KR101663660B1 - Method for preparing 2,5-diformyl furan using carbon-supported metal catalyst - Google Patents

Abstract

5-hydroxymethyl-2-furfural in a ketone compound solvent or an aromatic compound solvent to produce 2,5-dibromofuran, using a catalyst comprising a metal, A process for the preparation of wheyfuran is provided. The process for producing 2,5-difomylfuran of the present invention is easy to be linked with the production process of 5-hydroxymethyl-2-furfural by using an extraction solvent of 5-hydroxymethyl-2-furfural It is possible to reuse the heterogeneous metal catalyst and solvent, and the process cost can be reduced by using a heterogeneous metal catalyst using a low-cost metal such as vanadium rather than a noble metal.

Description

METHOD FOR PREPARING 2,5-DIFORMYL FURAN USING CARBON-SUPPORTED METAL CATALYST BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a process for producing 2,5-dimo-furfuran, and more particularly to a process for producing 2,5-difomylfuran using a metal catalyst supported on activated carbon and an extraction solvent of 5-hydroxymethyl-2-furfural ≪ / RTI >

To cope with the oil price era and global warming, countries around the world make great efforts to reduce dependence on petroleum, an irreversible fossil resource, and are trying to replace petroleum fuel or petrochemicals through biofuels and biochemicals.

As a result of this effort, 5-hydroxymethyl-2-furfural (HMF) represented by the following formula, which is a biomass-derived furan compound,

5-hydroxymethyl-2-furfural is a compound obtained through a dehydration process from a biomass-derived carbohydrate component having the greatest amount on the earth, and through oxidation, 2,5-diformylfuran , DFF) and 2,5-furan dicarboxylic acid (FDCA).

In particular, 2,5-dimo-furfuran represented by the following formula is an extremely useful compound that can be used as a bioplastic monomer or a precursor of a medicine, an antimicrobial agent, an insecticide, a binder and the like.

On the other hand, it is known that 5-hydroxymethyl-2-furfural is easily prepared in a high boiling solvent such as DMSO or DMF or an ionic liquid. However, since such high-boiling solvents or ionic liquids are difficult to remove through distillation, extraction is generally used to recover the 5-hydroxymethyl-2-furfural produced from the reaction mixture. At this time, the most widely used extraction solvent is MIBK (methyl isobutyl ketone).

Therefore, if the oxidation reaction of 5-hydroxymethyl-2-furfural can be carried out on MIBK, the process can be simplified because no separate MIBK distillation process is required.

Further, when 2,5-dimo-furfuran is produced through selective oxidation from 5-hydroxymethyl-2-furfural, the use of oxygen and heterogeneous catalyst as the oxidizing agent results in removal And the catalyst can be reused, so there are many advantages. To this end, studies have been made on heterogeneous metal catalysts supported on various supports, but up to now, it is known that only expensive noble metals have excellent catalytic activity.

Therefore, if 2,5-difomylfuran is produced from 5-hydroxymethyl-2-furfural by using 5-hydroxymethyl-2-furfural extraction solvent as a solvent and oxygen and heterogeneous catalyst as oxidants, Can be reduced, the removal of the oxidizing agent is easy, and the solvent and the catalyst can be reused.

DISCLOSURE Technical Problem Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide an oxidation reaction using a heterogeneous metal catalyst and oxygen as oxidizing agents in an extraction solvent of 5-hydroxymethyl-2-furfural Which is capable of easily removing the oxidizing agent and reusing the solvent and the catalyst, thereby simplifying the process and improving the yield.

It is another object of the present invention to provide a process for producing 2,5-dimo-furfuran which can improve the economical efficiency by lowering the process cost by using a metal catalyst using a low-priced metal rather than a noble metal.

According to one aspect of the present invention, there is provided a process for producing 5-hydroxymethyl-2-furfural by reacting 5-hydroxymethyl-2-furfural with a compound represented by the following formula (1) or a catalyst comprising a metal supported on an activated carbon in an aromatic compound solvent, A method for producing 2,5-diformylfuran can be provided.

[Chemical Formula 1]

In Formula 1,

R ¹ and R ² may be the same or different from each other, and R ¹ and R ² are each independently a C1 to C10 linear alkyl group, a C3 to C10 branched alkyl group, or a C3 to C14 cycloalkyl group.

Wherein the metal is at least one selected from the group consisting of Co, Cu, Fe, Mn, Mo, V, Cr, .

Preferably, the metal may be at least one selected from the group consisting of vanadium (V) and ruthenium (Ru).

The step of preparing 2,5-dimo-furfuran can be carried out by using the catalyst comprising 5-hydroxymethyl-2-furfural in the presence of a compound represented by the formula (1) or a metal supported on the activated carbon in an aromatic compound solvent , And using oxygen as an oxidizing agent to prepare 2,5-dimethylformamide.

The oxygen may be applied at a pressure of 10 to 150 psi.

The compound represented by Formula 1 may be selected from the group consisting of methyl isobutyl ketone, methyl isopropyl ketone, 3-methyl-2-pentanone, ethyl isopropyl ketone (1) selected from the group consisting of ethyl isopropyl ketone, 2-pentanone, 3-pentanone, cyclopentanone, butanone and isophorone. It can be more than a species.

The aromatic compound solvent may be at least one selected from the group consisting of benzene, toluene and xylene.

(A) preparing a metal salt aqueous solution containing the metal element, the catalyst comprising a metal supported on the activated carbon; (B) adding activated carbon to the metal salt aqueous solution to produce activated carbon carrying the metal element; And (c) calcining the activated carbon on which the metal element is supported.

The metal salt may be a metal halide or a metal sulfonate.

The content of the metal element may be 1 to 20 mol% based on the 5-hydroxymethyl-2-furfural.

 The step of preparing the 2,5-dimethylfuran can be carried out at a temperature of 50 to 200 ° C.

The activated carbon may have a surface area of 200 to 1500 m ² / g.

The process of the present invention for producing 2,5-dimo-furfuran can be carried out by using a ketone compound solvent such as methyl isobutyl ketone (MIBK) which is an extraction solvent of 5-hydroxymethyl-2-furfural, - It is easy to link with the furfural production process and omits a separate distillation process, and it is possible to reuse the heterogeneous metal catalyst and the solvent. In addition, by using a heterogeneous metal catalyst using a low-cost metal such as vanadium The cost can be reduced.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a process of the 2,5-dimethylfuran production process of the present invention. FIG.
FIG. 2 shows TEM images of (a) before use and (b) reproduced after use in the reaction of the vanadium catalyst supported on activated carbon prepared in Preparation Example 1 with 2,5-dimethylfuran.
FIG. 3 shows XPS analysis results of (a) before use and (b) reproduced after use in the reaction of the vanadium catalyst supported on activated carbon prepared in Preparation Example 1 with 2,5-dimofuran.
4 shows the yields of 2,5-dimethylformamide in Examples 1 to 8 and Comparative Example 1 in comparison.
5 shows the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-dimo-furfuran in Examples 1, 9, 10 and 11 in comparison.
FIG. 6 shows the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-dimethylfuran in Examples 14, 15 and 16 in comparison.
FIG. 7 shows the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-dimethylfuran in Examples 1, 17, 18 and 19 in comparison.
FIG. 8 shows XPS measurement results of the metal catalysts supported on the various supports used in Example 1, Comparative Examples 1 and 2. FIG.
FIG. 9 shows PXRD measurement results of the metal catalyst supported on the support used in Example 1 and Comparative Examples 2 to 4. FIG.
10 shows the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-diformylfuran in Examples 1, 20, 21 and 22 in comparison.

Hereinafter, embodiments and examples of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention.

It is to be understood, however, that the following description is not intended to limit the invention to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises ", or" having ", and the like, specify that the presence of stated features, integers, steps, operations, elements, or combinations thereof is contemplated by one or more other features But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims. As used herein, unless otherwise defined, the term "alkyl group" means a straight, branched or cyclic aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" which does not contain any double or triple bonds.

The alkyl group may be an "unsaturated alkyl group" comprising at least one double bond or triple bond.

The alkyl group may be a C1 to C14 alkyl group. More specifically, it may be a C1 to C10 alkyl group or a C1 to C6 alkyl group.

For example, the C1 to C4 alkyl groups may have 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, Indicating that they are selected from the group.

Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, ethenyl group, Butyl group, cyclopentyl group, cyclohexyl group, and the like.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic representation of a process for the preparation of 2,5-dimofulfuran of the present invention.

Hereinafter, a method for producing 2,5-dimethylfumaran of the present invention will be described with reference to FIG.

The process for producing 2,5-difomylfuran of the present invention is characterized in that 5-hydroxymethyl-2-furfural is reacted with a compound represented by the following general formula (1) or a catalyst comprising a metal supported on an activated carbon under an aromatic compound solvent , ≪ / RTI > 5-dimo-furfuran.

[Chemical Formula 1]

In Formula 1,

R ¹ and R ² may be the same or different from each other, and R ¹ and R ² are each independently a C1 to C10 linear alkyl group, a C3 to C10 branched alkyl group, or a C3 to C14 cycloalkyl group.

The metal used for the catalyst including the metal supported on the activated carbon may be cobalt, copper, iron, manganese, molybdenum, vanadium, chromium, ruthenium Or the like can be used, but more preferably one or more of vanadium and ruthenium can be used.

In the step of preparing 2,5-dimethylfuran, oxygen can be used as an oxidizing agent by adding oxygen at a predetermined pressure, and the pressure of oxygen can be 10 to 150 psi, preferably 40 to 100 psi have.

The compound represented by Chemical Formula 1 is a ketone compound solvent which can be used as an extraction solvent for 5-hydroxymethyl-2-furfural, and includes methyl isobutyl ketone (MIBK), methyl isopropyl ketone, 3-methyl-2-pentanone, ethyl isopropyl ketone, 2-pentanone, 3-pentanone, cyclohexane, Cyclopentanone, butanone, isophorone, and the like. Preferably, methyl isobutyl ketone can be used.

In some cases, water or an aromatic compound solvent may be used instead of the ketone compound solvent. As the aromatic compound solvent, benzene, toluene, xylene and the like can be used. Toluene can be preferably used.

The catalyst containing the metal supported on the activated carbon can be produced by the following method.

First, an aqueous metal salt solution containing the above-described metal element is prepared (step a).

Thereafter, activated carbon is added to the metal salt aqueous solution to produce the activated carbon bearing the metal element (step b).

At this time, it is preferable to add activated carbon and stir well at room temperature.

Next, the activated carbon carrying the metal element is calcined (step c).

The firing is preferably performed at a temperature of 300 to 500 ° C. in a nitrogen atmosphere for about 1 hour or so.

The metal salt is preferably a metal halide or a metal sulfonate.

The metal salt may be represented by the following formula:

(2)

MX _n

Here, M is the aforementioned metal ion, X is F ^-, Cl ^-, Br ^-, I ^-, and tosyl (OTs ^-) in any one, n is is as any one of an integer from 1 to 7, preferably And is an integer of 3 to 5.

The content of the metal element may be 1 to 20 mol%, more preferably 5 to 10 mol%, based on the 5-hydroxymethyl-2-furfural.

The preparation of the 2,5-dimethylfuran can be carried out at a temperature of from 50 to 200 ° C, more preferably from 60 to 120 ° C, and still more preferably from 80 to 100 ° C.

The activated carbon preferably has a surface area of 200 to 1500 m ² / g, more preferably 400 to 1200 m ² / g.

Hereinafter, the structure of the present invention will be described more specifically by way of the following examples, but the present invention is not limited thereto.

[Example]

Manufacturing example  One

Approximately 200 mg of vanadium chloride (VCl ₃ ) was dissolved in 100 mL of distilled water. 2 g of activated carbon was added to the solution, followed by stirring at room temperature for 3 hours. Thereafter, the activated carbon bearing vanadium was filtered, sufficiently washed with distilled water, and dried in a vacuum oven at 30 ° C. The dried vanadium-impregnated activated carbon was placed in a tube-type furnace and calcined at 400 ° C for 1 hour under a nitrogen atmosphere. Thereafter, the vanadium-supported activated carbon was washed with MIBK and dried in a vacuum oven.

Manufacturing example  2

Activated carbon bearing ruthenium was prepared in the same manner as in Production Example 1 except that ruthenium chloride (RuCl ₃ ) was used instead of vanadium chloride (VCl ₃ ).

Manufacturing example  3

Activated carbon bearing molybdenum was prepared by carrying out the same method as Preparation Example 1 except that molybdenum chloride (MoCl ₃ ) was used instead of vanadium chloride (VCl ₃ ).

Manufacturing example  4

Activated carbon bearing cobalt was prepared in the same manner as in Preparation Example 1 except that cobalt chloride (CoCl ₂ ) was used instead of vanadium chloride (VCl ₃ ).

Manufacturing example  5

Copper-supported activated carbon was prepared in the same manner as in Preparation Example 1 except that copper chloride (CuCl ₂ ) was used instead of vanadium chloride (VCl ₃ ).

Manufacturing example  6

Activated carbon bearing iron was prepared in the same manner as in Preparation Example 1 except that iron chloride (FeCl ₃ ) was used instead of vanadium chloride (VCl ₃ )

Manufacturing example  7

Manganese-supported activated carbon was prepared in the same manner as in Preparation Example 1, except that manganese chloride (MnCl ₂ ) was used instead of vanadium chloride (VCl ₃ ).

Manufacturing example  8

Chromium-supported activated carbon was prepared in the same manner as in Production Example 1 except that chromium chloride (CrCl ₃ ) was used instead of vanadium chloride (VCl ₃ )

Example  One

Hydroxymethyl-2-furfural (200 mg), MIBK (20 mL), and vanadium catalyst (V / HMF molar ratio = 5 mol%) supported on activated carbon prepared according to Preparation Example 1 were charged in a 50 mL Parr pressure reactor, And the reactor was flushed three times with oxygen. The oxygen was then pressurized to 40 psi and the temperature was heated to 100 < 0 > C. During the reaction, the reaction was continued for 4 hours while maintaining the oxygen pressure and the reaction temperature at 650 rpm.

After completion of the reaction, the reactor was cooled to room temperature, and the heterogeneous metal catalyst in the reaction mixture was filtered. The filtrate was subjected to vacuum distillation to remove MIBK, diluted with distilled water and analyzed by HPLC and GCMS. The analysis showed that the conversion of 5-hydroxymethyl-2-furfural to 64% and the selectivity to 2,5- Respectively.

Example  2

Except that the ruthenium catalyst supported on activated carbon prepared according to Production Example 2 was used in place of the vanadium catalyst supported on the activated carbon prepared according to Production Example 1, and 2,5-dimofulfuran was produced in the same manner as in Example 1 And analyzed by HPLC and GCMS. As a result of the analysis, the conversion of 5-hydroxymethyl-2-furfural to 78% and the selectivity to 2,5-dimo-furfuran of 97% were confirmed.

Example  3

The procedure of Example 1 was repeated except that the activated carbon-supported molybdenum catalyst prepared in Preparation Example 3 was used in place of the vanadium catalyst supported on activated carbon prepared according to Preparation Example 1, and 2,5-dimofulfuran was prepared And analyzed by HPLC and GCMS. As a result, the conversion of 5-hydroxymethyl-2-furfural to 11% and the selectivity to 2,5-dimo-furfuran of 93% were confirmed.

Example  4

Except that a cobalt catalyst supported on activated carbon prepared according to Production Example 4 was used in place of the vanadium catalyst supported on activated carbon prepared according to Production Example 1, 2,5-dimofulfuran was produced in the same manner as in Example 1 And analyzed by HPLC and GCMS. As a result, the conversion of 5-hydroxymethyl-2-furfural to 3.2% and the selectivity to 2,5-dimo-furfuran of 100% were confirmed.

Example  5

Except that a copper catalyst supported on activated carbon prepared according to Production Example 5 was used instead of the vanadium catalyst supported on the activated carbon prepared according to Production Example 1, 2,5-dimofulfuran was produced in the same manner as in Example 1 And analyzed by HPLC and GCMS. The analysis confirmed the 5-hydroxymethyl-2-furfural conversion of 3% and the 2,5-difomofuran selectivity of 55%.

Example  6

Except that an iron catalyst supported on activated carbon prepared according to Production Example 6 was used in place of the vanadium catalyst supported on activated carbon prepared according to Preparation Example 1, and 2,5-dimofulfuran was produced in the same manner as in Example 1 And analyzed by HPLC and GCMS. The analysis confirmed the conversion of 5-hydroxymethyl-2-furfural to 4.1% and the selectivity to 2,5-dimo-furfuran to 76%.

Example  7

Except that the vanadium catalyst supported on the activated carbon prepared according to Production Example 1 was replaced with the manganese catalyst supported on the activated carbon prepared according to Production Example 7, 2,5-dimofulfuran was produced in the same manner as in Example 1 And analyzed by HPLC and GCMS. As a result, the conversion of 5-hydroxymethyl-2-furfural to 1.9% and the selectivity to 2,5-dimo-furfuran of 100% were confirmed.

Example  8

The procedure of Example 1 was repeated except that a chromium catalyst supported on activated carbon prepared according to Production Example 9 was used instead of the vanadium catalyst supported on the activated carbon prepared according to Preparation Example 1 to prepare 2,5-dimofulfuran And analyzed by HPLC and GCMS. The analysis confirmed the conversion of 5-hydroxymethyl-2-furfural to 2.1% and the selectivity to 2,5-dimo-furfuran to 100%.

Example  9

2,5-Difluoro-furan was prepared and analyzed by HPLC and GCMS in the same manner as in Example 1, except that the temperature in the reactor was heated to 60 ° C instead of 100 ° C. The analysis confirmed the conversion of 5-hydroxymethyl-2-furfural to 2.4% and the selectivity to 2,5-difomofuran of 100%.

Example  10

2,5-Difluoro-furan was prepared and analyzed by HPLC and GCMS in the same manner as in Example 1, except that the temperature in the reactor was heated to 80 ° C instead of 100 ° C. As a result, the conversion of 5-hydroxymethyl-2-furfural to 25% and the selectivity to 2,5-dimo-furfuran of 98% were confirmed.

Example  11

2,5-Dimfurfurane was prepared and analyzed by HPLC and GCMS in the same manner as in Example 1, except that the temperature in the reactor was heated to 120 ° C instead of 100 ° C. As a result of the analysis, the conversion of 5-hydroxymethyl-2-furfural to 100% was confirmed, and the selectivity to 2,5-dimo-furfuran was 65% and the selectivity to FFCA was 33%.

Example  12

2,5-diphosphorylfuran was prepared in the same manner as in Example 1 except that the molar ratio of the vanadium catalyst (V / 5-hydroxymethyl-2-furfural molar ratio) was changed to 2.5 mol% instead of 5 mol% And analyzed by HPLC and GCMS. As a result, the conversion of 5-hydroxymethyl-2-furfural to 37% and the selectivity to 2,5-dimo-furfuran of 92% were confirmed.

Example  13

2,5-dimo-fumifuran was prepared and analyzed by HPLC and GCMS, except that the molar ratio (V / HMF molar ratio) of the vanadium catalyst was changed to 7.5 mol% instead of 5 mol%. The analysis confirmed the conversion of 5-hydroxymethyl-2-furfural to 86% and the selectivity to 2,5-dimo-furfuran to 97%.

Example  14

2,5-dimo-fumifuran was prepared and analyzed by HPLC and GCMS, except that the molar ratio (V / HMF molar ratio) of the vanadium catalyst was changed to 10 mol% instead of 5 mol%. The analysis showed 95% conversion of 5-hydroxymethyl-2-furfural and 96% 2,5-dimofurfuran selectivity.

Example  15

2,5-Difluoro-furan was prepared in the same manner as in Example 15 except that the reaction time was changed to 6 hours instead of 4 hours, and the result was analyzed by HPLC and GCMS. As a result, the conversion of 5-hydroxymethyl-2-furfural to 95% and the selectivity to 2,5-difomofuran of 89% were confirmed.

Example  16

2,5-Difluoro-furan was prepared in the same manner as in Example 15 except that the reaction time was changed to 8 hours instead of 4 hours, and the result was analyzed by HPLC and GCMS. As a result of the analysis, the conversion of 5-hydroxymethyl-2-furfural to 100% and the selectivity to 2,5-dimo-furfuran of 77% were confirmed.

Example  17

2,5-DMP was prepared and analyzed by HPLC and GCMS in the same manner as in Example 1, except that oxygen was pressurized to 60 psi instead of 40 psi. As a result, the conversion of 5-hydroxymethyl-2-furfural to 68% and the selectivity to 2,5-dimo-furfuran of 97% were confirmed.

Example  18

2,5-DMP was prepared and analyzed by HPLC and GCMS in the same manner as in Example 1, except that oxygen was pressurized to 80 psi instead of 40 psi. As a result, the conversion of 5-hydroxymethyl-2-furfural to 70% and the selectivity to 2,5-difomofuran of 95% were confirmed.

Example  19

2,5-DMP was prepared and analyzed by HPLC and GCMS in the same manner as in Example 1, except that oxygen was pressurized to 100 psi instead of 40 psi. As a result of the analysis, the conversion of 5-hydroxymethyl-2-furfural to 81% was confirmed, and the selectivity to 2,5-dimo-furfuran of 95% and the FFCA selectivity of 5% were confirmed.

Example  20

2,5-Difo-Methylfuran was prepared in the same manner as in Example 15 except that the recovered heterogeneous metal catalyst was cacinized and then reused once. As a result, the conversion of 5-hydroxymethyl-2-furfural to 93% and the selectivity to 2,5-dimo-furfuran of 92% were confirmed.

Example  21

2,5-Difo-Methylfuran was prepared in the same manner as in Example 15 except that the recovered heterogeneous metal catalyst was cacinized and then reused twice. The analysis showed 95% conversion of 5-hydroxymethyl-2-furfural and 85% 2,5-dimo-furan selectivity.

Example  22

2,5-Difo-Methylfuran was prepared in the same manner as in Example 15 except that the recovered heterogeneous metal catalyst was cacinized and then reused three times. As a result, the conversion of 5-hydroxymethyl-2-furfural to 88% and the selectivity to 2,5-dimo-furfuran of 93% were confirmed.

Example  23

2,5-Dipofylfuran was prepared and analyzed by HPLC and GCMS in the same manner as in Example 1, except that toluene was used as a solvent instead of MIBK. As a result, the conversion of 5-hydroxymethyl-2-furfural to 95% and the selectivity to 2,5-difomofuran of 98% were confirmed.

Comparative Example  One

2,5-Difluorofuran was prepared in the same manner as in Example 1 except that 200 mg of the catalyst-free activated carbon was used instead of the vanadium catalyst supported on the activated carbon prepared in Preparation Example 1, and HPLC and GCMS analysis Respectively. Analysis showed 5-hydroxymethyl-2-furfural conversion of 3% and 2,5-dimo-furan selectivity of less than 5%.

Comparative Example  2

2,5-DIPOH MILFURAN was prepared in the same manner as in Example 1 except that a vanadium catalyst supported on hydrotalcite was used instead of the vanadium catalyst supported on activated carbon prepared according to Production Example 1, and HPLC and GCMS Respectively. The analysis confirmed the conversion of 5-hydroxymethyl-2-furfural to 2.4% and the selectivity to 2,5-difomofuran of 71%.

Comparative Example  3

2,5-Dimfurfurane was prepared in the same manner as in Example 1 except that alumina-supported vanadium catalyst was used instead of the vanadium catalyst supported on activated carbon prepared in Production Example 1, and the result was analyzed by HPLC and GCMS . As a result, the conversion of 5-hydroxymethyl-2-furfural to 6.5% and the selectivity to 2,5-difomofuran of 100% were confirmed.

Comparative Example  4

Except that a vanadium catalyst supported on amorphous carbon having a surface area of 10 m < ² > / g or less was used instead of the vanadium catalyst supported on the activated carbon prepared according to Production Example 1, Methylfuran was prepared and analyzed by HPLC and GCMS. As a result of the analysis, the conversion of 5-hydroxymethyl-2-furfural to 100% and the selectivity to 2,5-dimo-furfuran of 6.8% were confirmed.

Comparative Example  5

2,5-DIPO MILFURRAN was prepared in the same manner as in Example 21 except that the recovered heterogeneous metal catalyst was reused as it was without cacification. The analysis confirmed the conversion of 5-hydroxymethyl-2-furfural to 62% and the selectivity to 2,5-difomofuran at 96%.

Comparative Example  6

2,5-Difluoro-furan was prepared in the same manner as in Example 1 except that the solvent was changed to acetonitrile instead of MIBK, and the result was analyzed by HPLC and GCMS. As a result of the analysis, the conversion of 5-hydroxymethyl-2-furfural to 39% and the selectivity to 2,5-dimo-furfuran of 100% were confirmed.

Comparative Example  7

2,5-Difluoro-furan was prepared in the same manner as in Example 1 except that the solvent was changed to DMF instead of MIBK, and the result was analyzed by HPLC and GCMS. As a result, the conversion of 5-hydroxymethyl-2-furfural to 52% and the selectivity to 2,5-dimo-furfuran of 88% were confirmed.

Comparative Example  8

2,5-Difo-Methylfuran was prepared and analyzed by HPLC and GCMS in the same manner as in Example 1, except that the solvent was changed to DMSO instead of MIBK. As a result, the conversion of 5-hydroxymethyl-2-furfural to 38% and the selectivity to 2,5-dimo-furfuran of 86% were confirmed.

Table 1 below summarizes the conditions for the production of 2,5-dimo-furfuran according to Examples 1 to 23 and Comparative Examples 1 to 5.

division Metal catalyst type Support type menstruum Reaction temperature (캜) Catalyst mole ratio
(metal / HMF molar ratio, mol%) Reaction time
(hour) Oxygen pressure
(psi) Number of catalyst reuse
(time) Whether or not the re-use catalyst is subjected to the calcination treatment
(O, X) HMF conversion rate
(%) DFF selectivity
(%) Example 1 vanadium Activated carbon MIBK 100 5 4 40 0 - 64 98 Example 2 ruthenium Activated carbon MIBK 100 5 4 40 0 - 78 97 Example 3 molybdenum Activated carbon MIBK 100 5 4 40 0 - 11 93 Example 4 cobalt Activated carbon MIBK 100 5 4 40 0 - 3.2 100 Example 5 Copper Activated carbon MIBK 100 5 4 40 0 - 3 55 Example 6 iron Activated carbon MIBK 100 5 4 40 0 - 4.1 76 Example 7 manganese Activated carbon MIBK 100 5 4 40 0 - 1.9 100 Example 8 chrome Activated carbon MIBK 100 5 4 40 0 - 2.1 100 Example 9 vanadium Activated carbon MIBK 60 5 4 40 0 - 2.4 100 Example 10 vanadium Activated carbon MIBK 80 5 4 40 0 - 25 98 Example 11 vanadium Activated carbon MIBK 120 5 4 40 0 - 65 33 Example 12 vanadium Activated carbon MIBK 100 2.5 4 40 0 - 37 92 Example 13 vanadium Activated carbon MIBK 100 7.5 4 40 0 - 86 97 Example 14 vanadium Activated carbon MIBK 100 10 4 40 0 - 95 96 Example 15 vanadium) Activated carbon MIBK 100 5 6 40 0 - 95 89 Example 16 vanadium Activated carbon MIBK 100 5 8 40 0 - 100 77 Example 17 vanadium Activated carbon MIBK 100 5 4 60 0 - 68 97 Example 18 vanadium Activated carbon MIBK 100 5 4 80 0 - 70 95 Example 19 vanadium Activated carbon MIBK 100 5 4 100 0 - 81 95 Example 20 vanadium Activated carbon MIBK 100 10 4 40 One O 93 92 Example 21 vanadium Activated carbon MIBK 100 10 4 40 2 O 95 85 Example 22 vanadium Activated carbon MIBK 100 10 4 40 3 O 88 93 Example 23 vanadium Activated carbon Toluene 100 10 4 40 0 O 95 98 Comparative Example 1 none Activated carbon MIBK 100 - 4 40 0 - 3 5 Comparative Example 2 vanadium Hydrotalcite MIBK 100 5 4 40 0 - 2.4 71 Comparative Example 3 vanadium Alumina MIBK 100 5 4 40 0 - 6.5 100 Comparative Example 4 vanadium Amorphous carbon MIBK 100 5 4 40 0 - 100 6.8 Comparative Example 5 vanadium Activated carbon MIBK 100 10 4 40 One X 62 96 Comparative Example 6 vanadium Activated carbon Acetonitrile 100 5 4 40 0 O 39 100 Comparative Example 7 vanadium Activated carbon DMF 100 5 4 40 0 O 52 88 Comparative Example 8 vanadium Activated carbon DMSO 100 5 4 40 0 O 38 86

[Test Example]

Test Example  1: Activated carbon Supported  Properties and oxidation mechanism of vanadium

Fig. 2 shows a TEM image of vanadium supported on activated carbon prepared according to Preparation Example 1 before and after the preparation of 2,5-dimo-furan in Example 1. Fig.

According to FIG. 2, the vanadium supported on activated carbon prepared according to Preparation Example 1 was analyzed by TEM-EDX (Transmission Electron Microscope-Energy dispersive X-ray). As a result, it was confirmed that vanadium element was uniformly distributed on the surface of activated carbon But no vanadium in particle form was present. Further, it was confirmed that the characteristic of the vanadium element stably remains after the selective oxidation reaction of 5-hydroxymethyl-2-furfural without any coagulation phenomenon.

In addition, according to FIG. 3, XPS (X-ray Photoelectron Spectroscopy) 2p 3 / peak corresponding to ₂ binding energy of the V ^{5 +} in the results, 517.5 eV by examining the oxidation number of the vanadium supported on activated carbon to have appear on the 517.5 eV And the oxidation number of the vanadium element was found to be five. It is considered that the trivalent vanadium ion generated from the vanadium salt (VCl ₃ ) in the aqueous solution is oxidized to the vanadium with the valence of vanadium in the process of being supported on the activated carbon. It is believed that the oxidized pentavalent vanadium acts as a catalyst for efficiently oxidizing 5-hydroxymethyl-2-furfural to 2,5-dimo-furfuran after being adsorbed on activated carbon in a stable form through a calcination process. In addition, when viewed as a selective oxidation peak corresponding to 2p _3/2 binding energy of the V ^{+ 5} in the same manner after that appears 517.5 eV was confirmed that the oxidation state of the vanadium is kept to be stable. This result is considered to be related to the fact that the vanadium pentavalent can oxidize 5-hydroxymethyl-2-furfural efficiently to 2,5-dimethyfuran under the conventional homogeneous reaction conditions.

Test Example  2: Activated carbon Carried  Influence of metal elements

The effect of the kind of the metal element supported on the activated carbon on the yield of 2,5-dimethylfuran was analyzed in the metal catalyst used in the production of the 2,5-dimethylfuran of the present invention.

For this purpose, the yields of 2,5-diformylfuran in Examples 1 to 8 and Comparative Example 1 were compared and shown in FIG.

4 and Table 1 show the best activity in Examples 1 and 2 using vanadium (V) and ruthenium (Ru) supported on activated carbon, showing a conversion of 5-hydroxymethyl-2-furfural to 60% % ≪ / RTI > of 2,5-difomofuran selectivity. In the case of molybdenum (Mo) supported on activated carbon, the yield of 5-hydroxymethyl-2-furfural was lower than that of ruthenium and vanadium. On the other hand, in the case of Comparative Example 1 in which only the activated carbon itself was not supported without supporting the metal element, the conversion of 5-hydroxymethyl-2-furfural was 3%, the conversion was 5% It was found that it was hardly produced.

Test Example  3: Influence of reaction temperature

The influence of the reaction temperature on the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-dimo-furfuran in the preparation of 2,5-dimofulfuran of the present invention was analyzed.

For this purpose, the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-diphosphifuran in Examples 1, 9, 10 and 11 are compared in FIG.

According to FIG. 5, the higher the reaction temperature, the higher the conversion of 5-hydroxymethyl-2-furfural. However, when the reaction temperature was raised above 100 ° C, the selectivity of 2,5-dimo-fumifuran was somewhat lowered. By-products such as 5-formyl-2-furancarboxylic acid (FFCA) and 2,5-furandicarboxylic acid The selectivity of the catalyst was increased.

Test Example  4: Effect of metal catalyst usage

The effect of the amount of the metal catalyst on the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-dimo-furfuran in the preparation of 2,5-dimofulfuran of the present invention was analyzed.

To this end, the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-dimo-furfuran in Examples 1, 12, 13 and 16 are summarized in Table 2 below.

Example V / HMF
mol% HMF conversion rate% DFF selectivity% FFCA selectivity% LA selectivity% Other material selectivity% One 5 64 93 2.2 0.0 0.0 12 2.5 37 92 0.0 2.4 5.7 13 7.5 86 97 3.5 0.0 0.0 16 10 95 96 3.6 0.0 0.0

According to Table 2, when the amount of vanadium catalyst is 10 mol% based on 5-hydroxymethyl-2-furfural, the conversion of 5-hydroxymethyl-2-furfural to 95% and the conversion of 2,5- Selectivity. When the amount of the metal catalyst is 2.5 mol% based on 5-hydroxymethyl-2-furfural, 5-hydroxymethyl-2-furfural is self-decomposed and a byproduct such as lubrinic acid (LA) .

Test Example  5: Effect of reaction time

The influence of the reaction time on the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-dimethylfuran was analyzed in the preparation of 2,5-dimo-furan of the present invention.

For this purpose, the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-diformylfuran in Examples 14, 15 and 16 are shown in FIG.

According to FIG. 6, it was confirmed that 90% of 5-hydroxymethyl-2-furfural was converted after 4 hours and 5-hydroxymethyl-2-furfural completely disappeared after 8 hours. However, after 4 hours, the selectivity of 2,5-dimo-furfuran was lowered to 80% or less, and the selectivity of 2,5-dimo-furfuran was increased to 17.5%.

Test Example  6: Influence of oxygen pressure

The effect of oxygen pressure on the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-dimethylmyrfuran in the preparation of 2,5-dimo-furfuran of the present invention was analyzed.

For comparison, the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-diphosphifuran in Examples 1, 17, 18 and 19 are shown in FIG.

According to Fig. 7, as the oxygen pressure was increased, the conversion of 5-hydroxymethyl-2-furfural also increased. As oxygen pressure increased from 40 psi to 100 psi, the conversion of 5-hydroxymethyl-2-furfural increased from 64% to 81%. However, as the oxygen pressure increases, the oxidizing power increases and the resulting 2,5-dimethylfuran is further oxidized, resulting in the formation of FFCA (Formyl furan dicarboxylic acid) as a by-product. When the oxygen pressure was 100 psi, about 5% of the FFCA was produced.

Test Example  7: Metal catalyst Carried  Influence of supports

The influence of the support on which the metal catalyst is supported on the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-dimethylmyrfuran in the preparation of the 2,5-dimo-furfuran of the present invention was analyzed.

To this end, the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-dimethylfuran were compared in Example 1 and Comparative Examples 2 to 4, and the results are summarized in Table 3 below.

division Support Surface area
(m2 / g) HMF conversion rate
(%) DFF selectivity
(%) FFCA selectivity
(%) Example 1 Activated carbon 930 64 98 2.2 Comparative Example 2 Hydrotalcite 141 2.4 71 29 Comparative Example 3 Alumina 101 6.5 100 0 Comparative Example 4 Amorphous carbon 10 100 6.8 24

According to Table 3, vanadium supported on alumina and hydrotalcite shows low 5-hydroxymethyl-2-furfural conversion of 2.4% and 6.5%, respectively, and vanadium supported on amorphous carbon has a high conversion rate of quantitative level But exhibited a low 2,5-dipalmitoyl furan selectivity of 6.8%, indicating a conversion of 5-hydroxymethyl-2-furfural to 64% and a selectivity of 2,5% It was found that the efficiency was very low as compared with Example 1.

For reference, the results of XPS measurement of the metal catalysts supported on the various supports used in Example 1 and Comparative Examples 1 and 2 are shown in FIG. 8, and the XPS measurement results of the metal catalyst supported on the support used in Example 1 and Comparative Examples 2 and 4 The PXRD measurement results of the metal catalyst are shown in FIG.

Referring to Figure 8 and 9, the peak corresponding to the V ^{5 +} 2p _3/2 binding energy, even when using the XPS results for the alumina and hydrotalcite as a support was confirmed to be the same as shown in the 517.5 eV. From these results, it can be concluded that trivalent vanadium is oxidized to pentavalent vanadium even in the process of supporting vanadium in alumina and hydrotalcite. Further, according to the PXRD results, it was confirmed that the vanadium element was dispersed on the support in the amorphous form rather than the crystal form.

Test Example  8: Effect of metal catalyst reuse

The effect of the reuse of the metal catalyst supported on activated carbon on the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-dimo-furfuran in the preparation of 2,5-dimofulfuran of the present invention Respectively.

To this end, the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-diformylfuran in Examples 1, 20, 21 and 22 are shown in FIG.

According to Fig. 10, in Examples 20 to 22 in which the regenerated catalyst was used, the catalyst could be used up to four times with almost no catalyst deactivation.

However, when calcination was not carried out during the preparation of the catalyst, the conversion of 5-hydroxymethyl-2-furfural was 95% or more in the first use (Example 1) 5), the conversion of 5-hydroxymethyl-2-furfural decreased to 65%.

Test Example  9: Influence by solvent

The effect of the solvent used in the preparation of 2,5-dimofulfuran of the present invention on the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-dimo-furfuran was analyzed.

For this purpose, the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-diformylfuran in Examples 1 and 23 and Comparative Examples 6 to 8 were compared and the results are summarized in Table 4 below .

division menstruum Boiling point
(? C) Dipole moment
(D) HMF conversion rate
(%) DFF selectivity
(%) FFCA selectivity
(%) Example 1 MIBK 117 2.8 64 98 2 Example 23 toluene 111 0.36 95 98 2 Comparative Example 6 Acetonitrile 82 3.92 39 100 0 Comparative Example 7 DMF 153 3.86 52 88 12 Comparative Example 8 DMSO 189 3.96 38 86 14

According to Table 4, the best activity was shown in Example 23 using toluene as the solvent as the solvent, and the conversion of 5-hydroxymethyl-2-furfural to 95% and the selectivity to 2,5-dimofurfuran of 98% . However, the toluene has a low dipole moment and thus it is considered that there is a limit to the use of 5-hydroxymethyl-2-furfural as an extraction solvent. On the other hand, in the case of Comparative Examples 6 to 8 in which acetonitrile, DMF and DMSO were used as solvents, the conversion of 5-hydroxymethyl-2-furfural and the selectivity of 2,5-dimo-furfuran were lower than those of MIBK and toluene appear.

The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.

Claims (12)

Preparing 5-hydroxymethyl-2-furfural using a catalyst comprising a metal supported on activated carbon in a solvent of methyl isobutyl ketone,
Wherein the metal is vanadium (V). delete delete The method according to claim 1,
Wherein the step of producing 2,5-dimethyl-fumarfuran comprises reacting the 5-hydroxymethyl-2-furfural with a catalyst containing vanadium (V) supported on the activated carbon in a solvent of methyl isobutyl ketone And the step of producing 2,5-dimo-fumirane using oxygen as an oxidizing agent. 5. The method of claim 4,
Wherein the oxygen is added at a pressure of 10 to 150 psi. delete delete The method according to claim 1,
The catalyst containing the metal supported on the activated carbon
(A) preparing an aqueous metal salt solution containing the metal element;
(B) adding activated carbon to the metal salt aqueous solution to produce activated carbon carrying the metal element; And
And (c) calcining the activated carbon on which the metal element is supported. The method for producing 2,5-dimethylfumaran according to claim 1, 9. The method of claim 8,
Wherein the metal salt is a metal halide or a metal sulfonate. 9. The method of claim 8,
Wherein the content of the metal element is 1 to 20 mol% with respect to the 5-hydroxymethyl-2-furfural. The method according to claim 1,
Wherein the step of preparing the 2,5-dimethylfuran is carried out at a temperature of 50 to 200 ° C. The method according to claim 1,
Wherein the activated carbon has a surface area of 200 to 1500 m ² / g.

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