.0 0.0 0.0 0.2 100 Ex. 2 MoO.sub.x—Pd/SiO.sub.2 873 50 0.2 96 3.1 0.3 0.1 0.2 0.0 0.0 0.0 0.1 95 Ex. 3 MoO.sub.x—Pd/SiO.sub.2 1073 64 2.0 96 1.8 0.1 0.1 0.2 0.0 0.0 0.0 0.0 97 Ex. 4 MoO.sub.x—Pd/SiO.sub.2 1173 65 3.2 95 1.5 0.1 0.1 0.1 0.0 0.0 0.0 0.0 96 Ex. 5 MoO.sub.x—Pd/SiO.sub.2 1273 63 1.3 95 3.0 0.2 0.1 0.3 0.0 0.0 0.0 0.0 98 Ex. 6 CoO.sub.x—Pd/SiO.sub.2 473 50 0.3 99 0.0 0.0 0.0 0.2 0.0 0.0 0.0 0.0 95 Ex. 7 CoO.sub.x—Pd/SiO.sub.2 573 63 0.7 99 0.1 0.0 0.0 0.2 0.0 0.0 0.1 0.0 102 Ex. 8 CoO.sub.x—Pd/SiO.sub.2 873 64 0.3 99 0.2 0.1 0.0 0.2 0.0 0.0 0.0 0.0 97 Ex. 9 CoO.sub.x—Pd/SiO.sub.2 873 60 0.0 99 0.2 0.2 0.0 0.6 0.0 0.0 0.0 0.0 96 Ex. 10 CoO.sub.x—Pd/SiO.sub.2 1173 63 0.0 99 0.2 0.2 0.0 0.5 0.0 0.0 0.1 0.0 99 Com. Ex. 2 MoO.sub.x/SiO.sub.2 1173 0.9 — — — — — — — — — — 106 Com. Ex. 3 Pd/SiO.sub.2 1173 0.6 — — — — — — — — — — 106 BDO: 1,4-butanediol, GBL: γ-butyrolactone, THF: tetrahydrofuran, BuA: butyric acid, BuOH: 1-butanol, PrA: propionic acid

(32) As shown in Table 1, regarding the Mo—Pd catalyst, the conversion is remarkably improved in Examples 1 to 5 in which the reduction was conducted at higher temperature, as compared with Comparative Example 1 in which the reduction temperature is 473 K. Furthermore, the selectivity of γ-butyrolactone as an intermediate was large and the selectivity of tetrahydrofuran was small. Regarding the Co—Pd catalyst, according to Examples 6 to 10, by reducing at high temperature of 400 K or higher, high conversion rate was obtained, selectivity of γ-butyrolactone was large and the selectivity of tetrahydrofuran was small.

(33) In Examples 1, 9 and 10, 1,4-butanediol is not formed. However, it is considered that in those examples, selectivity of γ-butyrolactone is high and γ-butyrolactone is converted to 1,4-butanediol by prolonging the reaction time of the hydrogenation reaction as is understood from the examples described after. Therefore, it is understood that the catalyst is useful as a catalyst for the production of 1,4-butanediol.

Examples 11 to 16

(34) The hydrogenation reaction of succinic acid was conducted in the same manner as in Example 4, except that in Example 4, Mo—Pd catalyst reduced at 1173 K in a gas phase was used, and the reaction time of the hydrogenation reaction was changed to 12 hours in Example 11, 24 hours in Example 12, 48 hours in Example 13, 72 hours in Example 14, 96 hours in Example 16 and 120 hours in Example 16, as shown in Table 2 below, and each product was analyzed. The results including Example 4 are shown in Table 2.

Examples 17 to 21

(35) The hydrogenation reaction of succinic acid was conducted in the same manner as in Example 7, except that in Example 7, Co—Pd catalyst reduced at 573 K in a gas phase was used, and the reaction time of the hydrogenation reaction was changed to 12 hours in Example 17, 24 hours in Example 18, 48 hours in Example 19, 72 hours in Example 20 and 96 hours in Example 21, as shown in Table 2 below, and each product was analyzed. The results including Example 7 are shown in Table 2.

(36) TABLE-US-00002 TABLE 2 Reaction Conversion Mass Time rate Selectivity (%) Balance Catalyst (h) (%) BDO GBL THF BuA BuOH PrA CO CO.sub.2 CH.sub.4 C.sub.2H.sub.6 (%) Ex. 4 MoO.sub.x—Pd/SiO.sub.2 4 65 3.2 95 1.5 0.1 0.1 0.1 0.0 0.0 0.0 0.0 96 Ex. 11 MoO.sub.x—Pd/SiO.sub.2 12 89 6.7 85 7.4 0.3 0.1 0.0 0.0 0.0 0.1 0.0 100 Ex. 12 MoO.sub.x—Pd/SiO.sub.2 24 >99 46 45 7.7 0.5 0.8 0.0 0.0 0.0 0.0 0.0 94 Ex. 13 MoO.sub.x—Pd/SiO.sub.2 48 >99 55 30 12 0.9 2.0 0.0 0.0 0.0 0.0 0.0 95 Ex. 14 MoO.sub.x—Pd/SiO.sub.2 72 >99 40 19 37 0.8 3.5 0.0 0.0 0.0 0.0 0.1 95 Ex. 15 MoO.sub.x—Pd/SiO.sub.2 96 >99 31 9.0 56 0.2 4.0 0.0 0.0 0.0 0.0 0.0 94 Ex. 16 MoO.sub.x—Pd/SiO.sub.2 120 >99 4.5 0.7 90 0.1 4.6 0.0 0.0 0.0 0.0 0.0 96 Ex. 7 CoO.sub.x—Pd/SiO.sub.2 4 63 0.7 99 0.1 0.0 0.0 0.2 0.0 0.0 0.1 0.0 102 Ex. 17 CoO.sub.x—Pd/SiO.sub.2 12 93 0.9 99 0.2 0.0 0.0 0.3 0.0 0.5 0.0 0.0 100 Ex. 18 CoO.sub.x—Pd/SiO.sub.2 24 >99 66 31 0.7 0.1 1.0 0.0 0.0 0.0 0.5 0.1 95 Ex. 19 CoO.sub.x—Pd/SiO.sub.2 48 >99 75 20 2.3 0.1 1.3 0.0 0.0 0.0 0.4 6.1 97 Ex. 20 CoO.sub.x—Pd/SiO.sub.2 72 98 86 7.1 3.6 0.2 2.8 0.5 0.0 0.0 0.0 0.0 94 Ex. 21 CoO.sub.x—Pd/SiO.sub.2 96 >99 81 5.5 9.4 0.1 3.2 0.5 0.0 0.0 0.0 0.0 99 BDO: 1,4-butanediol, GBL: γ-butyrolactone, THF: tetrahydrofuran, BuA: butyric acid, BuOH: 1-butanol, PrA: propionic acid

(37) As shown in Table 2, the selectivity of 1,4-butanediol could be increased by prolonging the reaction time of the hydrogenation reaction. As shown in Examples 4 and 11 to 16, in the Mo—Pd catalyst, the conversion could be about 100% by that the reaction time of the hydrogenation reaction was about 20 hours or longer, and additionally, the selectivity of 1,4-butanediol could be remarkably increased by that the reaction time was about 20 to 100 hours, and furthermore, about 20 to 80 tours. As shown in Examples 7 and 17 to 21, in the Co—Pd catalyst, the conversion could be about 100% by that the reaction time of the hydrogenation reaction was about 20 hours or longer, and additionally, the selectivity of 1,4-butanediol could be remarkably increased. Furthermore, in the Co—Pd catalyst, the hydrogenation of from γ-butyrolactone to 1,4-butanediol is accelerated and dehydration of from 1,4-butanediol to tetrahydrofuran is slow. Therefore, the yield of 1,4-butanediol is increased by prolonging the reaction time, and the maximum yield was higher than the case of the Mo—Pd catalyst.

Examples 22 to 26

(38) In Example 22, the hydrogenation reaction of succinic acid was conducted in the same manner as in Example 7, except that in Example 7, Co—Pd catalyst (Co/Pd (molar ratio)=20) reduced at 573 K in a gas phase was used and the reaction time of the hydrogenation reaction was changed to 2 hours, and the product, was analyzed. In Examples 23 to 26, gas phase reduction was conducted at 573 K for 1 hour in the same manner as in Example 7 using the Co—Pd catalyst (Co/Pd (molar ratio)=8, 12, 16 and 32) obtained in Production Example 5. Thereafter, the hydrogenation reaction was conducted for 2 hours in the same manner as in Example 22, and the products obtained were analyzed. The results are shown in Table 3.

(39) TABLE-US-00003 TABLE 3 Conversion Mass rate Selectivity (%) Balance Catalyst Co/Pd (%) BDO GBL THF BuA BuOH PrA CO CO.sub.2 CH.sub.4 C.sub.2H.sub.6 (%) Ex. 23 CoO.sub.x—Pd/SiO.sub.2 8 24 0.9 99 0.2 0.0 0.1 0.3 0.1 0.0 0.0 0.0 101 Ex. 24 CoO.sub.x—Pd/SiO.sub.2 12 35 0.0 99 0.2 0.0 0.1 0.3 0.0 0.0 0.0 0.0 99 Ex. 25 CoO.sub.x—Pd/SiO.sub.2 16 36 0.1 99 0.1 0.0 0.1 0.2 0.0 0.1 0.1 0.0 99 Ex. 22 CoO.sub.x—Pd/SiO.sub.2 20 39 0.1 99 0.3 0.2 0.0 0.3 0.0 0.0 0.1 0.1 101 Ex. 26 CoO.sub.x—Pd/SiO.sub.2 32 46 0.4 99 0.1 0.0 0.1 0.2 0.0 0.0 0.1 0.0 99 BDO: 1,4-butanediol, GBL: γ-butyrolactone, THF: tetrahydrofuran, BuA: butyric acid, BuOH: 1-butanol, PrA: propionic acid

(40) As shown in Table 3, in the Co—Pd catalyst, the activity in succinic acid hydrogenation and the yield of 1,4-butanediol were improved in association with the increase of the amount of Co supported, in a range of Co/Pd molar ratio of 8 to 32, and the activity was maximum in Co/Pd=32. In Examples 22 to 26, the amount of 1,4-butanediol formed is small, but the selectivity of γ-butyrolactone is high, and it is considered that γ-butyrolactone is converted to 1,4-butanediol by prolonging the reaction time of the hydrogenation reaction. Therefore, it is understood that the catalysts are useful as a catalyst for production of 1,4-butanediol.

(41) Although some embodiments of the present invention have been described above, those embodiments are exemplified as an example, and do not intend to limit the scope of the present invention. Those embodiments can be carried out in other various forms, and various omissions, replacements and changes can be made without departing the gist of the present, invention. Those embodiments and their omissions, replacements and changes are included in the scope and gist of the present invention and also in the invention described in the claim and its equivalent scope.