Catalyst for preparing 2,5-furancarboxylic acid and a method for preparing 2,5-furancarboxylic acid using the catalyst

Abstract

The present invention relates to a carboxylation catalyst, which catalyzes carboxylation of a furan-based compound containing a hydroxyl group and a carbonyl group or a derivative thereof to prepare 2,5-furandicarboxylic acid (FDCA), and is configured as a spinel support, and noble metal nanoparticles incorporated into the spinel support selected from the group consisting of MnCo.sub.2O.sub.4, CoMn.sub.2O.sub.4, and combinations thereof, and to a method of preparing 2,5-furandicarboxylic acid (FDCA), including providing a carboxylation catalyst configured such that noble metal nanoparticles are incorporated into a spinel support; and carboxylating a furan-based compound containing a hydroxyl group and a carbonyl group or a derivative thereof in the presence of the carboxylation catalyst.

Claims

1. A carboxylation catalyst which catalyzes carboxylation of a furan-based compound containing a hydroxyl group and a carbonyl group or a derivative thereof to prepare 2,5-furandicarboxylic acid (FDCA), comprising: a spinel support selected from the group consisting of MnCo.sub.2O.sub.4, CoMn.sub.2O.sub.4, and combinations thereof; and noble metal nanoparticles incorporated into the spinel support.

2. The carboxylation catalyst of claim 1, wherein the spinel support has an average particle size (D.sub.50) of 2.0 to 4.0 m.

3. The carboxylation catalyst of claim 1, wherein the noble metal is selected from the group consisting of platinum, palladium, ruthenium, and combinations thereof.

4. The carboxylation catalyst of claim 3, wherein the noble metal is ruthenium.

5. The carboxylation catalyst of claim 1, wherein the furan-based compound is 5-hydroxymethylfurfural (HMF).

6. The carboxylation catalyst of claim 1, wherein the derivative of the furan-based compound is 5-acetoxymethyl-2-furfural (AMF).

7. The carboxylation catalyst of claim 1, wherein the noble metal nanoparticles are used in an amount of 0.1 to 10 wt % based on total weight of the catalyst.

8. A method of preparing 2,5-furandicarboxylic acid (FDCA), comprising: providing a carboxylation catalyst configured such that noble metal nanoparticles are incorporated into a spinel support selected from the group consisting of MnCo.sub.2O.sub.4, CoMn.sub.2O.sub.4, and combinations thereof; and carboxylating a furan-based compound containing a hydroxyl group and a carbonyl group or a derivative thereof using the carboxylation catalyst.

9. The method of claim 8, wherein the furan-based compound is 5-hydroxymethylfurfural (HMF).

10. The method of claim 8, wherein the derivative of the furan-based compound is 5-acetoxymethyl-2-furfural (AMF).

11. The method of claim 8, wherein the noble metal nanoparticles are selected from the group consisting of platinum, palladium, ruthenium, and combinations thereof.

12. The method of claim 8, wherein oxidation of the furan-based compound is carried out under conditions of a temperature of 100 to 200 C., an air pressure of 80 to 1000 psi, and a reaction time of 3 to 12 hr.

13. The method of claim 8, wherein a molar ratio of the noble metal nanoparticles to the furan-based compound is 1:5-200.

14. The method of claim 8, wherein oxidation of the furan-based compound is carried out in a single vessel using water as a solvent under base-free conditions.

15. The method of claim 9, wherein the 5-hydroxymethylfurfural (HMF) is obtained from biomass containing cellulose or polysaccharides.

16. The method of claim 8, wherein the noble metal nanoparticles are used in an amount of 0.1 to 10 wt % based on a total weight of the catalyst.

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1 is an SEM image showing a spinel support according to an embodiment of the present invention;

(2) FIG. 2 is an SEM image showing microspheres of a spinel-type MnCo.sub.2O.sub.4 support according to an embodiment of the present invention;

(3) FIG. 3 is an SEM image showing a plurality of pores in the spinel-type MnCo.sub.2O.sub.4 support according to an embodiment of the present invention;

(4) FIG. 4 shows the results of energy-dispersive X-ray (EDX/EDS) spectrometry performed on a catalyst configured such that Ru nanoparticles are incorporated into a spinel-type MnCo.sub.2O.sub.4 support according to an embodiment of the present invention;

(5) FIG. 5 shows the results of X-ray photoelectron spectroscopy (XPS) performed on the catalyst configured such that Ru nanoparticles are incorporated into a spinel-type MnCo.sub.2O.sub.4 support according to an embodiment of the present invention; and

(6) FIG. 6 shows the results of HPLC of a solid obtained after the preparation of FDCA using the catalyst of Example 1 according to the present invention.

MODE FOR INVENTION

(7) An embodiment of the present invention pertains to a catalyst for preparing 2,5-furandicarboxylic acid (FDCA), which is a catalyst for carboxylation of a furan-based compound containing a hydroxyl group and a carbonyl group or a derivative thereof and is configured such that noble metal nanoparticles are incorporated into a spinel-type support.

(8) Here, the spinel-type support may be at least one selected from the group consisting of MnCo.sub.2O.sub.4, CoMn.sub.2O.sub.4, ZnAl.sub.2O.sub.4, FeAl.sub.2O.sub.4, CuFe.sub.2O.sub.4, ZnMn.sub.2O.sub.4, MnFe.sub.2O.sub.4, Fe.sub.3O.sub.4, TiFe.sub.2O.sub.4, ZnFe.sub.2O.sub.4, Mg.sub.2SiO.sub.4, and Fe.sub.2SiO.sub.4, and in an embodiment of the present invention, the spinel-type support may be MnCo.sub.2O.sub.4 or CoMn.sub.2O.sub.4.

(9) As shown in FIG. 1, representing the results of SEM of MnCo.sub.2O.sub.4, the MnCo.sub.2O.sub.4 or CoMn.sub.2O.sub.4 support has a spinel structure with an average particle size (D.sub.50) of 2.0 to 4.0 m, the structure being configured such that a plurality of microspheres ranging from 30 to 60 nm in size is aggregated, as shown in FIG. 2.

(10) As shown in the dotted line of FIG. 3, the MnCo.sub.2O.sub.4 support may contain therein a plurality of pores, and the noble metal nanoparticles may be incorporated into the support.

(11) In an embodiment of the present invention, the MnCo.sub.2O.sub.4 or CoMn.sub.2O.sub.4 support has the specific structure and size shown in FIGS. 1 to 3, and thus, when noble metal nanoparticles are reduced and thus incorporated into the support, an efficient configuration in which the nanoparticles are uniformly distributed in the support may result.

(12) The noble metal may be at least one selected from the group consisting of platinum, palladium, and ruthenium, and in an embodiment of the present invention, the noble metal may be ruthenium.

(13) In particular, the noble metal nanoparticles may have a particle size of 5 to 15 nm, and the noble metal nanoparticles having a size of 5 to 15 nm may be efficiently incorporated into the spinel-type support. Furthermore, the noble metal particles are uniformly dispersed in the structure of the spinel support in which a plurality of microspheres is aggregated, thereby inducing stable oxidation of the furan-based compound.

(14) Also, the noble metal nanoparticles may be used in an amount of 0.1 to 10 wt % based on the total weight of the catalyst including the support and the noble metal nanoparticles. If the amount of the noble metal nanoparticles is less than 0.1 wt %, the yield of 2,5-furandicarboxylic acid (FDCA) may decrease. On the other hand, if the amount thereof exceeds 10 wt %, the furan-based compound may be drastically oxidized and thus processing stability may become problematic, and excessive use of noble metal particles may increase the price of the catalyst, thus negating economic benefits.

(15) The method of preparing the spinel-type support is not particularly limited, and typical methods known in the art may be used. Also, the method of loading the noble metal nanoparticles into the spinel-type support is not particularly limited, but according to an embodiment of the present invention, the spinel-type support is impregnated with a noble metal salt hydrate in an aqueous solution phase, followed by reducing treatment, whereby the reduced noble metal is incorporated into the support.

(16) When the catalyst according to an embodiment of the present invention is used, efficient oxidation from HMF into FDCA may occur upon preparation of FDCA, and the preparation process may be performed at low temperature and low air pressure under base-free conditions without the use of an additional base material, unlike conventional techniques.

(17) Another aspect of the present invention pertains to a method of preparing 2,5-furandicarboxylic acid (FDCA), comprising carboxylating a furan-based compound containing a hydroxyl group and a carbonyl group or a derivative thereof in the presence of a catalyst configured such that noble metal nanoparticles are incorporated into a spinel-type support.

(18) The spinel-type support may be at least one selected from the group consisting of MnCo.sub.2O.sub.4, CoMn.sub.2O.sub.4, ZnAl.sub.2O.sub.4, FeAl.sub.2O.sub.4, CuFe.sub.2O.sub.4, ZnMn.sub.2O.sub.4, MnFe.sub.2O.sub.4, Fe.sub.3O.sub.4, TiFe.sub.2O.sub.4, ZnFe.sub.2O.sub.4, Mg.sub.2SiO.sub.4, and Fe.sub.2SiO.sub.4, and in an embodiment of the present invention, the spinel-type support may be MnCo.sub.2O.sub.4 or CoMn.sub.2O.sub.4.

(19) Here, the furan-based compound containing a hydroxyl group and a carbonyl group may be 5-hydroxymethylfurfural (HMF).

(20) In the present invention, the furan-based compound, particularly HMF, may be obtained through dehydration of sugar, especially hexose, for example, fructose and glucose, and the sugar may be obtained through hydrolysis of biomass containing cellulose or polysaccharides and possibly from glucose and fructose (high-sugar-content syrup) resulting from isomerization of glucose. Briefly, the furan-based compound used in the present invention may be regarded as being obtained from biomass containing cellulose or polysaccharides. The biomass containing cellulose or polysaccharides is an example of widely available natural materials, and is a renewable material for HMF.

(21) In another embodiment of the present invention, useful as a substrate for producing FDCA, a derivative of a furan-based compound containing a hydroxyl group and a carbonyl group may include a furan-based compound containing an acyloxy group and a carbonyl group. Specific examples thereof may include acetoxymethylfurfural (AMF), in which the hydroxyl group of HMF is substituted with an acetyloxy group.

(22) In the method of preparing FDCA according to the present invention, minimizing the yields of DFF and FFCA and maximizing the yield of FDCA were realized depending on changes in the catalyst, solvent, and pressure and temperature conditions.

(23) The noble metal nanoparticles may be at least one selected from the group consisting of platinum, palladium, and ruthenium. In the catalyst configured such that noble metal nanoparticles are incorporated into the spinel-type support, the molar ratio of the noble metal nanoparticles to the furan-based compound preferably falls in the range of 1:5-200, and more preferably 1:10-150, in order to realize efficient processing while maximizing the conversion of HMF and the yield of FDCA by optimizing the proportion of the noble metal.

(24) The oxidation of the furan-based compound is preferably carried out under conditions of an air pressure of 80 to 1000 psi in the reactor, a reaction temperature of 100 to 200 C. and a reaction time of 3 to 12 hr, and more preferably an air pressure of 100 to 500 psi, a reaction temperature of 120 to 150 C., and a reaction time of 5 to 10 hr. If the air pressure is less than 80 psi, the yield of FDCA and the amount of the final product are low. On the other hand, if the air pressure exceeds 1000 psi, the yield of FDCA is not significantly increased, but production and processing costs and processing simplicity under the low air pressure conditions desired in the present invention may become unfavorable due to excessively high pressure, and furthermore, byproducts may be generated in large amounts due to excessive air supply. If the reaction time is less than 3 hr, the yield of FDCA is low. On the other hand, if the reaction time exceeds 12 hr, the yield of byproducts and processing costs may increase. Also, if the reaction temperature is lower than 100 C., the yield of FDCA is low. On the other hand, if the reaction temperature is higher than 200 C., the process cannot be efficiently conducted in the low temperature range desired in the present invention.

(25) For example, various compounds may be produced depending on the extent of oxidation of HMF, as represented in Scheme 1 below.

(26) ##STR00001##

(27) In the preparation of FDCA from HMF using the catalyst according to an embodiment of the present invention, HMFCA, FFCA, DFF, and the like are regarded as byproducts because the extent of oxidation thereof is different from that of the finally obtained FDCA. Also, the produced HMFCA has very low solubility in the solvent and may thus have an adverse influence on the final yield of FDCA, which is a compound desired in the present invention. Hence, according to an embodiment of the present invention, water may be used as the solvent upon preparation of FDCA. When water is used as the solvent in this way, the generation of byproducts may be minimized, and the selectivity of FDCA may increase. Moreover, in an embodiment of the present invention, a base-free oxidation process may be carried out under mild conditions, without the use of a base material, for example, NaOH or Na.sub.2CO.sub.3, which is conventionally contained in the solvent to oxidize FDCA.

(28) Also, the reaction may be carried out in a single vessel.

(29) A better understanding of the present invention will be given through the following examples, which are set forth to more specifically describe the present invention but are not to be construed as limiting the scope of the present invention.

(30) Preparation of Spinel-Type MnCo.sub.2O.sub.4 Support

(31) As commercially available materials, 65.3 mmol of (CH.sub.3COO).sub.2Co.4H.sub.2O and 32.6 mmol of (CH.sub.3COO).sub.2Mn.4H.sub.2O (a molar ratio of Co:Mn=2:1) were dissolved in 400 mL of water and stirred for 30 min to thus homogenize the mixture.

(32) Separately, 50 g of ammonium sulfate was dissolved in 400 mL of water. The resulting solution was slowly stirred and mixed for 4 hr. The sufficiently dissolved aqueous solution of NH.sub.4HCO.sub.3 was then slowly mixed with the above solution, followed by stirring for 6 hr. Thereafter, the precipitate having a pale pink color was obtained through filtration, and was then washed with distilled water and anhydrous ethanol, followed by drying at 60 C. for 12 hr. The obtained carbonate precursor was thermally treated in a furnace at 425 C. (2 C./min) for 12 hr while air was supplied thereto, and was then slowly cooled to room temperature and maintained for 8 hr, thus yielding a spinel-type MnCo.sub.2O.sub.4 support.

(33) Preparation of Catalyst Configured Such that Ruthenium Noble Metal Nanoparticles were Incorporated into Spinel-Type MnCo.sub.2O.sub.4 Support

(34) 5 g of the spinel-type MnCo.sub.2O.sub.4 support thus prepared and 0.432 g of RuCl.sub.3.3H.sub.2O, corresponding to 4.0 wt % of Ru based on the total amount of the catalyst, were placed in a two-neck round-bottom flask (100 mL) containing about 20 mL of water in a cooling bath. The mixture was stirred for 12 hr in an N.sub.2 atmosphere. Thereafter, a NaBH.sub.4 aqueous solution was added dropwise in the flask in an amount at least 10 times as large as the amount of RuCl.sub.3.3H.sub.2O with stirring, after which stirring was performed at 500 rpm for one day at room temperature in an N.sub.2 atmosphere so that the reaction was thoroughly carried out. Through the reaction, Ru( ) was reduced into Ru(0), thus forming nanoparticles. The catalyst thus obtained was filtered, separated and washed with ethanol. By performing the above procedures, the resulting catalyst was configured such that ruthenium noble metal nanoparticles were incorporated into the dried spinel-type MnCo.sub.2O.sub.4 support having a dark black color. In order to analyze the catalyst, energy-dispersive X-ray (EDX/EDS) spectrometry and Quantax 200 zero measurement were performed. The results are shown in FIG. 4. As shown in FIG. 4, the ruthenium noble metal can be confirmed to be incorporated into the spinel-type MnCo.sub.2O.sub.4 support.

(35) Moreover, as shown in FIG. 5, the catalyst was analyzed through X-ray photoelectron spectroscopy (XPS). In FIG. 5(a), Co, Mn, O and Ru were confirmed to be present, and in FIG. 5(d), O atoms were confirmed to be present within spinel lattices based on a 1s spectrum of O. In FIG. 5(f), the maximum peak of 3P.sub.3/2 of Ru was present in 455 to 480 eV, corresponding to the 3d region of Ru, from which Ru was confirmed to be metal particles.

(36) Also, through HR TEM of the catalyst, the average diameter of Ru nanometal was determined to be 5 nm.

(37) Oxidation from HMF into FDCA (Examples 1 to 4 and Comparative Examples 1 to 9)

Example 1

(38) A 100 mL stainless steel high-pressure reactor was provided with a magnetic stirrer and an electric heater. 5-hydroxymethylfurfural (HMF) (0.2513 g, 2.0 mmol) and 20 mL of a water solvent were placed therein, and the catalyst was added thereto, as shown in Table 1 below, after which mixing was performed at room temperature for at least 5 min with stirring at 100 rpm. While air was continuously supplied into the reactor, the temperature and pressure of the reactor were maintained at 120 C. and 150 psi, after which the final air pressure in the reactor was set to 350 psi with stirring at 600 rpm and the reaction was carried out at 120 C. for 10 hr. The pressure was adjusted using a back-pressure regulator connected to a reservoir tank so that the pressure in the reactor was maintained constant during the reaction. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered, thus separating the solid product. The solid product thus separated was completely dried in a vacuum oven. The weight of FDCA produced after drying was measured, a portion thereof was dissolved in water containing H.sub.2SO.sub.4 (0.0005 M), and analysis was performed through HPLC (Agilent Technologies 1200 series, Bio-Rad Aminex HPX-87 H pre-packed column, and UV-detector), whereby the HMF conversion (C), FDCA yield (Y), and selectivity (S) of FDCA, FFCA and DFF were calculated using the following Equations (selectivity (S) of FFCA and DFF was calculated by being replaced with the yield of FFCA and DFF in the following Equation 3). The results of HPLC of Example 1 are shown in FIG. 6, and the calculated results are given in Table 1 below.

(39) $\begin{array}{cc}\mathrm{HMF}\mathrm{Conversion}\left(\%\right)=\frac{\mathrm{mol}\mathrm{of}\mathrm{reacted}\mathrm{HMF}}{\mathrm{mol}\mathrm{of}\mathrm{added}\mathrm{HMF}}100& \left[\mathrm{Equation}1\right]\\ \mathrm{FDCA}\mathrm{Yield}\left(\%\right)=\frac{\mathrm{actual}\mathrm{mol}\mathrm{of}\mathrm{produced}\mathrm{FDCA}}{\mathrm{theoretical}\mathrm{mol}\mathrm{of}\mathrm{produced}\mathrm{FDCA}}100& \left[\mathrm{Equation}2\right]\\ \mathrm{FDCA}\mathrm{Selectivity}\left(\%\right)=\frac{\mathrm{FDCA}\mathrm{yield}}{\mathrm{HMF}\mathrm{conversion}}100& \left[\mathrm{Equation}3\right]\end{array}$

Examples 2 to 4

(40) The procedures were performed under the same conditions as in Example 1, with the exception that the amount of the catalyst, the reaction temperature and the reaction time were differently set. The results are shown in Table 1 below. FDCA was prepared at high yield even under acidic conditions of pH 3 to 4 in the vessel after initiation of the reaction in Examples 1 to 4.

(41) TABLE-US-00001 TABLE 1 HMF/metal HMF molar Catalyst Temp. Time (mmol) ratio [metal (wt %)/support] C. (hr) C.sub.HMF, % Y.sub.FDCA, % S.sub.FDCA, % S.sub.FFCA, % S.sub.DFF, % Example 1 1.0 10 4.0% Ru/MnCo.sub.2O.sub.4 120 10 99.9 92.6 92.6 0.0 0.0 Example 2 1.0 25 1.8% Ru/MnCo.sub.2O.sub.4 120 10 99.0 87.9 88.8 4.7 0.0 Example 3 2.0 85 1.8% Ru/MnCo.sub.2O.sub.4 150 8 99.9 81.9 82.0 3.3 0.0 Example 4 2.0 150 1.8% Ru/MnCo.sub.2O.sub.4 150 5 100 43.7 43.7 29.8 0.5

Examples 5 to 8

(42) The procedures were performed under the same conditions as in Example 1 (temperature: 120 C., reaction time: 10 hr), with the exception that the HMF/metal molar ratio was differently set. The results are shown in Table 2 below.

(43) TABLE-US-00002 TABLE 2 HMF/metal HMF molar Catalyst (mmol) ratio [metal (wt %)/support] C.sub.HMF, % Y.sub.FDCA, % S.sub.FDCA, % S.sub.FFCA, % S.sub.DFF, % Example 5 2.0 10 4.0% Ru/MnCo.sub.2O.sub.4 100 96.9 96.9 0.0 0.0 Example 6 2.0 33.6 4.0% Ru/MnCo.sub.2O.sub.4 100 97.4 97.4 2.3 0.0 Example 7 2.0 50 4.0% Ru/MnCo.sub.2O.sub.4 100 70.1 70.1 15.0 0.0 Example 8 2.0 70 4.0% Ru/MnCo.sub.2O.sub.4 100 55.9 55.9 39.0 0.1

Examples 9 to 11

(44) The procedures were performed under the same conditions as in Example 6 (temperature: 120 C., reaction time: 10 hr), with the exception that the air pressure was differently set. The results are shown in Table 3 below.

(45) TABLE-US-00003 TABLE 3 HMF/metal HMF molar Catalyst Pressure (mmol) ratio [metal (wt %)/support] psi C.sub.HMF, % Y.sub.FDCA, % S.sub.FDCA, % S.sub.FFCA, % Example 9 2.0 33.6 4.0% Ru/MnCo.sub.2O.sub.4 150 100 67.3 67.3 21.7 Example 2.0 33.6 4.0% Ru/MnCo.sub.2O.sub.4 250 100 86.9 86.9 4.3 10 Example 6 2.0 33.6 4.0% Ru/MnCo.sub.2O.sub.4 350 100 97.4 97.4 2.3 Example 2.0 33.6 4.0% Ru/MnCo.sub.2O.sub.4 450 100 98.7 98.7 0.0 11

Examples 12 to 14

(46) The procedures were performed under the same conditions as in Example 6 (temperature: 120 C., reaction time: 10 hr, pressure: 350 psi), with the exception that the wt % of Ru nanometal based on the total weight of the catalyst of the invention was differently set. The results are shown in Table 4 below.

(47) TABLE-US-00004 TABLE 4 HMF Catalyst (mmol) [metal (wt %)/support] C.sub.HMF, % Y.sub.FDCA, % S.sub.FDCA, % S.sub.FFCA, % S.sub.DFF, % Example 2.0 1.0% Ru/MnCo.sub.2O.sub.4 87.4 17.8 20.4 54.2 13.4 12 Example 2.0 2.0% Ru/MnCo.sub.2O.sub.4 90.8 60.1 66.2 3.3 1.2 13 Example 6 2.0 4.0% Ru/MnCo.sub.2O.sub.4 100 97.4 97.4 2.3 0.0 Example 2.0 10.0% Ru/MnCo.sub.2O.sub.4 100 98.4 98.4 0.0 0.0 14

Example 15

(48) A spinel-type support, in which the molar ratio of Co:Mn was 1:2, was prepared using (CH.sub.3COO).sub.2Co.4H.sub.2O and (CH.sub.3COO).sub.2Mn.4H.sub.2O at a molar ratio of 1:2, and 4 wt % of Ru nanometal was incorporated into the support, after which the procedures were performed in the same manner as in Example 6 (temperature: 120 C., reaction time: 10 hr, pressure: 350 psi). The results are shown in Table 5 below.

(49) TABLE-US-00005 TABLE 5 HMF/metal HMF molar Catalyst (mmol) ratio [metal (wt %)/support] C.sub.HMF, % Y.sub.FDCA, % S.sub.FDCA, % S.sub.FFCA, % S.sub.DFF, % Example 6 2.0 33.6 4.0% Ru/MnCo.sub.2O.sub.4 100 97.4 97.4 2.3 0.0 Example 2.0 33.6 4.0% Ru/CoMn.sub.2O.sub.4 98.8 70.1 70.9 27.3 0.0 15

Example 16

(50) The procedures were performed under the same conditions as in Example 6, with the exception that AMF (5-acetoxymethyl-2-furfural) was used as the substrate in lieu of HMF. The results are shown in Table 6 below. FDCA was produced at high yield even when AMF was used as the substrate.

(51) TABLE-US-00006 TABLE 6 Substrate HMF/metal Catalyst (mmol) molar ratio [metal (wt %)/support] C.sub.HMF, % Y.sub.FDCA, % S.sub.FDCA, % S.sub.FFCA, % S.sub.DFF, % Example AMF 33.6 4.0% Ru/MnCo.sub.2O.sub.4 100 95.7 95.7 2.5 0 16 2.0

Comparative Example 1

(52) The procedures were performed under the same conditions as in Example 1, with the exception that a catalyst composed exclusively of MnCo.sub.2O.sub.4 without Ru metal was used and the temperature and reaction time were differently set. The results are shown in Table 7 below.

(53) TABLE-US-00007 TABLE 7 HMF Catalyst Temp. Time (mmol) [metal (wt %)/support] C. (hr) C.sub.HMF, % Y.sub.FDCA, % S.sub.FDCA, % S.sub.FFCA, % S.sub.DFF, % Comparative 2.0 MnCo.sub.2O.sub.4 150 5 42.8 2.0 4.7 10.8 24.9 Example 1

(54) As is apparent from the above Table, when the catalyst composed exclusively of the MnCo.sub.2O.sub.4 support without Ru was used, unlike the catalyst of Examples of the present invention, the HMF conversion, FDCA yield, and FDCA selectivity were significantly decreased.

Comparative Examples 2 and 3

(55) The procedures were performed under the same conditions as in Example 1, with the exception that Au metal nanoparticles and a MnCo.sub.2O.sub.4 support were used as shown in Table 8 below, and the reaction time and temperature were differently set. The results are shown in Table 8 below.

(56) TABLE-US-00008 TABLE 8 HMF/metal Catalyst HMF molar [metal (wt %)/ Time (mmol) ratio support] Temp. C. (hr) C.sub.HMF, % Y.sub.FDCA, % S.sub.FDCA, % S.sub.FFCA, % S.sub.DFF, % Comparative 2.0 250 2.1% Au/MnCo.sub.2O.sub.4 150 5 67.2 8.9 13.3 21.2 11.6 Example 2 Comparative 4.0 500 2.1% Au/MnCo.sub.2O.sub.4 150 2 88.5 0.04 Example 3

(57) As is apparent from the above Table, when the MnCo.sub.2O.sub.4 support containing Au was used as the catalyst, unlike the catalyst of Examples of the present invention, the FDCA yield was significantly decreased.

Comparative Examples 4 to 7

(58) The procedures were performed under the same conditions as in Example 6, with the exception that a catalyst comprising an Au metal/CeO.sub.2 support was used and some of the test conditions were differently set, as shown in Table 9 below. In Comparative Example 6, a solvent mixture of acetic acid and methanol at 8:2 was used, in lieu of the water solvent.

(59) TABLE-US-00009 TABLE 9 HMF Catalyst Temp. Time (mmol) [metal (wt %)/support] C. (hr) C.sub.HMF, % Y.sub.FDCA, % S.sub.FDCA, % S.sub.FFCA, % S.sub.DFF, % Comparative 2.0 2.1% Au/CeO.sub.2 150 2 68.8 1.7 2.5 3.7 8.0 Example 4 Comparative 2.0 2.1% Au/CeO.sub.2 150 5 93.8 2.2 2.3 1.5 0.9 Example 5 Comparative 8.0 2.1% Au/CeO.sub.2 150 2 45.4 0.01 0.03 0.03 13.7 Example 6 Comparative 4.0 2.1% Au/CeO.sub.2 150 2 81.05 0.01 Example 7

(60) *at 400 C., Au was reduced under H.sub.2 flow, 2.1% Au/CeO.sub.2

(61) As is apparent from the above Table, when the catalysts of Comparative Examples 4 to 7 including the support and the metal particles different from those of the catalyst of the present invention were used, the conversion, yield and selectivity were significantly lowered even at high reaction temperatures compared to Examples 1 to 6 according to the present invention. In particular, the 2.1% Au/CeO.sub.2 catalyst of Comparative Examples 4 to 7 was produced in a manner in which Au ions were reduced under strongly basic conditions (pH of about 10 or more, NaOH solution), incorporated into CeO.sub.2 and dried, whereby the catalyst itself was made to be strongly basic. When comparing the solvent of Comparative Example 6 (solvent, acetic acid:methanol=8:2) with the solvent of Comparative Examples 4, 5 and 7 (solvent, water), Comparative Example 6, using the acidic solvent, exhibited drastically lowered HMF conversion and very low FDCA yield and selectivity, from which the above catalyst was confirmed to be basic.

Comparative Example 8

(62) The procedures were performed under the same conditions as in Example 1, with the exception that a Ru metal/MgAl.sub.2O.sub.4 support was used as the catalyst.

(63) TABLE-US-00010 TABLE 10 HMF/metal HMF molar Catalyst Temp. Time (mmol) ratio [metal (wt %)/support] C. (hr) C.sub.HMF, % Y.sub.FDCA, % S.sub.FDCA, % S.sub.FFCA, % S.sub.DFF, % Comparative 1.0 33.3 4% Ru/MgAl.sub.2O.sub.4 120 10 90.5 53.7 59.4 10.5 1.0 Example 8

(64) As described above, in Comparative Example 8 using the support (MgAl.sub.2O.sub.4) other than the spinel support of the present invention, even when the Ru catalyst was used in the same amount, the FDCA selectivity did not reach 60%, unlike Example 1 of the present invention, and the yield was also remarkably low.

Comparative Example 9

(65) The procedures were performed under the same conditions as in Example 6, with the exception that a Ru metal/carbon was used as the catalyst and the base materials Na.sub.2CO.sub.3 and NaHCO.sub.3 were placed in the reactor. The pH in the reactor after initiation of the reaction of Comparative Example 9 was 7 to 8. Furthermore, the procedures were performed under the same conditions (base-free conditions) as in Example 6 using the same catalyst (Ru metal/carbon).

(66) TABLE-US-00011 TABLE 11 HMF/metal HMF molar Catalyst Base Time (mmol) ratio [metal (wt %)/support] material (hr) C.sub.HMF, % Y.sub.FDCA, % S.sub.FDCA, % S.sub.FFCA, % S.sub.DFF, % Comparative 2.0 33.3 4% Ru/carbon NaHCO.sub.3 10 100 85.1 85.1 10.1 0.9 Example 9 Comparative 2.0 33.3 4% Ru/carbon 10 50.4 35.1 69.9 15.3 0 Example 10

(67) As is apparent from Table 11, when the Ru metal/carbon support was used under basic conditions, the FDCA yield was low compared to Example 6 of the present invention, and very poor results were obtained under base-free conditions.

Comparative Example 10 to 12

(68) The procedures were performed as shown in Table 8 in the same manner as in Example 6, with the exception that different kinds of supports were used, as shown in Table 12 below.

(69) TABLE-US-00012 TABLE 12 HMF HMF/metal Catalyst (mmol) molar ratio [metal (wt %)/support] C.sub.HMF, % Y.sub.FDCA, % S.sub.FDCA, % S.sub.FFCA, % S.sub.DFF, % Example 6 2.0 33.6 4.0% Ru/MnCo.sub.2O.sub.4 100 100 97.4 2.3 0.0 Comparative 2.0 33.6 4.0% Ru/CoO 91.1 17.8 19.5 54.2 13.4 Example 11 Comparative 2.0 33.6 4.0% Ru/MnCo.sub.2CO.sub.3 100 69.9 69.9 15.5 0.0 Example 12 Comparative 2.0 33.6 4.0% Ru/MnO.sub.2 98.8 31.1 31.5 37.3 1.2 Example 13

(70) As is apparent from Table 12, even when the Ru nano metal was used in the same amount, the FDCA yield and selectivity were remarkably lowered in Comparative Examples 11, 12 and 13, which did not include the support (MnCo.sub.2O.sub.4) according to an embodiment of the present invention.