KR101937362B1 - Method for preparing fdca from hmf using gold-palladium bimetallic nanoparticles supported on an anion exchange resin - Google Patents

Abstract

[화학식 2]

The present invention relates to a process for preparing 2,5-furan dicarboxylic acid (FDCA) represented by the following formula (2) by an oxidation reaction of HMF (5-Hydroxymethylfurfural) represented by the following formula Wherein the catalyst comprises an anion exchange resin and AuPd Bimetallic nanoparticles carried on the anion exchange resin, wherein the gold (Au) -palladium (Pd) bimetallic moles (Au) -Palladium (Pd) bimetallic nanoparticle catalyst supported on anion exchange resin has a characteristic of maintaining high activity even when reused. have.
[Chemical Formula 1]

(2)

Description

Technical Field [0001] The present invention relates to a method for preparing FDCA from HMF using gold palladium bimetallic nanoparticles supported on an anion exchange resin, and a method for producing FDCA from HMF using gold palladium bimetallic nanoparticles supported on an anion exchange resin.

The present invention relates to a process for preparing FDCA from HMF using gold palladium bimetallic nanoparticles supported on an anion exchange resin, and more particularly to a process for preparing FDCA from gold phalladium bimetallic nanoparticles supported on an anion exchange resin, And a process for obtaining FDCA from HMF at a high yield by a simple process.

The steep decline in petroleum resources with limited reserves and the surge in oil demand due to the growth of emerging economies are leading to an era of high oil prices, triggering an imbalance in market supply and demand. Moreover, irreversible greenhouse gases arising from the indiscriminate use of oil are causing serious environmental problems such as global warming.

Already, countries around the world are making efforts to replace petroleum resources through renewable and sustainable biomass. Biofuels such as bioethanol and biodiesel, and bioplastic monomers such as lactic acid and propanediol, To replace transportation fuels or petrochemicals.

As a result of this effort, it has been proposed that a substance which has recently been spotlighted is 5-hydroxymethyl-2-furfural (HMF) represented by the following reaction formula, which is a biomass-derived furan compound, 2,5-Furandicarboxylic acid (FDCA).

[Reaction Scheme]

FDCA can be used to prepare polyester polymers with furan derivatives containing two carboxylic acids by oxidizing the aldehyde groups and alcohol groups of HMF, and FDCA esters can be used as substitutes for phthalate plasticizers There are characteristics.

Studies have been conducted to prepare FDCA from 5- (acetoxymethyl) furfural (AMF) ester formed through the reaction of HMF with an acetic acid solvent (WO 2011/043661), but the yield is low and the productivity is low .

In addition, a technique for manufacturing FDCA at a temperature higher than 140 ° C. by using an oxidation catalyst based on cobalt and manganese and containing bromide has been studied. However, the FDCA obtained using this method has a disadvantage of only 70% .

Therefore, it is necessary to develop an FDCA manufacturing method which can improve the usability to industry by simplifying the process and high productivity, by developing a highly recyclable catalyst and manufacturing FDCA from HMF using the same.

Disclosure of the Invention The object of the present invention is to solve the above problems, and it is an object of the present invention to simplify the process of producing FDCA from HMF by using gold palladium bimetallic nanoparticles supported on an anion exchange resin as a catalyst, ) Ratio (molar ratio) is controlled to obtain FDCA of 90% or higher yield, and a method for producing FDCA from HMF having excellent selectivity is provided.

Also provided is a method for preparing FDCA from HMF using a small amount of base, by using a metal catalyst comprising an anion exchange resin with weak basicity.

Also provided is a gold palladium bimetallic nanoparticle catalyst supported on an anion exchange resin which can be used for commercial continuous processes while maintaining high activity even after reuse.

According to an aspect of the present invention, there is provided a process for producing 2,5-furandicarboxylic acid (FDCA) represented by the following formula (2) by oxidizing HMF (5-Hydroxymethylfurfural) represented by the following formula Wherein the catalyst comprises an anion exchange resin and gold palladium bimetallic nanoparticles carried on the anion exchange resin.

[Formula 1]

(2)

The molar ratio of gold (Au): palladium (Pd) of the gold palladium bimetallic nanoparticles may be 0.5: 1.0 to 6.0: 1.0.

The anion exchange resin may comprise a support and an amine group covalently bonded on the support.

The anion exchange resin may be one represented by the following structural formula 1 or a salt thereof.

[Structural formula 1]

In formula 1,

X is an atomic bond, a C1 to C10 alkylene group, or a C6 to C10 arylene group,

R ¹ and R ² are the same or different from each other, and each is a hydrogen atom, a substituted or unsubstituted C 1 to C 15 linear alkyl group with a hydroxy group, or a substituted or unsubstituted C 3 to C 15 branched alkyl group having a hydroxy group.

The anion exchange resin may be one represented by the following structural formula 2 or a salt thereof.

[Structural formula 2]

In formula 2,

R ¹ and R ² are the same or different from each other and each is a hydrogen atom, a substituted or unsubstituted C1 to C15 linear alkyl group with a hydroxy group, or a substituted or unsubstituted C3 to C15 branched alkyl group having a hydroxy group,

m is an integer of 1 to 3;

The anion exchange resin may be one represented by the following structural formula 3 or a salt thereof.

[Structural Formula 3]

In Structure 3,

R ³ is a hydrogen atom, a C1 to C10 straight chain alkyl group, or a C3 to C10 branched alkyl group.

m and n are the same or different and each independently is an integer of 1 to 3,

and q is an integer of 1 to 10.

The anion exchange resin may be covalently bonded with a glucamine group or a salt thereof on the support.

The support may be porous or gel-like and may be swelled under a solvent.

The support may comprise at least one polymer selected from polystyrene, cross-linked polystyrene, copolymerized polystyrene and grafted polystyrene.

The anion exchange resin may be basic.

During the oxidation reaction, sodium carbonate (Na ₂ CO ₃ ), sodium methoxide, sodium hydrogencarbonate (NaHCO ₃ ), potassium carbonate (K ₂ CO ₃ ), potassium bicarbonate (KHCO ₃ ) NaOH) and potassium hydroxide (KOH) may be further added to perform the oxidation reaction.

The solvent may be a polar solvent.

The catalyst can be reused.

The yield of 2,5-furandicarboxylic acid (FDCA) may be 80 to 99%.

The preparation of the furan-based compound for preparing 2,5-furandicarboxylic acid (FDCA) can be carried out at room temperature.

The catalyst may be prepared by reacting a reducing agent, an anion exchange resin, a gold (Au) precursor and a palladium (Pd) precursor in a solvent.

The gold (Au) precursor may include at least one selected from gold chloride (AuCl ₃ ) and gold bromide (AuBr ₃ ).

The palladium (Pd) precursor may include at least one selected from the group consisting of palladium chloride (PdCl ₂ ), palladium bromide (PdBr ₂ ) and palladium acetate (Pd (OAc) ₂ ).

Wherein the reducing agent is selected from the group consisting of sodium borohydride (NaBH ₄ ), sodium cyanoborohydride (NaBH ₃ CN), lithium aluminum hydride (LiAlH ₄ ) and hydrazine (N ₂ H ₄ ) It may be at least one selected.

The method of producing the furan compound of the present invention can simplify the process for producing FDCA from HMF by using bimetallic nanoparticles of gold (Au) -palladium (Pd) supported on an anion exchange resin as a catalyst, By controlling the ratio of gold (Au) to palladium (Pd), FDCA having a yield of 90% or more is obtained, and it has an effect of having excellent selectivity.

Further, by using an anion exchange resin having weak basicity, FDCA can be produced from HMF using a small amount of a base.

In addition, the gold palladium bimetallic nanoparticle nanoparticle catalyst supported on the anion exchange resin maintains high activity even after reuse, and is applicable to a commercial continuous process.

1 is an XPS image of a gold palladium bimetallic nanoparticle nanoparticle catalyst supported on an anion exchange resin.
2 is a TEM image of a gold palladium bimetallic nanoparticle nanoparticle catalyst supported on an anion exchange resin.
FIG. 3 is a graph showing a time-dependent analysis of the oxidation of HMF to FDCA.
FIG. 4 is a graph showing the conversion of HMF and the selectivity of FDCA according to the type of anion exchange resin carrying gold palladium bimetallic nanoparticles.
FIG. 5 is an analysis of the catalyst recyclability of gold palladium bimetallic nanoparticles carried on an anion exchange resin.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention.

However, the following description does not limit the present invention to specific embodiments. In the following description of the present invention, detailed description of related arts will be omitted if it is determined that the gist of the present invention may be blurred .

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, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.

A method for producing 2,5-furandicarboxylic acid (FDCA) using gold palladium bimetallic nanoparticles supported on an anion exchange resin of the present invention will be described.

The present invention relates to a process for preparing 2,5-furandicarboxylic acid (FDCA) represented by the following formula (2) by oxidation reaction of HMF (Hydroxy Methyl Furfural) represented by the following formula (1) Wherein the anion exchange resin comprises an anion exchange resin and gold palladium bimetallic nanoparticles carried on the anion exchange resin.

[Chemical Formula 1]

(2)

The molar ratio of gold (Au): palladium (Pd) of the gold palladium bimetallic nanoparticles may be 0.5: 1.0 to 6.0: 1.0.

The anion exchange resin may comprise a support and an amine group covalently bonded to the support.

The anion exchange resin may be one represented by the following structural formula 1 or a salt thereof,

[Structural formula 1]

In formula 1,

X is an atomic bond, a C1 to C10 alkylene group, or a C6 to C10 arylene group,

R ¹ and R ² are the same or different from each other and are each independently a hydrogen atom, a substituted or unsubstituted C1 to C15 linear alkyl group with a hydroxy group, or a substituted or unsubstituted C3 to C15 branched alkyl group having a hydroxy group.

Preferably, the anion exchange resin may be one represented by the following structural formula 2 or a salt thereof,

[Structural formula 2]

In formula 2,

R ¹ and R ² are the same or different from each other and each is a hydrogen atom, a substituted or unsubstituted C1 to C15 linear alkyl group with a hydroxy group, or a substituted or unsubstituted C3 to C15 branched alkyl group having a hydroxy group,

m is an integer of 1 to 3;

More preferably, the anion exchange resin may be one represented by the following structural formula 3 or a salt thereof.

[Structural Formula 3]

In Structure 3,

R ³ is a hydrogen atom, a C1 to C10 straight chain alkyl group, or a C3 to C10 branched alkyl group.

m and n are the same or different and each independently is an integer of 1 to 3,

and q is an integer of 1 to 10.

The anion exchange resin may be covalently bonded with a glucamine group or a salt thereof on the support.

The support may be porous or gel-like and may be swelled under a solvent.

The support may comprise a polymer such as polystyrene, cross-linked polystyrene, copolymerized polystyrene, grafted polystyrene, or the like.

The anion exchange resin may be basic.

(Na ₂ CO ₃ ), sodium hydrogencarbonate (NaHCO ₃ ), potassium carbonate (K ₂ CO ₃ ), potassium bicarbonate (KHCO ₃ ), sodium hydroxide (NaOH), potassium hydroxide (KOH) May be further added to carry out the oxidation reaction.

The solvent may be a polar solvent, water may be used, and a polar organic solvent which can be mixed with water may be used together. Specific examples of the polar organic solvent include methanol, ethanol, n-propanol, iso- But are not limited to, dioxane, dimethylsulfoxide (DMSO), dimethylformamide (DMF), and the like.

The catalyst can be reused and the catalyst of the present invention can be reused 5 to 10 times to oxidize HMF to produce FDCA.

The yield of 2,5-furan dicarboxylic acid (FDCA) may be 80 to 99%.

The preparation of the furan-based compound for preparing 2,5-furandicarboxylic acid (FDCA) can be carried out at room temperature.

The catalyst may be prepared by reacting a reducing agent, an anion exchange resin, a gold (Au) precursor and a palladium (Pd) precursor in a solvent.

The gold (Au) precursor may be gold chloride (AuCl ₃ ), gold bromide (AuBr ₃ ), or the like.

The palladium (Pd) precursor may be palladium chloride (PdCl ₂ ), palladium bromide (PdBr ₂ ), palladium acetate (Pd (OAc) ₂ ) or the like.

However, the range of the gold (Au) precursor and the palladium (Pd) precursor of the present invention is not limited thereto.

The reducing agent may be selected from the group consisting of sodium borohydride (NaBH ₄ ), sodium cyanoborohydride (NaBH ₃ CN), lithium aluminum hydride (LiAlH ₄ ), hydrazine (N ₂ H ₄ ) Can be used.

Hereinafter, the structure of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[Example]

Manufacturing example  One: HMF  Produce

430 mg of high fructose corn syrup (HFCS) (300 mg of carbohydrates, 270 mg of fructose in carbohydrates, 1.5 mmol) is placed in a tubular type reactor. Next, 300 mg of Amberlyst 15 resin (Aldrich, 4.7 meq of H ^& lt ^{; +} & gt ^; / g resin) to which a sulfonic acid group is attached to a polystyrene support is charged into the reactor (1.4 mmol of Bronsted acid in a solid acid catalyst). Subsequently, 3 mL of 1,4-dioxane was added to the reactor, and the mixture was stirred for 4 hours while gradually heating to 100 to obtain 5-hydroxymethyl-2-furfural ( HMF) (yield: 81% or more).

Manufacturing example  2: Anion exchange resin Supported  Gold (Au) palladium (Pd) ( 0.5: 1 ) By Metallic  The nanoparticle catalyst (2% AuPd ( 0.5: 1 ) - IRA743 )Produce

First, the gold (Au) precursor Gold (III) chloride trihydrate (AuCl ₃ .3H ₂ O 99.9%) and the palladium (Pd) precursor Palladium (II) were mixed to provide a molar ratio of gold (Au) and palladium (Pd) chloride (PdCl ₂ , 99.9 +%) was weighed and added to 200 ml of ethanol to prepare a mixed solution. In the mixed solution, gold (Au) and palladium (Pd) account for 2 wt%. To the mixed solution, 5 g of an anion exchange resin represented by the following structural formula 4 (IRA743 resin, commercial resin dried under vacuum at 313 K overnight) was added and the resin beads were stirred for 24 hours to prepare a mixture. The anion exchange resin is filtered, and gold (Au) and palladium (Pd) are reduced using sodium borohydride, filtered, washed with 400 ml of ethanol and vacuum dried to obtain gold palladium bimetallic nano particle catalyst .

[Structural Formula 4]

Production Example 3: Preparation of 2% AuPd (1: 1) -IRA743 catalyst

Except that the molar ratio of gold (Au) to palladium (Pd) was 0.5: 1, weighed to 1: 1 instead of adding to ethanol, and added to ethanol to prepare a catalyst Respectively.

Preparation Example 4: Preparation of 2% AuPd (2: 1) -IRA743 catalyst

A catalyst was prepared in the same manner as in Production Example 2 except that the molar ratio of gold (Au) and palladium (Pd) was 0.5: 1 and was weighed to be 2: 1 instead of adding to ethanol and then added to ethanol .

Preparation Example 5: Preparation of 2% AuPd (3: 1) -IRA743 catalyst

Except that the molar ratio of gold (Au) to palladium (Pd) was 0.5: 1 and was weighed to be 3: 1 instead of adding to ethanol and added to ethanol. Respectively.

Production Example 6: Preparation of 2% AuPd (6: 1) -IRA743 catalyst

Except that the molar ratio of gold (Au) to palladium (Pd) was 0.5: 1, and the weight was added to ethanol instead of adding to ethanol, and the mixture was added to ethanol. Respectively.

Preparation Example 7: Preparation of 2% AuPd (1: 1) -IRA900 catalyst

A catalyst was prepared in the same manner as in Preparation Example 2, except that IRA900 was used instead of IRA743 as the anion exchange resin.

Production Example 8: Preparation of 2% AuPd (1: 1) -IRA400 catalyst

A catalyst was prepared in the same manner as in Preparation Example 2, except that IRA400 was used instead of IRA743 as the anion exchange resin.

Example 1: 2% AuPd ( 0.5: 1 ) - IRA743  Catalyst-based 2,5- Furan dicarboxylic  acid (FDCA) manufacture

200 mg of gold palladium bimetallic nanoparticles (2% AuPd-IRA 743) prepared in accordance with Production Example 2 (2 mM) and 20 mg of water were added to 20 ml of water using ₂ mM Na ₂ CO _{3 as a} base and ₂ mM of Sigma-Aldrich HMF 2,5-Furan dicarboxylic acid (FDCA) was prepared by oxidizing HMF by reacting for 4 hours at 373K (99.85 ℃) with oxygen gas at 10 bar pressure as an oxidizer.

Example 2: 2% AuPd (1: 1) - IRA743  Catalyst-based 2,5- Furan dicarboxylic  acid (FDCA) manufacture

FDCA was prepared in the same manner as in Example 1, except that the catalyst of Preparation Example 3 was used in place of the catalyst of Production Example 2.

Example 3: 2% AuPd (2: 1) - IRA743  Catalyzed 2,5- Furan dicarboxylic  acid (FDCA) manufacture

FDCA was prepared in the same manner as in Example 1, except that the catalyst of Production Example 4 was used in place of the catalyst of Production Example 2.

Example 4: 2% AuPd (3: 1) - IRA743  Catalyst-based 2,5- Furan dicarboxylic  acid (FDCA) manufacture

FDCA was prepared in the same manner as in Example 1, except that the catalyst of Preparation Example 5 was used in place of the catalyst of Production Example 2.

Example 5: 2% AuPd (6: 1) - IRA743  Catalyst-based 2,5- Furan dicarboxylic  acid (FDCA) manufacture

FDCA was prepared in the same manner as in Example 1, except that the catalyst of Preparation Example 6 was used in place of the catalyst of Production Example 2.

Example 6: 2% AuPd (1: 1) - IRA743  Catalyst-based 2,5- Furan dicarboxylic  acid (FDCA) manufacture

The oxidation reaction was carried out in the same manner as in Example 1, except that HMF prepared in Preparation Example 1 was used instead of Aldrich's HMF in Example 2.

Example 7: 2% AuPd (1: 1) - IRA743  Catalyst-based 2,5- Furan dicarboxylic  acid (FDCA) manufacture

The oxidation reaction was carried out in the same manner as in Example 2, except that the oxygen gas of 15 bar was used instead of the oxygen gas of 10 bar.

Example 8: 2% AuPd (1: 1) - IRA900  Catalyst-based 2,5- Furan dicarboxylic  acid (FDCA) manufacture

The oxidation reaction was carried out in the same manner as in Example 2, except that 2% AuPd (1: 1) -IRA900 in Production Example 7 was used instead of 2% AuPd (1: 1) -IRA743 in Production Example 3.

Example 9: 2% AuPd (1: 1) - IRA400  Catalyst-based 2,5- Furan dicarboxylic  acid (FDCA) manufacture

An oxidation reaction was carried out in the same manner as in Example 2, except that IRA400 represented by the following structural formula 5 was used instead of 2% AuPd (1: 1) -IRA743 in Production Example 3.

[Structural Formula 5]

Comparative Example 1: Preparation of 2,5-Furan dicarboxylic acid (FDCA) using IRA743

2,5-Furan dicarboxylic acid (FDCA) was prepared in the same manner as in Example 1, except that IRA743 was used instead of 2% AuPd-IRA743 in Example 1.

Comparative Example 2: 1%  Au- IRA743  Catalyst-based 2,5- Furan dicarboxylic acid (FDCA) manufacture

(Step 1: 1% Au-IRA743 catalyst preparation)

A catalyst was prepared in the same manner as in Production Example 2, except that the mixed solution was prepared so as to be 1 wt% of gold (Au) instead of 2 wt% of gold (Au) and palladium (Pd) in the mixed solution in Production Example 2.

(Step 2: HMF oxidation with 1% Au-IRA743 catalyst)

2,5-Furan dicarboxylic acid (FDCA) was prepared in the same manner as in Example 1, except that 1% Au-IRA743 was used as a catalyst instead of 2% AuPd-IRA743.

Comparative Example 3: 2%  Au- IRA743  Catalysts using 2,5- Furan dicarboxylic acid (FDCA) manufacture

(2% Au-IRA743 catalyst preparation)

A catalyst was prepared in the same manner as in Production Example 2 except that a mixed solution was prepared so that gold (Au) was 2 wt% instead of gold (Au) and palladium (Pd) 2 wt% in the mixed solution in Production Example 2.

 (HMF oxidation with 2% Au-IRA743)

2,5-Furan dicarboxylic acid (FDCA) was prepared in the same manner as in Example 1, except that 2% Au-IRA743 was used instead of 2% AuPd-IRA743.

Comparative Example 4: Preparation of 2,5-Furan dicarboxylic acid (FDCA) using 1% Pd-IRA743

(1% Pd-IRA743 catalyst preparation)

A catalyst was prepared in the same manner as in Production Example 2, except that the mixed solution was prepared so that palladium (Pd) was 1 wt% instead of gold (Au) and palladium (Pd) 2 wt% in the mixed solution in Production Example 2.

(HMF oxidation with 1% Pd-IRA743)

2,5-Furan dicarboxylic acid (FDCA) was prepared in the same manner as in Example 1, except that 1% Pd-IRA743 was used instead of 2% AuPd-IRA743.

Comparative Example 5: Preparation of 2,5-Furan dicarboxylic acid (FDCA) using 2% Pd-IRA743

(2% Pd-IRA743 catalyst preparation)

A catalyst was prepared in the same manner as in Preparation Example 2 except that a mixed solution was prepared so that palladium (Pd) was 2 wt% instead of gold (Au) and palladium (Pd) 2 wt% in the mixed solution in Production Example 2.

(HMF oxidation with 2% Pd-IRA743)

2,5-Furan dicarboxylic acid (FDCA) was prepared in the same manner as in Example 1, except that 2% Pd-IRA743 was used instead of 2% AuPd-IRA743.

Comparative Example  6: Basic Under the conditions 2% AuPd (1: 1) - IRA743  Preparation of 2,5-Furan dicarboxylic acid (FDCA) by Catalysis

FDCA was prepared in the same manner as in Example 1 except that ₂ mM Na ₂ CO ₃ base was not used .

Comparative Example 7: 1%  Au- IRA743  And 1% Pd- Of IRA743  The 2,5- Furan  dicarboxylic acid (FDCA) manufacture

2% AuPd-IRA743 instead of Comparative Example 2 and Comparative Example 4 2,5-Furandicarboxylicacid (FDCA) was prepared in the same manner as in Example 1 except that the catalyst mixture (1% Au-IRA743 + 1% Pd-IRA743 , 200 mg each) was used.

[Test Example]

Test Example  1: Anion exchange resin Supported  Gold (Au) -Palladium (Pd) By Metallic  XPS analysis of nanoparticles

FIG. 1 shows XPS analysis results of the gold palladium bimetallic nano-particle catalyst supported on the anion exchange resin of Production Example 3 and the gold (Au) nanoparticles supported on the anion exchange resin included in Comparative Example 2. FIG.

In that: (1 1) -IRA743 the Au 4f _7/2 binding energy of 83.8eV: Referring to Figure 1, XPS of 2% Au-IRA743 the Au 4f _7/2 binding energy of 84.0eV is 2% Au Pd I can confirm, 2% of the XPS Pd-IRA743 is Pd 3d _5/2 binding energy and is 335.1eV 2% Au: Pd (1 : 1) -IRA743 was confirmed that the Pd 3d _5/2 binding energy of 336.6eV.

These results are believed to be due to the energy transfer from Pd to Au by alloy formation and Au-Pd alloy severs as a catalyst.

Therefore, it was confirmed that the gold palladium bimetallic nanoparticles supported on the anion exchange resin prepared according to Preparation Example 3 formed an alloy, and thus Pd and Au interacted with each other.

Test Example  2: Anion exchange resin Supported  Gold (Au) -Palladium (Pd) By Metallic  TEM image analysis of nanoparticles

Fig. 2 is a graph showing the results of a comparison between gold (Au) -palladium (Pd) supported on an exchange resin of Comparative Example 1, anion exchange resin of gold (Au) -palladium (Pd) bimetallic nanoparticles prepared according to Production Example 3 and Production Example 6, TEM image of bimetallic nanoparticles.

Referring to FIG. 2, it was confirmed that gold (Au) -palladium (Pd) bimetallic nanoparticles having a size of 5-20 nm were dispersed throughout the anion exchange resin.

Test Example 3: Analysis of catalytic reactivity of metal nanoparticles carried on an anion exchange resin

Table 1 below shows the results of conversion of HMF and selectivity of FDCA in the oxidation reaction of HMF prepared according to Examples 1 to 9 and Comparative Examples 1 to 6.

division Catalyst (metal-ion exchange resin) Oxidation, % HMF conversion FDCA selectivity Example 1 2% AuPd (0.5: 1) -IRA743 100 85.3 Example 2 2% AuPd (1: 1) -IRA743 100 93.2 Example 3 2% AuPd (2: 1) -IRA743 100 79.9 Example 4 2% AuPd (3: 1) -IRA743 100 75.2 Example 5 2% AuPd (6: 1) -IRA743 100 55.1 Example 6 2% AuPd (1: 1) -IRA743 100 91.1 Example 7 2% AuPd (1: 1) -IRA743 100 66.4 Example 8 2% AuPd (1: 1) -IRA900 91.0 5.0 Example 9 2% AuPd (1: 1) -IRA400 98.0 26 Comparative Example 1 IRA743 68.7 2.3 Comparative Example 2 1% Au-IRA743 100 27.6 Comparative Example 3 2% Au-IRA743 100 39.1 Comparative Example 4 1% Pd-IRA743 80.4 7.0 Comparative Example 5 2% Pd-IRA743 83.5 17.4 Comparative Example 6 2% AuPd (1: 1) -IRA743 No base 17.2 0 Comparative Example 7 1% Au-IRA743 + 1% Pd-IRA743 100 52.0

Referring to Table 1, the catalyst of Comparative Example 2 exhibited 100% conversion of HMF, but FDCA selectivity was only 28%. The catalyst of Comparative Example 3 increased the FDCA selectivity to 39%, but the selectivity was relatively low.

Comparative Example 1 using an active metal-free catalyst showed an FDCA selectivity of 2.3% at a conversion of 68%, and Comparative Example 5 using an activated catalyst without a base showed a conversion rate of HMF of 17% The oxidation reaction of Example 4 had 7% FDCA selectivity and the conversion of HMF was 80%.

The oxidation reaction of Example 2 showed 100% conversion of HMF and FDCA selectivity of 93%, and it was confirmed that the catalyst containing palladium (Pd) added to gold (Au) greatly influences FDCA selectivity.

Test Example 4: Time course of oxidation process of HMF

FIG. 3 shows the results of time-course analysis of the oxidation of HMF of Comparative Examples 2 to 4 and Example 2 to FDCA.

Referring to FIG. 3, the oxidation reaction of Comparative Example 2 showed 85% HMF conversion for 1 hour and 77% 5-hydroxymethylfuran-2-carboxylic acid (HMFCA) selectivity. As time progressed, the selectivity of FDCA increased from 5 hours to 5 hours from 0.5 hours to 36 hours due to consumption of HMFCA, but the selectivity of 5-formylfuran-2-carboxylic acid (FFCA) %. As a result, the additional FDCA can be formed with a longer reaction interval, but the longer the reaction time, the less economical effect on production.

In addition, the catalyst of Comparative Example 4 showed a different reaction from the catalyst containing gold only, i.e., the HMFCA selectivity was maintained at about 50% from 0.5 hour to 5 hours. Similarly, FFCA and FDCA selectivity remained stable during the reaction. These results suggest that the catalyst does not tend to shift the equilibrium towards FDCA.

The oxidation reaction of Example 2 showed 95% HMF conversion with 61% FFCA selectivity in 0.5 hour reaction. As time progressed, the selectivity of FDCA increased, reaching 91% selectivity over 3 hours and reaching 95% selectivity over 5 hours. According to these results, FDCA produced in the oxidation reaction of Example 2 is stable in a long time reaction condition, and it is considered that the economical efficiency for industrial production is high.

Test Example 5: Analysis of catalytic reactivity according to the molar ratio of gold (Au) and palladium (Pd)

To analyze the effect of palladium (Pd) on gold (Au), the oxidation reactivity of Examples 1 to 5 was analyzed. Table 2 shows the conversion of HMF and the selectivity of FDCA according to the molar ratio of metal by changing the molar ratio of Au-Pd from 0.5: 1 to 6: 1.

division Catalyst (metal-ion exchange resin) Oxidation, % HMF conversion FDCA selectivity Example 1 2% AuPd (0.5: 1) -IRA743 100 85.3 Example 2 2% AuPd (1: 1) -IRA743 100 93.2 Example 3 2% AuPd (2: 1) -IRA743 100 79.9 Example 4 2% AuPd (3: 1) -IRA743 100 75.2 Example 5 2% AuPd (6: 1) -IRA743 100 55.1

According to Table 2, 2% AuPd (6: 1) -IRA743 having a relatively low palladium (Pd) concentration showed 100% conversion with 55.1% FDCA selectivity and 2% AuPd with a relatively high palladium (Pd) concentration : 1) -IRA743 was 93.2% FDCA selectivity with 100% conversion.

As a result, FDCA selectivity increased as the concentration of palladium (Pd) increased in gold (Au). However, when palladium (Pd) had a higher concentration than gold (Au) And no improvement in selectivity was observed.

Therefore, it is considered that the gold (Au) -palladium (Pd) bimetallic nanoparticles carried on the anion exchange resin are most suitably mixed at a molar ratio of 1: 1.

Test Example  6: The type of anion exchange resin is HMF  Analysis of effect on oxidation

FIG. 4 shows the results of analyzing the conversion of HMF and the selectivity of FDCA according to the kind of anion exchange resin in which gold (Au) and palladium (Pd) are supported.

IRA743 showed 91% conversion with 2% AuPd (1: 1) -IRA900 with 5% FDCA selectivity and 98% conversion with 2% AuPd (1: 1) -IRA400 with 26% FDCA selectivity Respectively.

Therefore, it is considered that IRA743 is an anion exchange resin among materials that can be used as a catalyst for producing FDCA.

Test Example  7: Anion exchange resin Supported  Gold (Au) -Palladium (Pd) By Metallic  Re-use effect of nanoparticle catalyst

FIG. 5 shows the result of analyzing the recycle of the catalyst in the oxidation reaction of Example 2. When the catalyst used in the production of FDCA was filtered, washed and dried and reused, the conversion and selectivity were analyzed The results are shown.

Referring to FIG. 5, it can be confirmed that the conversion rate and selectivity are maintained to be almost the same when reused up to six times.

Therefore, it is considered that gold (Au) -palladium (Pd) bimetallic nanoparticles supported on anion exchange resin can be used up to six times for the oxidation of HMF to FDCA.

Test Example  8: Of HMF  Analysis of Oxidation Reactivity by Product

Table 3 below shows the results of analysis of the HMF oxidation reactions of Examples 2, 6 and 7. [

division HMF type HMF conversion rate,% FFCA selectivity. % FDCA selectivity. % HMFCA selectivity. % Other Selectivity. % Example 2 Aldrich HMF 100 3.3 93.2 0 3.5 Example 6 Production Example 1 100 8.9 91.1 0 0 Example 7 Aldrich HMF - 15 bar air 100 28.8 66.4 0 4.8

Referring to Table 3, the conversion of HMF in the HMF oxidation reaction of Example 2 and the oxidation reaction of Example 6 were all 100%, and the FDCA selectivities were 93.8% and 91.1%, respectively.

According to these results, the gold-palladium bimetallic nanoparticle catalyst supported on the anion exchange resin produced according to the production method of the present invention is not limited to the commercial HMF distributed in the market, but also to the crude HMF which is not a commercial product synthesized in the laboratory The activity was confirmed to be high. Also, when the reaction was carried out using an oxygen pressure of 15 bar as an oxidizing agent, 100% conversion of HMF and 66% FDCA selectivity were exhibited.

Therefore, it is considered that the gold-palladium bimetallic nanoparticles supported on the anion exchange resin prepared according to the production method of the present invention is suitable for industrial use as a catalyst.

Test Example  9: on anion exchange resin Supported  Depending on the type of metal nanoparticles FDCA  Yield analysis

Table 4 below shows FDCA yields of Comparative Example 2, Comparative Example 4, Comparative Example 5 and Example 2 in comparison.

division Catalyst (metal-ion exchange resin) Oxidation, % HMF conversion FDCA selectivity Example 2 2% AuPd (1: 1) -IRA743 100 93.2 Comparative Example 3 2% Au-IRA743 100 39.1 Comparative Example 5 2% Pd-IRA743 83.5 17.04 Comparative Example 6 1% Au-IRA743 + 1% -IRA743 100 52.0

Referring to Table 4, when the FDCA was produced using the 2% AuPd (1: 1) -IRA743 catalyst of Example 2, the yield was the highest at 90% or more. However, as in Comparative Example 6, when the oxidation reaction was carried out by simply mixing 1% Au-IRA743 and 1% -IRA743, the yield was 52%, indicating that the efficiency was low.

Therefore, when the gold-palladium bimetallic nano-particle catalyst supported on the anion exchange resin is used as a mixed catalyst in which the gold nanoparticles supported on the anion exchange resin and the palladium nanoparticles supported on the anion exchange resin are simply mixed, It is considered that the efficiency of the catalyst for forming bimetallic alloy of gold and palladium in accordance with the present invention is much better.

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 (19)

A process for preparing 2,5-furan dicarboxylic acid (FDCA) represented by the following formula (2) by oxidation of HMF (5-Hydroxymethylfurfural) represented by the following formula (1)
Wherein the catalyst comprises an anion exchange resin and gold palladium bimetallic nanoparticles carried on the anion exchange resin,
Wherein the anion exchange resin is one represented by the following structural formula 3 or a salt thereof,
Wherein the anion exchange resin is basic,
Sodium carbonate (Na ₂ CO ₃ ), sodium hydrogencarbonate (NaHCO ₃ ), potassium carbonate (K ₂ CO ₃ ), potassium bicarbonate (KHCO ₃ ), sodium hydroxide (NaOH) and potassium hydroxide (KOH) And the oxidation reaction is carried out.
[Chemical Formula 1]

(2)

[Structural Formula 3]

In Structure 3,
R ³ is a hydrogen atom, a C1 to C10 straight chain alkyl group, or a C3 to C10 branched alkyl group.
m and n are the same or different and each independently is an integer of 1 to 3,
and q is an integer of 1 to 10. The method according to claim 1,
Wherein the molar ratio of gold (Au): palladium (Pd) of the gold palladium bimetallic nanoparticles is 0.5: 1.0 to 6.0: 1.0. The method according to claim 1,
Wherein the anion exchange resin comprises a support and an amine group covalently bonded to the support. delete delete delete The method of claim 3,
Wherein the anion exchange resin is covalently bonded with a glucamine group or a salt thereof on the support. The method of claim 3,
Wherein the support is porous or gel-like, and is swelled under a solvent. The method of claim 3,
Wherein the support comprises at least one polymer selected from the group consisting of polystyrene, cross-linked polystyrene, copolymerized polystyrene and grafted polystyrene. delete delete The method according to claim 1,
Wherein the solvent is a polar solvent. The method according to claim 1,
Lt; RTI ID = 0.0 > FDCA. ≪ / RTI > The method according to claim 1,
Wherein the yield of FDCA (2,5-furandicarboxylic acid) is 80 to 99%. The method according to claim 1,
Wherein the preparation of the furan compound for preparing the 2,5-furandicarboxylic acid (FDCA) is carried out at room temperature. The method according to claim 1,
Wherein the catalyst is prepared by preparing a reducing agent, an anion exchange resin, a gold (Au) precursor and a palladium (Pd) precursor in a solvent. 17. The method of claim 16,
Wherein the gold (Au) precursor comprises at least one selected from gold chloride (AuCl ₃ ) and gold bromide (AuBr ₃ ). 17. The method of claim 16,
The palladium (Pd) precursor is palladium chloride (PdCl _2), palladium bromide (PdBr _2), and palladium acetate (Pd (OAc) ₂₎ Wherein the FDCA comprises at least one member selected from the group consisting of a fluorine-containing compound and a fluorine-containing compound. 17. The method of claim 16,
Wherein the reducing agent is selected from the group consisting of sodium borohydride (NaBH ₄ ), sodium cyanoborohydride (NaBH ₃ CN), lithium aluminum hydride (LiAlH ₄ ) and hydrazine (N ₂ H ₄ ) Wherein the FDCA is at least one species selected from the group consisting of FDCA and FDCA.

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