KR20200112149A - Preparing method for alkoxy-methylfurfural and 2,5-furandicarboxylic acid from fructose - Google Patents

Abstract

The present invention provides a method for manufacturing 2,5-furandicarboxylic acid comprising the following steps of: (a) manufacturing a mixed solution by mixing fructose and an organic solvent; (b) heating the mixed solution under a solid acid catalyst and conducting a reaction to manufacture alkoxy-methyl furfural; (c) filtering and separating the solid acid catalyst from an alkoxy-methyl furfural solution in which the solid acid catalyst is mixed; and (d) pressurizing and reacting a solution from which the solid acid catalyst is separated under an oxidation catalyst to manufacture 2,5-furandicarboxylic acid. Therefore, it is possible to economically manufacture 2,5-furandicarboxylic acid from fructose.

Description

Preparation method for alkoxy-methylfurfural and 2,5-furandicarboxylic acid from fructose

The present invention relates to a method for preparing 2,5-furandicarboxylic acid from fructose, and in more detail, alkoxy as an intermediate from fructose using a solid acid catalyst. -It relates to a method of preparing alkoxy-methylfurfural and preparing 2,5-furandicarboxylic acid therefrom.

2,5-Furandicarboxylic acid (hereinafter referred to as'FDCA') is an organic compound in which two carboxylic acids are bonded to the furan ring, and as an alternative to petroleum-derived terephthalic acid, interest has recently increased. It is a chemical substance.

In addition, FDCA can be manufactured from renewable resources and is an intermediate used in various fields such as pesticides, pharmaceuticals, pesticides, pharmaceuticals or antibacterial agents.

In general, FDCA synthesizes FDCA by oxidizing 5-hydroxymethyl furfural (hereinafter'HMF'), which is induced by the dehydration of hexose derivatives, through a catalyst.

The oxidation of HMF produces diformylfuran (DFF) or hydroxymerylfurancarboxylic acid (5-hydroxymethyl-2-furancarboxylic acid, HFCA) as an intermediate product, and formylfurancarboxylic acid (5 -formyl-2-furancarboxylic acid, FCA) to produce FDCA.

On the other hand, fructose (Fructose) is a monosaccharide having a ketone as a reducing group, one of the hexose and widely present in the plant world, it is contained in fruit with glucose in a free form or combined with glucose to exist as sucrose.

In order to prepare FDCA from fructose, HMF is prepared through a fructose dehydration reaction in one step, and HMF is oxidized in a second step.

When the first step, fructose dehydration, is carried out in an aqueous solution, the generated HMF is easily decomposed into levulinic acid and formic acid by a secondary reaction with water, so in order to increase the HMF yield, a high boiling point organic solvent (ex. It is advantageous to use 1-Butanol, GVL, DMF, etc.) (Non-Patent Document 1, Green Chem., Non-Patent Document 2 2015, 17, 3310; Green Chem., 2011, 13, 754).

In order to increase the FDCA yield in the oxidation reaction of HMF, it is advantageous to perform the reaction in an aqueous solution (Patent Document 1, Korean Laid-Open Patent Publication No. 10-2018-7018309)

Therefore, in order to prepare FDCA from fructose in high yield, HMF must be prepared in a high boiling point organic solvent and then HMF must be separated from the organic solvent before the HMF oxidation reaction.

However, much effort is required to separate the organic solvent from HMF, and loss of HMF in the separation process cannot be avoided.

For example, in the case of removing the solvent by evaporation, the reaction temperature must be kept below 50° C. in order not to decompose HMF.

Accordingly, very low pressure is required to remove the high boiling point solvent, which is almost impossible and not economical to carry out in large-scale industrial processes.

As another method, techniques for separating HMF from a high boiling point organic solvent using an organic solvent extractant have been introduced, but there is a problem in that the efficiency is inferior due to the limitation of HMF solubility in the organic solvent extractant, which is also not economical. . (Non-patent document 3. Nature, 2007, 447, 982)

Therefore, in order to economically manufacture FDCA from fructose, it is ideal to proceed with the oxidation reaction immediately after the first step fructose dehydration reaction without additional post-treatment.

In addition, a method of generating FDCA using a homogeneous catalyst such as Co/Mn/Br in an acetic acid medium in the HMF oxidation reaction is known, but it is difficult to recover and reuse the catalyst, and there is a problem of environmental pollution due to waste generation, which is not preferable.

Therefore, as an alternative to the homogeneous catalyst technology, it is very necessary to develop a manufacturing method that increases the FDCA yield using a heterogeneous catalyst.

(1) Korean Patent Application Publication No. 10-2018-7018309 (published on August 13, 2018)

(1) Green Chem., 2015, 17, 3310 (2) Green Chem., 2011, 13, 754 (3) Nature, 2007, 447, 982

Accordingly, the present invention is to provide a method for economically producing FDCA from fructose.

Specifically, it provides a catalytic process technology for producing FDCA without the process of separating the intermediate after fructose dehydration using a solid acid catalyst.In addition, a catalyst with high economic efficiency by using a heterogeneous catalyst instead of a homogeneous catalyst in the FDCA generation step It provides a method of manufacturing FDCA by replacing it with a substance.

The problem to be solved by the present invention is not limited to the problem(s) mentioned above, and another problem(s) that is not mentioned will be clearly understood by those skilled in the art from the following description.

In order to solve the above problem, a method for preparing alkoxy-methylfurfural from fructose according to an embodiment of the present invention is

(a-1) preparing a mixed solution by mixing fructose and an organic solvent;

(a-2) heating the mixed solution under a solid acid catalyst and reacting to prepare alkoxy-methylfurfural; And

(a-3) separating the solid acid catalyst from the alkoxy-methylfurfural solution through filtration; includes

In addition, the organic solvent may be methanol or ethanol.

In addition, the solid acid catalyst may be a graphene oxide (graphene oxide) or activated carbon (activated carbon) as a support, sulfonic acid (-SO ₃ H) is bonded to a functional group.

In addition, the filtration may be performed using a filter paper after cooling the alkoxy-methylfurfural solution to room temperature of 20 to 30°C.

A method for preparing 2,5-furandicarboxylic acid from alkoxy-methylfurfural according to another embodiment of the present invention

The alkoxy-methylfurfural solution may be pressurized and reacted under an oxidation catalyst to prepare 2,5-furandicarboxylic acid.

In addition, the pressurization may pressurize oxygen gas or air at 10 to 30 bar for 1 to 3 hours.

In addition, the oxidation catalyst is any one selected from the group consisting of activated carbon, zinc oxide, silicon dioxide, zirconium dioxide (ZrO ₂ ), hydrotalcite, cerium oxide, and aluminum oxide (Al ₂ O ₃ ).

It may be characterized in that any one metal selected from the group consisting of gold, platinum, palladium, and ruthenium is supported.

A method for preparing 2,5-furandicarboxylic acid from fructose according to another embodiment of the present invention

(a) preparing a mixed solution by mixing fructose and an organic solvent;

(b) heating and reacting the mixed solution under a solid acid catalyst to prepare alkoxy-methylfurfural;

(c) filtering and separating the solid acid catalyst from the alkoxy-methylfurfural solution in which the solid acid catalyst is mixed; And

(d) preparing 2,5-furandicarboxylic acid by pressing and reacting the solution from which the solid acid catalyst is separated under an oxidation catalyst.

In addition, the organic solvent may be methanol or ethanol.

In addition, the solid acid catalyst may be a graphene oxide (graphene oxide) or activated carbon (activated carbon) as a support, sulfonic acid (-SO ₃ H) is bonded to a functional group.

In addition, the pressurization may pressurize oxygen gas or air at 10 to 30 bar for 1 to 3 hours.

In addition, the oxidation catalyst is gold, platinum, palladium on a support selected from the group consisting of activated carbon, zinc oxide, silicon dioxide, zirconium dioxide (ZrO ₂ ), hydrotalcite, cerium oxide, and aluminum oxide (Al ₂ O ₃ ). And any one metal selected from the group consisting of ruthenium may be supported.

According to the present invention, 2,5-furandicarboxylic acid can be economically prepared from fructose, which is very abundant in the plant world.

In addition, after dehydration of fructose using a solid acid catalyst, the oxidation reaction can proceed immediately without additional post-treatment.

Also, by reacting fructose with a solid acid catalyst, alkoxy-methylfurfural can be prepared in a very high yield.

In addition, after preparing alkoxy-methylfurfural, 2,5-furandicarboxylic acid may be prepared and recovered in high yield by using a more economical heterogeneous oxidation catalyst.

In addition, after the dehydration reaction from fructose, 2,5-furandicarboxylic acid can be prepared and recovered through a one-pot process without a separate process of separating the intermediate.

In addition, the manufacturing process of 2,5-furandicarboxylic acid from fructose can be greatly reduced, thereby greatly reducing the manufacturing cost.

The effects of the invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a process flow diagram showing a process of a method for manufacturing alkoxy-methylfurfural using a solid acid catalyst according to an embodiment of the present invention.
2 is a process flow diagram showing a process of a method for producing 2,5-furandicarboxylic acid using a catalyst according to another embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Advantages and features of the present invention, and a method of achieving the same will become apparent with reference to the embodiments described below in detail together with the accompanying drawings.

However, the present invention is not limited by the embodiments disclosed below, but will be implemented in a variety of different forms, only these embodiments are intended to complete the disclosure of the present invention, and common knowledge in the technical field to which the present invention pertains. It is provided to completely inform the scope of the invention to those who have, and the invention is only defined by the scope of the claims.

In addition, when it is determined that related well-known technologies or the like may obscure the subject matter of the present invention in describing the present invention, detailed descriptions thereof will be omitted.

The present inventors believe that when the dehydration reaction of fructose is performed in an aqueous solution, the resulting 5-hydroxymethyl-2-furfural (hereinafter referred to as'HMF') is a secondary reaction with water. By confirming that it is easily decomposed into levulinic acid and formic acid, alkoxy-methylfurfural was first prepared using a solid acid catalyst in the presence of alcohol, and the solid acid catalyst was filtered. After removal, the final product 2,5-furandicarboxylic acid (hereinafter referred to as'FDCA') is used in high yield through an oxidation reaction using a heterogeneous oxidation catalyst without a separate treatment process. The present invention was completed by confirming what can be obtained.

As far as the present inventors know, FDCA is prepared through an oxidation reaction using a heterogeneous oxidation catalyst without alkoxy-methylfurfural separation after preparing alkoxy-methylfurfural from fructose. No method has been disclosed.

1 is a process flow diagram showing a process of a method for producing alkoxy-methylfurfural from fructose according to an embodiment of the present invention, and FIG. 2 is a process flow diagram showing a process of a method for producing alkoxy-methylfurfural from fructose according to another embodiment of the present invention. ,5-furandicarboxylic acid is a process flow diagram showing the process of the manufacturing method.

The present invention is a method of preparing an intermediate alkoxy-methylfurfural from fructose using a solid acid catalyst, and reacting the intermediate alkoxy-methylfurfural with a heterogeneous oxidation catalyst to obtain 2,5-furandicar in high yield. It provides a method for preparing 2,5-furandicarboxylic acid from fructose, including a method for preparing an acid.

First, referring to FIG. 1, a method for preparing alkoxy-methylfurfural from fructose according to an embodiment of the present invention is

(a-1) preparing a mixed solution by mixing fructose and an organic solvent;

(a-2) heating the mixed solution under a solid acid catalyst and reacting to prepare alkoxy-methylfurfural; And

(a-3) separating the solid acid catalyst by filtering the mixed solution containing the alkoxy-methylfurfural; includes

First, a mixed solution is prepared by mixing fructose and an organic solvent (S10).

The fructus is a carbohydrate and is converted to alkoxy-methylfurfural by dehydration.

The alkoxy-methylfurfural is 5-methoxymethylfurfural (“MMF”) or 5-ethoxymethylfurfural (“EMF”).

The organic solvent is methanol or ethanol.

C ₃ or more alcohols other than methanol or ethanol are difficult to convert to alkoxy-methylfurfural by dehydrating fructose using a solid acid catalyst, and there is a problem of generating by-products after the reaction.

The mixed solution may be heated and reacted under a solid acid catalyst to prepare alkoxy-methylfurfural (S20).

The solid acid catalyst acts as a proton donor or electron acceptor and is used as a catalyst for dehydration.

The solid acid catalyst may be a graphene oxide (graphene oxide) or activated carbon (activated carbon) as a support, sulfonic acid (-SO ₃ H) is bonded to a functional group.

Hereinafter, GO-SO ₃ H means that sulfonic acid is bonded to graphene oxide, and AC-SO ₃ H means that sulfonic acid is bonded to activated carbon.

In the graphene oxide and activated carbon, the sulfonic acid functional group acts as a Bronsted acidic function.

Therefore, the solid acid catalyst has very high catalytic activity and is very advantageous for dehydration reaction.

Except for the solid acid catalyst, the conversion rate of fructose is low, and a reaction temperature of 90° C. or higher is required during the heating reaction, thereby reducing process efficiency.

The heating may be performed at 60 to 80° C. for 12 to 32 hours.

In the above heating range, fructose may be converted to 100%, and EMF or MMF may be prepared in a yield of 70 to 90%.

When the heating temperature is lower than 60° C., there is a disadvantage in that the dehydration reaction rate of fructose is low, and when it is higher than 80° C., loss due to evaporation of alcohol during normal pressure reaction and side reactions occur.

The solid acid catalyst is separated from the mixed solution containing the alkoxy-methylfurfural through filtration (S30).

The filtration may be performed using a filter paper after cooling the alkoxy-methylfurfural solution to room temperature of 20 to 30°C.

The reaction catalyst may be removed through the filtration.

If the solid acid catalyst is not separated by filtration, there is a problem in that by-products are generated or the FDCA generation rate is lowered in the step of generating FDCA from the subsequent alkoxy-methylfurfural under the oxidation catalyst.

Therefore, EMF or MMF can be prepared using a solid acid catalyst, and unlike a separate treatment process for separating the conventional high boiling point organic solvent phase, the solid acid catalyst is very effectively removed through filtration and alkoxy-methylfurfural (alkoxy-methylfurfural) can be prepared.

A method for preparing 2,5-furandicarboxylic acid from alkoxy-methylfurfural according to another embodiment of the present invention

The alkoxy-methylfurfural solution may be pressurized and reacted under an oxidation catalyst to prepare 2,5-furandicarboxylic acid.

The pressurization may pressurize oxygen gas or air at 10 to 30 bar for 1 to 3 hours.

FDCA can be manufactured with high efficiency by using an oxidation catalyst within the pressurized range, and if it is not within the above range, the yield due to the oxidation reaction is low, and if it exceeds the above range, the reaction yield does not increase and energy is reduced. There is a problem that is consumed more.

The oxidation catalyst is gold, platinum, palladium, and any one selected from the group consisting of activated carbon, zinc oxide, silicon dioxide, zirconium dioxide (ZrO ₂ ), hydrotalcite, cerium oxide, and aluminum oxide (Al ₂ O ₃ ). Any one metal selected from the group consisting of ruthenium may be supported.

The oxidation catalyst is a heterogeneous catalyst, and since it is easier to separate the catalyst from the FDCA after an oxidation reaction compared to a conventional homogeneous catalyst, it is environmentally friendly and can greatly reduce the process cost.

Referring to Figure 2, a method for preparing 2,5-furandicarboxylic acid using a catalyst according to another embodiment of the present invention

(a) preparing a mixed solution by mixing fructose and an organic solvent;

(b) heating and reacting the mixed solution under a solid acid catalyst to prepare alkoxy-methylfurfural;

(c) filtering and separating the solid acid catalyst from the alkoxy-methylfurfural solution in which the solid acid catalyst is mixed; And

(d) pressurizing and reacting the solution from which the solid acid catalyst is separated under an oxidation catalyst to prepare 2,5-furandicarboxylic acid.

In addition, the method for producing FDCA from fructus using the solid acid catalyst and the oxidation catalyst may be performed according to the following Scheme 1.

[Scheme 1]

In one embodiment of the present invention, fructose is mixed with ethanol under a solid acid catalyst to generate EMF, an intermediate, and is converted to FDCA by reacting with a Pt/C oxidation catalyst under oxygen pressure.

First, a mixed solution is prepared by mixing fructose and an organic solvent (S100).

The organic solvent may be methanol or ethanol.

C ₃ or more alcohols other than methanol or ethanol are difficult to convert to alkoxy-methylfurfural by dehydrating fructose using a solid acid catalyst, and there is a problem of generating by-products after the reaction.

The mixed solution is heated and reacted under a solid acid catalyst to prepare alkoxy-methylfurfural (S200).

The solid acid catalyst may be a graphene oxide (graphene oxide) or activated carbon (activated carbon) as a support, sulfonic acid (-SO ₃ H) is bonded to a functional group.

It is difficult for sulfonic acid to be bonded to functional groups other than the support.

The solid acid catalyst in which the sulfonic acid is bonded to a functional group acts as a proton donor or electron acceptor and is used as a catalyst for dehydration reaction.

In the graphene oxide and activated carbon, the sulfonic acid functional group acts as a Bronsted acidic function.

Therefore, the solid acid catalyst has very high catalytic activity and is very advantageous for dehydration reaction.

Except for the solid acid catalyst, the conversion rate of fructose is low, and a reaction temperature of 90° C. or higher is required during the heating reaction, thereby reducing process efficiency.

The heating may be performed at 60 to 80° C. for 12 to 32 hours.

In the above heating range, fructose may be converted to 100%, and EMF or MMF may be prepared in a yield of 70 to 90%.

The solid acid catalyst is filtered and separated from the alkoxy-methylfurfural solution in which the solid acid catalyst is mixed (S300).

The reaction catalyst may be removed through the filtration.

EMF or MMF can be prepared using a solid acid catalyst, and unlike a separate treatment process for separating the conventional high boiling point organic solvent phase, the solid acid catalyst is very effectively removed through filtration, and EMF or MMF is obtained at a high conversion rate. Alkoxy-methylfurfural can be prepared.

The solution from which the solid acid catalyst is separated is pressurized and reacted under an oxidation catalyst to prepare 2,5-furandicarboxylic acid (S400).

The pressurization may pressurize oxygen gas or air at 10 to 30 bar for 1 to 3 hours.

FDCA can be produced with high efficiency by using an oxidation catalyst within the pressurized range, and if it is not within the above range, the yield due to the oxidation reaction is low, and if it exceeds the above range, energy is not increased without increasing the reaction yield. There is a problem that is consumed more.

The oxidation catalyst is made of gold, platinum, palladium, and ruthenium on a support selected from the group consisting of activated carbon, zinc oxide, silicon dioxide, hydrotalcite, cerium oxide (CeO ₂ ) and aluminum oxide (Al ₂ O ₃ ). Any one metal selected from the group may be supported.

By using the support, a heterogeneous catalyst can be prepared to perform an oxidation reaction, and the catalyst can be easily recovered and reused, thereby reducing the overall process cost and increasing the efficiency of the process.

Under the oxidation catalyst, the oxidation reaction of EMF or MMF may be performed by pressurization within the above range, and FDCA may be prepared in a yield of 90% or more.

Hereinafter, preferred examples are presented to aid in the understanding of the present invention, but the following examples are only illustrative of the present invention, and the scope of the present invention is not limited to the following examples.

Experimental Example 1. Preparation of solid acid catalyst

Graphene according to the literature (PP Upare, J.-W. Yoon, H.-Y. Kang, DW Hwang, YK Hwang, HH Kung, J.-S. Chang, Green Chem. 15 (2013) 2935-2943) Sulfonation of the oxide and activated carbon was performed to prepare solid acid catalysts GO-SO ₃ H and AC-SO ₃ H.

The content of the sulfone group (S-density, mmol/g) was confirmed through elemental analysis of the sulfonated material.

AC-SO ₃ H contained 2.5 mmol/g -SO ₃ H group, which was confirmed to be about twice as much as 1.2 mmol/g of GO-SO ₃ H, so that AC-SO ₃ H has a stronger acidic point (acidic site).

In addition, AC-SO ₃ H and GO-SO ₃ H have higher S-density than that of MTS-GO (methoxytrimethylsiliane-graphene oxide) or Zr(SO ₄ ) ₂ catalyst, so it was predicted to be very effective in the dehydration reaction of fructose.

Example 1. Preparation of 5-ethoxymethylfurfural (EMF) from fructose

1 g of fructose was mixed with 9 ml of ethanol and 1.0 g of a solid acid catalyst (GO-SO ₃ H) in which sulfonic acid is bound to graphene oxide, and heated to 70° C., followed by reaction for 24 hours. After the reaction, the sample was cooled to room temperature, and the GO-SO ₃ H catalyst was separated from the solution through filtration.

As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the EMF yield was 72%.

Example 2. Preparation of 5-ethoxymethylfurfural (EMF) from fructose

1 g of fructose was mixed with 9 ml of ethanol and 1.0 g of a GO-SO ₃ H catalyst, heated to 70° C., and reacted for 30 hours. After the reaction, the sample was cooled to room temperature, and the GO-SO ₃ H catalyst was separated from the solution through filtration.

As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the EMF yield was 90%.

Example 3. Preparation of 5-ethoxymethylfurfural (EMF) from fructose

1 g of fructose was mixed with 9 ml of ethanol and 1.0 g of AC-SO ₃ H catalyst, heated to 70° C., and reacted for 32 hours. After the reaction, the sample was cooled to room temperature, and the AC-SO3H catalyst was separated from the solution through filtration.

As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the EMF yield was 91%.

The EMF/ethanol solution obtained through the above process was heated to 60° C., maintained for 48 hours, and then cooled to room temperature.

As a result of analyzing the solution through liquid chromatography, there was almost no change in the concentration of EMF.

Therefore, when EMF is prepared in an ethanol solvent using an AC-SO ₃ H catalyst, EMF can be obtained in a high yield of 90% or more, and when the catalyst is removed after the catalytic reaction is completed, the secondary reaction of EMF can be suppressed. You can see that there is.

Example 4. Preparation of 5-methoxymethylfurfural (MMF) from fructose

1 g of fructose was mixed with 9 ml of methanol and 1.0 g of a GO-SO ₃ H catalyst, heated to 60° C., and reacted for 30 hours. After the reaction, the sample was cooled to room temperature, and the GO-SO ₃ H catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the MMF yield was 91%.

The MMF/methanol solution obtained through the above process was heated to 60° C., maintained for 48 hours, and then cooled to room temperature. As a result of analyzing the solution through liquid chromatography, there was almost no change in the concentration of MMF.

Therefore, when MMF is prepared in a methanol solvent using an AC-SO ₃ H catalyst, MMF can be obtained in a high yield of 90% or more, and when the catalyst is removed after the catalytic reaction is completed, the secondary reaction of MMF can be suppressed. You can see that you can.

Example 5. Preparation of 5-Methoxymethylfurfural (MMF) from fructose

1 g of fructose was mixed with 9 ml of methanol and 1.5 g of a catalyst (hereinafter referred to as “AC-SO ₃ H”) in which a sulfonic acid was bonded to a functional group on an activated carbon support, heated to 60° C., and reacted for 21 hours.

After the reaction, the sample was cooled to room temperature, and the AC-SO ₃ H catalyst was separated from the solution through filtration.

As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the MMF yield was 90%.

Thus, the AC-SO case of preparing MMF on a methanol solvent using a ₃ H catalyst, AC-SO ₃ as H is increased amount of catalyst, and the MMF production rate to find out faster, this AC-SO ₃ H catalyst with MMF yield and reaction time can be controlled by adjusting the amount.

Example 6. Preparation of 5-methoxymethylfurfural (MMF) from fructose

1 g of fructose was mixed with 9 ml of methanol and 1.0 g of an AC-SO ₃ H catalyst, heated to 80° C., and reacted for 12 hours.

After the reaction, the sample was cooled to room temperature, and the AC-SO ₃ H catalyst was separated from the solution through filtration.

As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the MMF yield was 79%.

When confirming Examples 1 to 6, it can be seen that fructose can be mixed with a solid acid catalyst and heated to obtain an alkoxy-methylfurfural EMF or MMF with a high conversion rate.

Example 7. Preparation of FDCA from EMF

The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with platinum on an activated carbon support (hereinafter'Pt(5%)/C'), heated to 100° C., and then heated to 15 bar using O ₂ gas. After raising the pressure, the reaction was carried out for 2 hours.

After the reaction, the sample was cooled to room temperature of 27° C., and the solid mixture was separated from the solution through filtration.

The solid mixture was mixed with 10 ml of a dimethylformamide (hereinafter referred to as'DMF') solvent, and then the catalyst was separated from the solution through filtration.

As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 97%.

In the case of using a heterogeneous oxidation catalyst coated with a small amount of platinum on the activated carbon support, it has the advantage of being able to reuse the catalyst because it is easy to separate the reaction solution from the catalyst because it can be easily separated from FDCA through filtration after FDCA generation. .

Example 8. Preparation of FDCA from EMF

The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with gold on a hydrotalcite support (hereinafter, referred to as'Au(5%)/hydrotalcite'), heated to 100° C., and then used O ₂ gas. After raising the pressure to 15 bar, the reaction was carried out for 2 hours.

After the reaction, the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.

After mixing the solid mixture with 10 ml of a DMF solvent, the catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 95%.

Example 9. Preparation of FDCA from EMF

The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of Au (5%)/hydrotalcite catalyst, heated to 100° C., and the pressure was raised to 10 bar using O ₂ gas, and the reaction was carried out for 2 hours.

After the reaction, the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.

After mixing the solid mixture with 10 ml of a DMF solvent, the catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 90%.

Example 10. Preparation of FDCA from EMF

The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a ruthenium-coated catalyst (hereinafter referred to as'Ru(5%)/C') on an activated carbon support, heated to 100° C., and then heated to 15 bar using O ₂ gas. After raising the pressure, the reaction was carried out for 2 hours.

After the reaction, the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.

After mixing the solid mixture with 10 ml of a DMF solvent, the catalyst was separated from the solution through filtration.

As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 96%.

Example 11. Preparation of FDCA from EMF

The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with ruthenium on a cerium oxide support (hereinafter, referred to as'Ru(5%)/CeO ₂ '), heated to 100° C., and then 15 using O ₂ gas. After raising the pressure to bar, the reaction was carried out for 2 hours.

After the reaction, the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.

After mixing the solid mixture with 10 ml of a DMF solvent, the catalyst was separated from the solution through filtration.

As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 95%.

Example 12. Preparation of FDCA from EMF

The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with palladium on an activated carbon support (hereinafter referred to as'Pd(5%)/C'), heated to 100° C., and then 15 bar using O ₂ gas. After raising the pressure, the reaction was carried out for 2 hours.

After the reaction, the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.

After mixing the solid mixture with 10 ml of a DMF solvent, the catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 92%.

Example 13. Preparation of FDCA from EMF

The EMF/ethanol solution prepared in Example 1 was mixed with 0.5 g of a catalyst coated with platinum on an activated carbon support (hereinafter, referred to as'Pt(5%)/C'), heated to 100° C., and then pressurized to 20 bar using air. After raising the reaction was carried out for 2 hours.

After the reaction, the sample was cooled to room temperature, and the solid mixture was separated from the solution through filtration.

After mixing the solid mixture with 10 ml of a DMF solvent, the catalyst was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the EMF conversion rate was 100% and the FDCA yield was 93%.

Comparative Example 1. Preparation of 5-ethoxymethylfurfural (EMF) from fructose

1 g of fructose was mixed with 9 ml of ethanol and 1.0 g of Amberlsyt-15 resin, a commercial catalyst, and heated to 70° C., followed by reaction for 24 hours.

After the reaction, the sample was cooled to room temperature, and amberlyst-15 resin was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 61% and the EMF yield was 31%.

Comparative Example 2. Preparation of 5-ethoxymethylfurfural (EMF) from fructose

1 g of fructose was mixed with 9 ml of ethanol and 1.0 g of Amberlsyt-15 resin, heated to 80°C, and reacted for 24 hours. After the reaction, the sample was cooled to room temperature, and amberlyst-15 resin was separated from the solution through filtration. As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 73% and the EMF yield was 38%.

Comparative Example 3. Preparation of 5-ethoxymethylfurfural (EMF) from fructose

1 g of fructose was mixed with 9 ml of ethanol and 1.0 g of Amberlsyt-131 resin, heated to 80°C, and reacted for 46 hours. After the reaction, the sample was cooled to room temperature, and amberlyst-15 resin was separated from the solution through filtration.

As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the EMF yield was 86%.

Comparative Example 4. Preparation of 5-hydroxymethylfurfural (HMF) from fructose

1 g of fructose was mixed with 9 ml of 1-butanol and 1.0 g of Amberlsyt-15 resin, heated to 100° C., and reacted for 5 hours. After the reaction, the sample was cooled to room temperature, and amberlyst-15 resin was separated from the solution through filtration.

As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the HMF yield was 86%.

Comparative Example 5. Preparation of 5-hydroxymethylfurfural (HMF) from fructose

1 g of fructose was mixed with 9 ml of isopropyl alcohol and 1.0 g of Amberlsyt-15 resin, heated to 100° C., and reacted for 5 hours. After the reaction, the sample was cooled to room temperature, and amberlyst-15 resin was separated from the solution through filtration.

As a result of analyzing the separated solution through liquid chromatography, it was confirmed that the fructose conversion rate was 100% and the HMF yield was 42%.

Therefore, it was confirmed that the EMF generation rate was slow and the yield was very low when the conventional commercial catalyst Amberlyst resin was used.

In addition, when isopropyl alcohol or 1-butanol other than methanol or ethanol was used as a solvent, alkoxy-methylfurfural was not produced, and 5-hydroxymethylfurfural (HMF) was mainly produced. have.

Comparative Example 6. Preparation of FDCA from EMF

The EMF/ethanol solution prepared in Example 1 was heated to 100° C. without an oxidation catalyst, and the pressure was raised to 20 bar using air, and the reaction was carried out for 2 hours.

After the reaction, the sample was cooled to room temperature, the solid mixture was mixed with 10 ml of a DMF solvent, and analyzed by liquid chromatography. As a result, the EMF conversion was found to be 15% and the FDCA yield was 10%.

So far, a method for preparing alkoxy-methylfurfural from fructose according to an embodiment of the present invention, a method for preparing 2,5-furandicarboxylic acid from alkoxy-methylfurfural, and 2,5-furandicar from fructose Although specific examples of the method for preparing carboxylic acid have been described, it is obvious that various implementation modifications are possible within the limit not departing from the scope of the present invention.

Therefore, the scope of the present invention is limited to the described embodiments and should not be defined, and should be defined by the claims and equivalents as well as the claims to be described later.

That is, it should be understood that the above-described embodiments are illustrative in all respects and not limiting, and the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and the meaning and scope of the claims and All changes or modified forms derived from the equivalent concept should be interpreted as being included in the scope of the present invention.

Claims (12)

(a-1) preparing a mixed solution by mixing fructose and an organic solvent;
(a-2) heating the mixed solution under a solid acid catalyst and reacting to prepare alkoxy-methylfurfural; And
(a-3) Separating the solid acid catalyst by filtering the mixed solution containing the alkoxy-methylfurfural; Method for producing alkoxy-methylfurfural from fructose comprising.
The method of claim 1,
The organic solvent is
Method for producing alkoxy-methylfurfural from fructose, characterized in that methanol or ethanol.
The method of claim 1,
The solid acid catalyst is
A method of producing alkoxy-methylfurfural from fructose, characterized in that sulfonic acid (-SO ₃ H) is bonded to a functional group using graphene oxide or activated carbon as a support.
The method of claim 1,
The filtration is
Method for producing alkoxy-methylfurfural from fructose, characterized in that the alkoxy-methylfurfural solution is cooled to room temperature at 20 to 30° C. and then performed using a filter paper.
An alkoxy-methylper, characterized in that the alkoxy-methylfurfural solution prepared by the method of claim 1 is pressurized and reacted under an oxidation catalyst to produce 2,5-furandicarboxylic acid. A method of producing 2,5-furandicarboxylic acid from fural.
The method of claim 5,
The pressurization is a method for producing 2,5-furandicarboxylic acid from alkoxy-methylfurfural, characterized in that the pressurization of oxygen gas or air at 10 to 30 bar for 1 to 3 hours.
The method of claim 6,
The oxidation catalyst is
Activated carbon, zinc oxide, silicon dioxide, zirconium dioxide (ZrO ₂ ), hydrotalcite, cerium oxide, and aluminum oxide (Al ₂ O ₃ ) to any one selected from the group consisting of a support
Method for producing 2,5-furandicarboxylic acid from alkoxy-methylfurfural, characterized in that any one metal selected from the group consisting of gold, platinum, palladium, and ruthenium is supported.
(a) preparing a mixed solution by mixing fructose and an organic solvent;
(b) heating and reacting the mixed solution under a solid acid catalyst to prepare alkoxy-methylfurfural;
(c) filtering and separating the solid acid catalyst from the alkoxy-methylfurfural solution in which the solid acid catalyst is mixed; And
(D) preparing 2,5-furandicarboxylic acid by pressurizing and reacting the solution from which the solid acid catalyst is separated under an oxidation catalyst to prepare 2,5-furandicarboxylic acid from fructose.
The method of claim 8,
The organic solvent is
Method for producing 2,5-furandicarboxylic acid from fructose, characterized in that it is methanol or ethanol.
The method of claim 8,
The solid acid catalyst is
Graphene oxide (graphene oxide) or activated carbon (activated carbon) as a support, characterized in that the sulfonic acid (-SO ₃ H) is bonded to a functional group, characterized in that the 2,5-furandicarboxylic acid production method from fructose.
The method of claim 9,
The pressurization is
Method for producing 2,5-furandicarboxylic acid from fructose using a catalyst, characterized in that oxygen gas or air is pressurized at 10 to 30 bar for 1 to 3 hours.
The method of claim 9,
The oxidation catalyst is
Activated carbon, zinc oxide, silicon dioxide, zirconium dioxide (ZrO2), hydrotalcite, cerium oxide, and aluminum oxide (Al ₂ O ₃ ) in any one selected from the group consisting of a support
Method for producing 2,5-furandicarboxylic acid from fructose, characterized in that any one metal selected from the group consisting of gold, platinum, palladium and ruthenium is supported.

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