KR101835608B1 - Catalyst for producing 2,5-diformylfuran and method for producing 2,5-diformylfuran using the same - Google Patents

Catalyst for producing 2,5-diformylfuran and method for producing 2,5-diformylfuran using the same Download PDF

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KR101835608B1
KR101835608B1 KR1020160026920A KR20160026920A KR101835608B1 KR 101835608 B1 KR101835608 B1 KR 101835608B1 KR 1020160026920 A KR1020160026920 A KR 1020160026920A KR 20160026920 A KR20160026920 A KR 20160026920A KR 101835608 B1 KR101835608 B1 KR 101835608B1
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catalyst
dff
noble metal
support
furan
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KR20170104215A (en
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김용진
조진구
신승한
이홍식
쿠마르 미슈라 디네쉬
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한국생산기술연구원
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B01J32/00—
    • B01J35/023—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural

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Abstract

The present invention relates to a catalyst for aldehyde formation of a furan compound containing a hydroxyl group and a carbonyl group, wherein in the presence of a catalyst for preparing a DFF in which noble metal nanoparticles are contained in a support having a spinel structure and a catalyst containing noble metal nanoparticles in a support having a spinel structure, And oxidizing the furan-based compound containing a carbonyl group.
According to the method for producing a DFF using the catalyst of the present invention, the conversion rate and the yield are significantly higher than those obtained by the conventional DFF production method, and the process can be simplified by the reaction in a single vessel, 2 ), or an air pressure condition.

Description

A catalyst for the production of 2,5-diformylfuran and a process for producing 2,5-diformylfuran and a method for producing 2,5-diformylfuran using the same,

The present invention relates to a method for producing 2,5-diformylfuran from a furan compound containing a hydroxyl group and a carbonyl group by using a catalyst containing noble metal nanoparticles in a support having a spinel structure will be.

Recently, a number of scientists and researchers have shown considerable interest in biomass-derived molecules, called platform molecules or building blocks.

As a typical example of such a platform molecule, 5-hydroxymethyl-2-furfural (hereinafter referred to as HMF) is used as a biomass-derived furan compound, 2,5-diformylfuran (hereinafter referred to as DFF) produced through an oxidation reaction.

In particular, DFF is a very useful compound that can be used as a precursor of a bioplastic monomer or a drug, an antibacterial agent, an insecticide, a binder, etc. as a platform molecule.

US Patent Publication No. US 2012/0059178 A1 discloses a process for the oxidation of furan aldehydes such as HMF using a Co / Mn two component catalyst system and using Co / Mn and MEK (methyl ethyl ketone) as catalyst Is selectively oxidized with DFF in the case of using Co / Mn and bromide as a catalyst, and 2,5-furandicarboxylic acid (hereinafter referred to as FDCA) in the case of using Co / Mn and bromide as a catalyst.

However, these methods are complicated and require high temperatures and pressures, low purity and productivity of the final products, and low yields of 5-hydroxymethyl-2-furancarboxylic acid ( 5-hydroxymethyl-2-furancarboxylic acid (hereinafter referred to as HMFCA), 5-formyl-2-furancarboxylic acid (hereinafter referred to as FFCA) and FDCA And there is a constant demand for improvement of processes for selective oxidation of DFF.

US Patent Publication No. 2012/0059178

The present invention relates to a method for producing a DFF, which comprises the steps of: ( 1 ) preparing a DFF having a high purity DFF while minimizing the generation of byproducts from a furan compound containing a hydroxyl group and a carbonyl group under low temperature, low pressure oxygen (O 2 ) And to provide a method capable of producing at a high yield.

The present inventors have intensively studied in order to solve the above problems, and as a result, it is an object of the present invention to provide a catalyst for the production of DFF in which noble metal nanoparticles are contained in a support having a spinel structure, as aldehyde catalysts for a furan compound containing a hydroxyl group and a carbonyl group.

Another aspect of the present invention is to provide a method for producing DFF, which comprises oxidizing a furan compound containing a hydroxyl group and a carbonyl group in the presence of a catalyst containing noble metal nanoparticles in a spinel structure support.

Further, the furan-based compound containing a hydroxyl group and a carbonyl group which are raw materials used in the method for producing the DFF of the present invention may be obtained from a biomass containing cellulose or a polysaccharide, though not limited thereto.

Using a catalyst containing the noble metal nanoparticles in the support of the spinel structure of the present invention, it is possible to produce DFFs in a high yield, low pressure and low pressure oxygen (O 2 ) or air pressure conditions But also the occurrence of by-products can be minimized.

1 is a SEM photograph of a MnCo 2 O 4 support having a spinel structure according to an embodiment of the present invention.
2 is a SEM photograph of a microsphere of a MnCo 2 O 4 support having a spinel structure according to an embodiment of the present invention.
FIG. 3 is a SEM photograph showing a plurality of pores in a MnCo 2 O 4 support having a spinel structure according to an embodiment of the present invention.
4 is an Energy-Dispersive X-ray (EDX / EDS) spectrometer of a catalyst including Ru nanoparticles in a MnCo 2 O 4 support having a spinel structure according to an embodiment of the present invention.
5 is a photoelectron spectroscopy (XPS) of a catalyst containing Ru nanoparticles in a MnCo 2 O 4 support having a spinel structure according to an embodiment of the present invention.

According to an embodiment of the present invention, there is provided a catalyst for the production of 2,5-diformylfuran (DFF) containing noble metal nanoparticles in a support having a spinel structure as an aldehyde catalyst for a furan compound containing a hydroxyl group and a carbonyl group can do.

The support of the spinel structure may include MnCo 2 O 4 , CoMn 2 O 4 , ZnAl 2 O 4 , FeAl 2 O 4 , CuFe 2 O 4 , ZnMn 2 O 4 , MnFe 2 O 4 , Fe 3 O 4 , TiFe 2 O 4 , ZnFe 2 O 4 , Mg 2 SiO 4 , and Fe 2 SiO 4. According to one embodiment of the present invention, the support having the spinel structure may be MnCo 2 O 4 or CoMn 2 O 4 .

The MnCo 2 O 4 and CoMn 2 O 4 scaffolds can be MnCo 2 O 4 as a spinel structure as shown in FIG. 1, and their average particle diameter (D 50 ) can be 2.0 to 4.0 μm. It may be a structure in which many microspheres of 30 to 60 nm shown in FIG. 2 are accumulated.

3, the MnCo 2 O 4 support may include a plurality of pores, and the noble metal nanoparticles may be included in the pores of the support.

The MnCo 2 O 4 and CoMn 2 O 4 supports according to an embodiment of the present invention have a unique structure and size as shown in FIGS. 1 to 3. Thus, when the noble metal nanoparticles are reduced and contained in the support, Has an efficient structure that can be formed evenly distributed in the support.

The noble metal may be at least one selected from the group consisting of platinum, palladium, and ruthenium. According to one embodiment of the present invention, the noble metal may be ruthenium.

Particularly, the noble metal nanoparticles may have a particle size of 5 to 15 nm, and the noble metal nanoparticles of 5 to 15 nm in size may efficiently contain the support having the spinel structure therein, The noble metal particles can be uniformly dispersed in the structure in which a plurality of microspheres are integrated, and the stable oxidation reaction of the furan compound can be induced.

In addition, the noble metal nanoparticles may be contained in an amount of 0.1 to 10 wt% based on the weight of the catalyst precursor including the support and the noble metal nanoparticles. If the noble metal nanoparticles are contained in an amount of less than 0.1% by weight, the yield of 2,5-diformylfuran (DFF) may be lowered. If the noble metal nanoparticles are contained in an amount of more than 10% by weight, And excessive use of noble metal particles may affect the price increase of the catalyst, which may be uneconomical.

The method of producing the support having the spinel structure is not particularly limited and it is possible to use a conventional method in this field that can be produced and a method of carrying noble metal nanoparticles in a support having a spinel structure. However, according to one embodiment of the present invention, the noble metal salt hydrate may be impregnated into a spinel structure support in an aqueous solution, and subjected to a reduction treatment so that the reduced noble metal is contained in the support.

By using a catalyst according to one embodiment of the present invention, efficient, yet can cause oxidation of the DFF, the low-temperature, oxygen pressure of the low pressure than the prior art from when DFF manufacture, HMF (O 2) or air-pressure process in (air) Can be performed.

According to another aspect of the present invention, there is provided a process for preparing 2,5-diformylfuran (hereinafter referred to as " furane compound ") comprising oxidizing a furan compound containing a hydroxyl group and a carbonyl group in the presence of a catalyst containing a noble metal nano- DFF). ≪ / RTI >

The support of the spinel structure may be MnCo 2 O 4 , CoMn 2 O 4 , ZnAl 2 O 4 , FeAl 2 O 4 , CuFe 2 O 4 , ZnMn 2 O 4 , MnFe 2 O 4 , Fe 3 O 4 , TiFe 2 O 4 , ZnFe 2 O 4 , Mg 2 SiO 4 , and Fe 2 SiO 4. According to one embodiment of the present invention, the support of the spinel structure may be MnCo 2 O 4 .

Here, the furan compound containing the hydroxyl group and the carbonyl group may be 5-hydroxymethyl furfural (HMF).

The furan-based compounds of the present invention, particularly HMF, can be obtained by dehydration of sugars, particularly of the hexose, such as fructose and glucose, which hydrolyze cellulose and polysaccharide containing biomass, as well as glucose, (High fructose syrup) obtained from fructose obtained by the method of the present invention, that is, the furan compound used in the present invention can be said to be obtained from cellulose or polysaccharide containing biomass. This cellulosic or polysaccharide containing biomass is an example of widely available raw materials in nature and is a renewable raw material for HMF.

In the method of manufacturing DFF according to the present invention, the production method of maximizing the yield of FFFA and FDCA and maximizing the yield of DFF by realizing different catalyst, solvent, pressure and temperature conditions are realized.

The noble metal nanoparticles may be at least one selected from the group consisting of platinum, palladium, and ruthenium. In the catalyst having the noble metal nanoparticles in the support of the spinel structure, the ratio of the noble metal may be the conversion ratio of HMF and the yield of DFF In order to maximize efficiency and realize an efficient process, the molar ratio of the furan compound to the noble metal nanoparticles is preferably 1: 25 to 500, more preferably 1: 75 to 1: 300.

The oxidation of the furan compound is preferably performed under the conditions of an oxygen (O 2 ) pressure in the reactor of 20 to 150 Psi or an air pressure of 100 to 500 Psi, a reaction temperature of 60 to 145 ° C and a reaction time of 1 to 4 hours, An oxygen pressure of 30 to 60 Psi, or an air pressure of 150 to 400 Psi, a reaction temperature of 130 to 145 DEG C, and a reaction time of 2 to 3 hours. If the oxygen pressure is 20 Psi or the air pressure is less than 100 PSI, the yield of the DFF and the amount of the final product are low, and if the oxygen pressure is 150 Psi or the air pressure exceeds 500 PSI, the yield of the DFF is greatly increased However, due to excessively high pressure, it is not preferable from the viewpoint of process cost and process simplicity, and the rate of occurrence of by-products can be increased due to excessive oxygen supply. If the reaction time is less than 1 hour, the yield of DFF is low, and if the reaction time exceeds 4 hours, the yield of the byproduct is increased and the process cost is further added. If the reaction temperature is less than 60 ° C, the yield of DFF is low, and if the reaction temperature exceeds 145 ° C, the yield of DFF is rather low.

For example, the oxidation of HMF can generate various compounds depending on the degree of oxidation as shown in the following reaction formula (1).

[Reaction Scheme 1]

Figure 112016021712587-pat00001

HMFCA, FFCA, FDCA and the like in the process of preparing DFF using a catalyst according to an embodiment of the present invention, which are different from the final obtained DFF, are different from each other and correspond to by-products. In addition, HMFCA, FDCA and the like are very low in solubility in solvents after production, which may adversely affect the final yield of the desired compound, DFF. Thus, according to one embodiment of the present invention, toluene may be used as a solvent used in the production of DFF. By using the solvent as the toluene, by-products can be minimized and the selectivity of the DFF can be enhanced.

The reaction may also be such that the reaction takes place in a single vessel.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are intended to further illustrate the present invention, and the scope of the present invention is not limited thereto.

MnCo of spinel structure 2 O 4  Preparation of support

65.3 mmol of commercially available (CH 3 COO) 2- Co · 4H 2 O and 32.6 mmol (Co: Mn molar ratio 2: 1) of (CH 3 COO) 2 Mn · 4H 2 O were dissolved in 400 mL of water , Homogenize by stirring for 30 minutes.

Independently, dissolve 50 g of ammonium sulfate in 400 mL of water. The solution is slowly stirred and mixed for 4 hours. NH 4 HCO 3 is slowly added to the solution and stirred for 6 hours. A pale pink precipitate is obtained by filtration and washed with distilled water and anhydrous ethanol. And then dried at 60 DEG C for 12 hours. The obtained carbonate precursor was annealed in a furnace at 425 ° C (2 ° C / min) for 12 hours while supplying air, then slowly lowered to room temperature and maintained for 8 hours to obtain MnCo 2 O 4 To obtain a spinel structure.

Spinel  Structural MnCo 2 O 4  Preparation of catalyst containing nano-ruthenium noble metal particles in a support

5 g of the MnCo 2 O 4 support having the spinel structure prepared above and 0.082 g of RuCl 3 .3H 2 O so that the Ru content could be 1.8 wt% based on the entire catalyst , about 20 ml of water immersed in a cooling bath (100 ml). The mixture is stirred under N 2 atmosphere for 12 hours. Thereafter, NaBH 4 was added in an amount of 10 times or more the amount of RuCl 3 .3H 2 O, The aqueous solution is dropped by one drop into the flask and stirring is carried out at a rate of 500 rpm for one day at room temperature and under N 2 atmosphere so that the reaction can proceed completely. Through this reaction, Ru (III) is reduced to Ru (0) to form nanoparticles. Finally, the catalyst obtained through the reaction is separated by filtration and washed with ethanol. The above process was repeated to produce a dried dark-colored A catalyst containing nano-ruthenium noble metal particles in a MnCo 2 O 4 support having a spinel structure was obtained. In order to analyze the catalyst, Energy-Dispersive X-ray (EDX / EDS) Spectrometer and Quantax 200 were measured and the results are shown in FIG. As shown in FIG. 4, it was confirmed that the ruthenium precious metal was included in the MnCo 2 O 4 support of the spinel structure.

In addition, when the catalyst is analyzed by X-ray photoelectron spectroscopy (XPS) as shown in FIG. 5, it can be seen that Co, Mn, O and Ru are present in FIG. 5 (a) d), it can be seen that the O atom is present in the spinel lattice from the 1s spectrum of O and that the maximum value of the peak of 3P 3/2 of Ru in Fig. 5 (f) exists at 455 to 480 eV, which is the 3d region of Ru It can be confirmed that Ru is a metal particle.

Further, when the particle diameter of the Ru nano metal was measured by HR TEM, the average particle diameter of the catalyst was found to be 5 nm.

From HMF To DMF  Performing Oxidation Processes ( Example  1 to 4 and Comparative Example  1 to 19)

[ Example  One]

A magnetic stirrer and an electric heater are provided in a 100-mL stainless steel high-pressure reactor. 5-Hydroxymethyl furfural (HMF) (0.2513 g, 2.0 mmol) and toluene as a solvent were charged together with 15 ml of toluene as a solvent, and the catalyst added as shown in Table 1 was charged and stirred at 100 rpm After the mixing was carried out at room temperature for 5 minutes, oxygen (O 2 ) was continuously fed into the reactor while maintaining the temperature of the reactor at 120 ° C., the pressure in the vessel at 40 Psi, stirring at 600 rpm, Lt; / RTI > The pressure was controlled by a back pressure regulator connected to the reservoir tank so that the pressure in the reactor was kept constant during the reaction. At the end of the reaction, the reaction mixture was cooled to room temperature and filtered to separate the solid product. The separated solid product was then completely dried in a vacuum oven. After drying, the weight of the DFF was measured, and a part of the DFF was dissolved in water containing H 2 SO 4 (0.0005 M) and then analyzed by HPLC (Agilent Technologies 1200 series, Bio-Rad Aminex HPX-87H pre-packed column (C), DFF production yield (Y), and DFF selectivity (S) were calculated by the following mathematical formula. The calculated results are shown in Table 1.

[Equation 1]

Figure 112016021712587-pat00002

&Quot; (2) "

Figure 112016021712587-pat00003

&Quot; (3) "

Figure 112016021712587-pat00004

[ Example  2 to 4]

Experiments were carried out under the same conditions as in Example 1 except that the amount of catalyst was varied.

catalyst The amount of catalyst (g) HMF / Metal
Molar ratio O 2 (Psi) C% Y% S% Example 1 1.8 wt% Ru
MnCo 2 O 4 support 0.15 75 40 98.3 98.3 100 Example 2 1.8 wt% Ru
MnCo 2 O 4 support 0.11 100 40 89.6 87.9 98.1 Example 3 1.8 wt% Ru
MnCo 2 O 4 support 0.0742 150 40 75.4 75.4 100 Example 4 1.8 wt% Ru
MnCo 2 O 4 support 0.0374 300 40 72.2 72.2 100

[ Example  5]

When the support producing a spinel structure, (CH 3 COO) 2- Co · mol number and the 4H 2 O (CH 3 COO) 2 Mn · 1 of the 4H 2 O: 2 by changing a Co: the molar ratio of Mn 1: 2 And 4% by weight of Ru nano metal was contained in the support. The results are shown in Table 2.

catalyst The amount of catalyst (g) HMF / Metal
Molar ratio O 2 (Psi) C% Y% S% Example 5 1.8 wt% Ru
CoMn 2 O 4 support 0.15 75 40 82.3 55.0 66.8

[ Example  6 to 9]

Experiments were carried out under the same conditions as in Example 1 except that the air to be supplied was replaced with air, and the results obtained in the same manner as in Example 1 are shown below, except for the environment shown in Table 3. FDCA and FFCA as reaction by-products were not found, and the yields were all 0%.

catalyst Amount of catalyst
(g) HMF /
metal
Molar ratio air
(Psi) Temperature (℃) C% Y% S% Example 6 4.0 wt% Ru
MnCo 2 O 4 support 0.10 50 100 120 61.8 61.0 98.6 Example 7 4.0 wt% Ru
MnCo 2 O 4 support 0.10 50 350 130 92.07 63.4 68.9 Example 8 4.0 wt% Ru
MnCo 2 O 4 support 0.15 33.6 350 130 97.8 69.1 70.6 Example 9 4.0 wt% Ru
MnCo 2 O 4 support 0.15 33.6 350 120 99.2 97.7 98.4

[ Comparative Example  One]

Experiments were carried out under the same conditions as in Example 1 except that the oxygen pressure in the reactor was changed and the catalyst used was 1.8 wt% Ru and Hydrotalcite, and the results are shown in Table 4.

catalyst The amount of catalyst (g) HMF / Metal
Molar ratio O 2 (Psi) C% Y% S% Comparative Example 1 1.8 wt% Ru
Hydrotalcite support 0.2 - 100 60 47.5 79.1

As shown in the above table, in the case of using a catalyst containing nano-ruthenium noble metal particles in a support having no spinel structure, the conversion rate, yield and selectivity were all significantly low even at 2.5 times higher oxygen pressure than the above- .

[ Comparative Example  2 to 6]

Experiments were carried out under the same conditions as in Example 1 except that only the MnCo 2 O 4 catalyst was used as shown in Table 5 and the oxygen pressure in the reactor was changed to some extent. In Comparative Examples 4 and 6, the reaction temperature was 150 Lt; 0 > C.

catalyst The amount of catalyst (g) HMF / Metal
Molar ratio O 2 (Psi) C% Y% S% Comparative Example 2 MnCo 2 O 4 0.18 - 40 70.1 70.1 100 Comparative Example 3 MnCo 2 O 4 0.15 - 40 66.0 66.0 100 Comparative Example 4 MnCo 2 O 4 0.15 - 40 73.1 73.1 100 Comparative Example 5 MnCo 2 O 4 0.20 - 40 71.2 71.2 100 Comparative Example 6 MnCo 2 O 4 0.20 - 100 78.8 78.8 100

As shown in the above table, unlike the catalyst used in the present embodiment, MnCo 2 O 4 excluding Ru When only the support was used as the catalyst, it was confirmed that the conversion and the yield were all lowered. Further, when the results of Comparative Example 3 (130 ° C) and Comparative Example 4 (150 ° C) were compared at the reaction temperature, it was confirmed that the conversion and yield were increased.

[ Comparative Example  7 to 8]

Experiments were carried out under the same conditions as in Example 1 except that the catalyst used and the O 2 pressure were varied as shown in Table 6

catalyst The amount of catalyst (g) HMF / Metal
Molar ratio O 2 (Psi) C% Y% S% Comparative Example 7 5.0 wt% Co
Al 2 O 3 support 0.2 - 100 60.3 11.2 18.5 Comparative Example 8 5.0 wt% Co
Ceria backing 0.2 - 100 60.0 13.3 22.0

As shown in the above table, when the catalysts of Comparative Examples 7 to 8 in which the support and the metal particles were different from the present invention were used, the conversion, yield and selectivity were remarkably low even at oxygen pressures higher than those of Examples 1 to 4 I could.

[ Comparative Example  9 To 18]

Experiments were carried out under the same conditions as in Example 1 except that the catalyst and O 2 pressure were different as shown in Table 7. In the case of Comparative Example 9, the reaction temperature was 150 ° C.

catalyst The amount of catalyst (g) HMF / Metal
Molar ratio O 2 (Psi) C% Y% S% Comparative Example 9 Hydrotalcite (HT) 0.2 - 100 60 47.5 79.1 Comparative Example 10 MgO 0.2 - 100 67.1 61.9 92.0 Comparative Example 11 ZnO 0.2 - 100 84.9 74.5 87.7 Comparative Example 12 ZrO 2 0.2 - 100 91.7 66.0 72.4 Comparative Example 13 Ceria 0.2 - 100 84.9 87.2 73.9 Comparative Example 14 WO 3 0.2 - 100 79.0 26.2 33.0 Comparative Example 15 SnO 0.2 - 100 80.2 44.5 55.4 Comparative Example 16 NiO 0.2 - 100 87.3 55.4 63.5 Comparative Example 17 Co (II, III) oxide 0.2 - 100 92.5 79.2 85.6 Comparative Example 18 Ag 2 O 0.2 - 100 94.7 62.8 66.3

As shown in the above table, in Comparative Examples 9 to 18 using various catalysts conventionally used, low conversion rate, yield and selectivity are shown even at high pressure (O 2 supply pressure 100 Psi) as compared with Examples 1 to 4 And it was confirmed that Comparative Example 9 exhibited a low conversion rate, yield and selectivity even though the temperature was higher than that in the Example of the present invention.

[ Comparative Example  19]

Experiments were carried out under the same conditions as in Example 1 except that a Ru metal / MgAl 2 O 4 support was used as a catalyst to be used.

catalyst The amount of catalyst (g) HMF / Metal
Molar ratio O 2 (Psi) C% Y% S% Comparative Example 19 1.8 wt% Ru
MgAl 2 O 4 support 0.15 75 40 80.03 53.08 61.2

As can be seen from the above, in the case of Comparative Example 19 using MgAl 2 O 4 other than the spinel support of the present invention, although the same amount of Ru catalyst was used, the DFF selectivity, yield and the like were comparable to those of Example 1 , It was confirmed that it was not reached to the level of 60%, and the yield was also remarkably low.

[ Comparative Example  20]

Experiments were carried out under the same conditions as in Example 1 except that the gas to be supplied was replaced with air as shown in Table 1 and 20 ml of H 2 O was used as a solvent to be used. The results are shown below.

catalyst The amount of catalyst (g) HMF / Metal
Molar ratio air
(Psi) Temperature (℃) C% Y% S% Comparative Example 20 4.0 wt% Ru
MnCo 2 O 4 support 0.10 50 100 120 100 0.0 0.0

As can be seen from the above table, when the water of Comparative Example 20 was used instead of toluene in the air pressure conditions of Examples 6 to 9, the desired DFF could not be obtained, FDCA and FFCA were produced, FDCA production yield was 60.9% and FFCA production yield was 38.5%.

As described above, according to the process for producing DFF using the catalyst of the present invention, the conversion rate, yield and selectivity are significantly higher than those obtained by the conventional DFF production method, and the process can be simplified by reaction in a single vessel. The reaction can be carried out under low pressure, low pressure, oxygen pressure (O 2 ) or air pressure conditions.

Claims (15)

As an aldehyde catalyst for a furan-based compound containing a hydroxyl group and a carbonyl group,
MnCo 2 O 4 and CoMn 2 O 4 . A catalyst for the production of 2,5-diformylfuran (DFF) wherein noble metal nanoparticles are contained in a support of a spinel structure. delete The method according to claim 1,
Wherein the support has an average particle diameter (D 50 ) of 2.0 to 4.0 탆. The method according to claim 1,
Wherein the noble metal is at least one selected from the group consisting of platinum, palladium, and ruthenium. The method of claim 4,
Wherein the noble metal is ruthenium. 2. A catalyst for the production of 2,5-diformylfuran (DFF). The method according to claim 1,
Wherein the furan compound is 5-hydroxymethyl furfural (HMF). The method according to claim 1,
Wherein the noble metal nanoparticles are contained in an amount of 0.1 to 10 wt% based on the total weight of the catalyst. In the presence of a catalyst containing noble metal nanoparticles in a support having a spinel structure containing at least one of MnCo 2 O 4 and CoMn 2 O 4 ,
(DFF) which comprises oxidizing a furan-based compound comprising a hydroxyl group and a carbonyl group. The method of claim 8,
Wherein the furan compound containing a hydroxyl group and a carbonyl group is 5-hydroxymethyl furfural (HMF). The method of claim 8,
Wherein the noble metal nanoparticles are at least one selected from the group consisting of platinum, palladium, and ruthenium. The method of claim 8,
The oxygen of the furan-based oxide of the compound is from 60 to 145 ℃ temperature of 20 to 80 Psi (O 2) (DFF) at a pressure of 100 to 500 PSI and a reaction time of 1 to 4 hours. The method of claim 8,
Wherein the molar ratio of the furan compound to the noble metal nanoparticles is from 1: 25 to 500. 5. The process for producing 2,5-diformylfuran (DFF) according to claim 1, The method of claim 8,
Wherein the oxidation of the furan compound is carried out in a single vessel using toluene as a solvent. ≪ RTI ID = 0.0 > (DFF) < / RTI > The method of claim 9,
Wherein the 5-hydroxymethyl furfural (HMF) is obtained from cellulose or polysaccharide containing biomass. delete
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