CATALYST FOR PREPARING 1,3-CYCLOPENTANEDIOL, METHOD FOR PREPARING 1,3-CYCLOPENTANEDIOL BY USING SAME, AND 1,3-CYCLOPENTANEDIOL PREPARED THEREBY

Abstract

Provided is a catalyst for preparing 1,3-cyclopentanediol by hydrogenation of 4-hydroxy-2-cyclopentenone, the catalyst including: a carrier including -Al.sub.2O.sub.3; and an active metal supported on the carrier.

Claims

1. A catalyst for preparing 1,3-cyclopentanediol by hydrogenation of 4-hydroxy-2-cyclopentenone, comprising a carrier including -Al.sub.2O.sub.3, and an active metal supported on the carrier.

2. The catalyst of claim 1, wherein the -Al.sub.2O.sub.3 has an acid point of 10 mmol/g or less when measured using an ammonia desorption method.

3. The catalyst of claim 1, wherein the -Al.sub.2O.sub.3 has a specific surface area (BET) of 0.1 m.sup.2/g to 50.0 m.sup.2/g, a pore volume of 0.10 ml/g to 0.85 ml/g, and a lateral crushing strength of 20 N/particle to 200 N/particle.

4. The catalyst of claim 1, wherein the carrier is the -Al.sub.2O.sub.3, and the carrier includes crystalline silica alumina, amorphous silica, amorphous silica alumina, or a combination thereof.

5. The catalyst of claim 4, wherein the carrier includes, based on a total weight of the carrier, 65 wt % to 99.9 wt % of -Al.sub.2O.sub.3, and 0.1 wt % to 35 wt % of crystalline silica alumina, amorphous silica, amorphous silica alumina, or a combination thereof.

6. The catalyst of claim 1, wherein the active metal includes Pt, Pd, Ru, Ir, Ni, Co, Cu, or a combination thereof.

7. The catalyst of claim 1, wherein the catalyst includes 0.1 wt % to 10 wt % of the active metal based on a total weight of the catalyst.

8. A method for preparing 1,3-cyclopentanediol, comprising preparing 1,3-cyclopentanediol by hydrogenating 4-hydroxy-2-cyclopentenone in the presence of a catalyst, wherein the catalyst includes a carrier including -Al.sub.2O.sub.3, and an active metal supported on a carrier.

9. The method of claim 8, wherein the preparing of the 1,3-cyclopentanediol is performed by adding a catalyst to a solution of 4-hydroxy-2-cyclopentenone in an organic solvent.

10. The method of claim 9, wherein the 4-hydroxy-2-cyclopentenone is included in an amount of 0.01 wt % to 50 wt % based on a total weight of the solution.

11. The method of claim 9, wherein the organic solvent includes 2-methyltetrahydrofuran, methanol, acetone, or a combination thereof.

12. The method of claim 8, wherein in the preparing of 1,3-cyclopentanediol, 0.05 to 0.3 parts by weight of catalyst is added based on 100 parts by weight of 4-hydroxy-2-cyclopentenone.

13. The method of claim 8, wherein the preparing of 1,3-cyclopentanediol is performed under a hydrogen atmosphere, a temperature of 70 C. to 200 C., and a pressure of 10 bar to 70 bar.

14. The method of claim 8, wherein the preparing of 1,3-cyclopentanediol is performed for 10 minutes to 2 hours.

15. The method of claim 8, wherein the method for preparing 1,3-cyclopentanediol further includes preparing 4-hydroxy-2-cyclopentenone by adding a catalyst to an aqueous solution of furfuryl alcohol before the preparing of 1,3-cyclopentanediol.

16. The method of claim 15, wherein the furfuryl alcohol is a biomass derived compound.

17. The method of claim 15, wherein the catalyst includes calcium oxide, lead oxide, aluminum oxide, iron oxide, calcium chloride, zinc acetate, paratoluene sulfonic acid, stannous chloride, stannous sulfate, stannous oxide, stannic oxide, stannous octylate, tetraphenyl tin, a tin powder, titanium tetrachloride, or a combination thereof.

18. The method of claim 15, wherein in the preparing of 4-hydroxy-2-cyclopentenone, 0.1 to 10 parts by weight of catalyst is added based on 100 parts by weight of furfuryl alcohol.

19. 1,3-Cyclopentanediol prepared by the method of claim 8.

20. The 1,3-cyclopentanediol of claim 19, wherein the 1,3-cyclopentanediol includes 1 wt % or less of by-products including cyclopentanone, cyclopentanol, 1,3-cyclopentanediol, or a combination thereof.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0082] Hereinafter, specific examples of the invention are presented. However, the examples described below are only intended to specifically illustrate or describe the invention, and this should not limit the scope of the invention.

Preparation Example: Preparation of 1,3-Cyclopentanediol

Example 1

[0083] An aqueous solution was prepared by dissolving 14 g of furfuryl alcohol, a derivative of furfural extracted from biomass, in 685.97 ml of water. To the aqueous solution, 0.028 g of a calcium oxide catalyst was added and then, stirred at 200 C. for 0.5 hour to prepare 4-hydroxy-2-cyclopentenone.

[0084] A catalyst (Ru/-Al.sub.2O.sub.3) having 5 wt % of a Ru content and supported on -Al.sub.2O.sub.3 was prepared. Herein, the -Al.sub.2O.sub.3 had an acid point of 0.001 mmol/g, a BET surface area of 7.2 m.sup.2/g, and a pore volume of 0.44 cm.sup.3/g. The -Al.sub.2O.sub.3 used to prepare the catalyst was a product No. SA52238 manufactured by Saint-Gobain (France).

[0085] 0.25 g of the catalyst was added to 4-hydroxy-2-cyclopentenone (a concentration: 10 wt %, a solvent: ethanol), and 50 bar of hydrogen was charged in a batch reactor. Herein, a reaction was performed at 120 C. for 1 hour. After completing the reaction, 1,3-cyclopentanediol was obtained.

Example 2

[0086] An aqueous solution was prepared by dissolving 14 g of furfuryl alcohol, a derivative of furfural extracted from biomass, in 685.97 ml of water. To the aqueous solution, 0.028 g of a calcium oxide catalyst was added and then, stirred at 200 C. for 0.5 hour to prepare 4-hydroxy-2-cyclopentenone.

[0087] A catalyst (Ru/-Al.sub.2O.sub.3) having 5 wt % of a Ru content and supported on -Al.sub.2O.sub.3 was prepared. Herein, the -Al.sub.2O.sub.3 had an acid point of 0.001 mmol/g, a BET surface area of 7.2 m.sup.2/g, and a pore volume of 0.44 cm.sup.3/g. The -Al.sub.2O.sub.3 used to prepare the catalyst was a product No. SA52238 manufactured by Saint-Gobain (France).

[0088] 0.25 g of the catalyst was added to 4-hydroxy-2-cyclopentenone (a concentration: 10 wt %, a solvent: ethanol), and 50 bar of hydrogen was charged in a batch reactor. Herein, a reaction was performed at 120 C. for 1 hour. After completing the reaction, 1,3-cyclopentanediol was obtained.

Example 3

[0089] An aqueous solution was prepared by dissolving 14 g of furfuryl alcohol, a derivative of furfural extracted from biomass, in 685.97 mL of water. To the aqueous solution, 0.028 g of a calcium oxide catalyst was added and then, stirred at 200 C. for 0.5 hour to prepare 4-hydroxy-2-cyclopentenone.

[0090] A catalyst (Ru/-Al.sub.2O.sub.3) having 5 wt % of a Ru content and supported on -Al.sub.2O.sub.3 was prepared. Herein, the -Al.sub.2O.sub.3 had an acid point of 0.001 mmol/g, a BET surface area of 7.2 m.sup.2/g, and a pore volume of 0.44 cm.sup.3/g. The -Al.sub.2O.sub.3 used to prepare the catalyst was a product No. SA52238 manufactured by Saint-Gobain (France).

[0091] 0.25 g of the catalyst was added to 4-hydroxy-2-cyclopentenone (a concentration: 10 wt %, a solvent: ethanol), and 50 bar of hydrogen was charged in a batch reactor. Herein, a reaction was performed at 120 C. for 1 hour. After completing the reaction, 1,3-cyclopentanediol was obtained.

Comparative Example 1

[0092] An aqueous solution was prepared by dissolving 14 g of furfuryl alcohol, a derivative of furfural extracted from biomass, in 685.97 ml of water. To the aqueous solution, 0.028 g of a calcium oxide catalyst was added and then, stirred at 200 C. for 0.5 hour to prepare 4-hydroxy-2-cyclopentenone.

[0093] A catalyst (Ru/C) having 5 wt % of a Ru content and supported on activated carbon was prepared.

[0094] 0.25 g of the catalyst was added to 4-hydroxy-2-cyclopentenone (a concentration: 10 wt %, a solvent: ethanol), and 50 bar of hydrogen was charged in a batch reactor. Herein, a reaction was performed at 120 C. for 1 hour. After completing the reaction, 1,3-cyclopentanediol was obtained.

Comparative Example 2

[0095] An aqueous solution was prepared by dissolving 14 g of furfuryl alcohol, a derivative of furfural extracted from biomass, in 685.97 ml of water. To the aqueous solution, 0.028 g of a calcium oxide catalyst was added and then, stirred at 200 C. for 0.5 hour to prepare 4-hydroxy-2-cyclopentenone.

[0096] A catalyst (Ru/-Al.sub.2O.sub.3) having 5 wt % of a Ru content and supported on -Al.sub.2O.sub.3 was prepared. Herein, the -Al.sub.2O.sub.3 had an acid point of 0.8 mmol/g, a BET surface area of 187 m.sup.2/g, and a pore volume of 0.43 cm.sup.3/g. The -Al.sub.2O.sub.3 used to prepare the catalyst was a product manufactured by Sasol (Germany).

[0097] 0.25 g of the catalyst was added to 4-hydroxy-2-cyclopentenone (a concentration: 10 wt %, a solvent: ethanol), and 50 bar of hydrogen was charged in a batch reactor. Herein, a reaction was performed at 120 C. for 1 hour. After completing the reaction, 1,3-cyclopentanediol was obtained.

Experimental Example: Conversion Rate and Yield of 1,3-Cyclopentanediol

[0098] The 1,3-cyclopentanediols according to Examples 1 to 3 and Comparative Examples 1 to 2 were measured with respect to a conversion rate and a yield by using GC-FID (Agilent 7890B GC/flame ionization detector (FID)), and the results are shown in Table 1.

[0099] The reaction conditions for GC-FID are as follows.

<Reaction Condition of GC-FID>

[0100] Injector conditions: 250 C., 4 L, Split=20:1 [0101] Column: HP-INNOWAX (30 m0.32 mm0.25 m) [0102] Pressure rate: 2.33 mL/min [0103] Mobile Phase: He, 1 mL/min [0104] Oven temperature (Oven Temp.): From 80 C., 10 C./min to 320 C., hold 5 min [0105] Detector: Flame Ionized Detector [0106] Injection method (Sampling): Direct injection

TABLE-US-00001 TABLE 1 Ru Ru content supported Product yield (%) (wt %) catalyst HCPone.sup.a) CPone.sup.b) CPol.sup.c) CPdiol.sup.d) Comparative 5 Ru/C 0.0 0.0 3.4 96.5 Example 1 Comparative 5 Ru/-Al.sub.2O.sub.3 0.0 0.0 7.2 92.8 Example 2 Example 1 5 Ru/-Al.sub.2O.sub.3 5.1 0.2 1.0 93.7 Example 2 0.5 Ru/-Al.sub.2O.sub.3 27.8 0.0 2.3 69.9 Example 3 1 Ru/-Al.sub.2O.sub.3 0.0 0.0 0.4 99.6 .sup.a)HCPone: Hydroxycyclopentanone .sup.b)CPone: cyclopentanone .sup.c)CPol: cyclopentanol .sup.d)CPdiol: 1,3-cyclopentanediol

[0107] Referring to Table 1, when a catalyst supported on -Al.sub.2O.sub.3 was applied to a hydrogenation reaction, a final product of 1,3-cyclopentanediol (CPdiol) was produced on the catalysts supported by 0.5 wt % to 5 wt % of a Ru metal according to Examples 1 to 3. In Examples 1 to 3, the reactant of 4-hydroxy-2-cyclopentenone (HCPenone) was 100% converted.

[0108] Comparing Example 3 with Comparative Example 1, even though Ru was included in a small content of 1%, 1,3-cyclopentanediol (CPdiol) was obtained at a yield of 99.6%. Accordingly, the Ru/-Al.sub.2O.sub.3 catalyst may be advantageously used in the process by replacing a Ru catalyst supported on a carbon carrier.

[0109] While this invention has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

INDUSTRIAL APPLICABILITY

[0110] The present invention relates to a catalyst for preparing 1,3-cyclopentanediol, which is used to hydrogenate 4-hydroxy-2-cyclopentenone to prepare 1,3-cyclopentanediol.