KR102117340B1 - Method for producing 2,5-furan dicarboxylic acid using an alkali metal-azolide-based catalyst - Google Patents

Abstract

One embodiment of the present invention provides a method for producing 2,5-furandicarboxylic acid using carbon dioxide. More specifically, a step of forming a mixture by mixing a catalyst comprising 2-Furoic acid (FA) and triazolide, injecting carbon dioxide into the mixture to produce a reactant, and stirring the reactant It provides a method for producing 2,5-furandicarboxylic acid, characterized in that.

Description

Method for producing 2,5-furan dicarboxylic acid using an alkali metal-azolide catalyst {Method for producing 2,5-furan dicarboxylic acid using an alkali metal-azolide-based catalyst}

The present invention relates to a method for producing 2,5-furandicarboxylic acid using an alkali metal-azolide-based catalyst, and more specifically, using carbon dioxide and furfural in a solvent-free condition using a triazolide catalyst 2, It relates to a method for directly producing 5-furandicarboxylic acid.

As the industrial production system was established from the start of World War II, plastics based on various resins began to be mass-produced as consumer goods. In particular, from the late 1970s, more than 300 million tons of plastic has been produced and consumed worldwide, exceeding steel production. However, since plastic is produced using naphtha from the oil refining process, petroleum resource depletion and carbon dioxide emissions are a problem, and as it is used as a main material for disposable products, a large amount of plastic is discarded as it is disposed of immediately after product use. When it is difficult to reclaim because it does not rot, incineration substances such as dioxin are released into the atmosphere, causing environmental problems, and research on alternative materials for this is ongoing.

As a substitute for plastics, scientists are working hard to develop bioplastic materials using plant starch or cellulose. In particular, one of the materials in the spotlight among bioplastic materials is a plastic manufactured based on 2,5-furandicarboxylic acid (FDCA).

However, in the case of FDCA, 5-hydroxylfurfural (HMF), which has a limitation in securing raw materials, is produced through an oxidation reaction using an explosive oxidizing agent such as air or pure oxygen in the presence of a precious metal catalyst. It is common. However, HMF, which is a hexahedral sugar, has a problem in that it is difficult to manufacture FDCA on a large scale because there is a difficulty in supplying raw materials, mass production is difficult, and when an oxidation reaction is performed, an explosive oxidizing agent must be used.

In this regard, in the case of U.S. Patent No. 8,519,167 (hereinafter referred to as Cited Reference 1), it is related to a method of manufacturing FDCA and manufacturing FDCA using HMF as a feed material. In addition, it can be seen that there is still a problem in the production of FDCA in that it is produced by causing an oxidation reaction using an oxidizing agent having a risk of explosion.

In addition, in the case of non-patent documents 1 to 2, non-patent documents 2 present a three-step process of preparing FDCA by preparing FDCA salt by preparing FDCA salt by furoic acid, reacting it with carbon dioxide, and acidifying it with water.

Therefore, there is a need for a process capable of preparing the FDCA salt in a single reaction by avoiding the oxidation process of HMF, a hexose sugar, and using a cheap and abundant carbon dioxide and a pentasaccharide material (perfural), which is industrially useful.

US registered patent US 8,519,167

 Tao Pan, Jin Deng, Qing Xu, Yong Zuo, Qing-Xiang Guo, and Yao Fu, "Catalytic Conversion of furfural into FDCA and Polymer", ChemSusChem, DOI: 10.1002 / cssc.201200652  Aanindeeta Banerjee, Graham R. Dick, Tatsuhiko Yoshino & Matthew W. Kanan, “Carbon dioxide utilization via carbonate-promoted C-H carboxlation”, Nature, doi: 10.1038 / nature17185

The technical problem to be achieved by the present invention is to provide a method for producing 2,5-furandicarboxylic acid using an alkali metal-azole catalyst.

More specifically, the salt compound of 2,5-furandicarboxylic acid is reacted with carbon dioxide by reacting furoic acid obtained by oxidizing perfural, a representative material of pentasaccharide, which is industrially highly applicable, by avoiding the acid ring process of HMF, a hexahedral sugar. And 2,5-furandicarboxylic acid (FDCA).

The technical problem to be achieved by the present invention is not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by a person having ordinary knowledge in the technical field to which the present invention belongs from the following description. There will be.

In order to achieve the above technical problem, one embodiment of the present invention provides a method for producing 2,5-furandicarboxylic acid using an alkali metal-azole catalyst. The 2,5-furandicarboxylic acid manufacturing method comprises the steps of forming a mixture by mixing a catalyst comprising 2-Furoic acid (FA) and triazolide and injecting carbon dioxide into the mixture to produce a reactant. It may be characterized by including.

In addition, the step of forming the mixture is characterized in that the solvent-free reaction.

In addition, the catalyst comprising the triazolide is characterized in that it is an M triazolide catalyst, M of the M triazole is characterized in that it contains an alkali metal.

In addition, the catalyst comprising the triazolide includes Li [triazolide], Na [triazolide], K [triazolide], Rb [triazolide], Cs [triazolide], Cs [Benzotriazolide] or Cs [Amino-triazolide] It is characterized by.

In addition, the reaction temperature in the step of forming the mixture is characterized in that it is 100 ℃ to 300 ℃.

In addition, the 2-Furoic acid (FA) is characterized in that the catalyst is 0.5mmol to 0.7mmol based on 1mmol.

In addition, the step of injecting the carbon dioxide to produce a reactant

And injecting carbon dioxide into the mixture at a first pressure, agitating the mixture injecting carbon dioxide at the first pressure, and injecting carbon dioxide at a second pressure into the stirred mixture.

In addition, the first pressure is characterized in that 10psi to 90psi, the second pressure is characterized in that 200psi to 600psi.

In order to achieve the above technical problem, another embodiment of the present invention is used to synthesize 2,5-furandicarboxylic acid from 5 carbonaceous substances and carbon dioxide, and 2,5- characterized in that it contains M triazolide. Provided is a catalyst for producing furandicarboxylic acid.

According to an embodiment of the present invention, 2-Furoic acid and carbon dioxide can be directly reacted in a simple process in a single container to produce a high yield of 2,5-furandicarboxylic acid.

In addition, salt compounds of 2,5-furandicarboxylic acid and 2,5-furandicarboxylic acid are used as raw materials using inexpensive and abundant carbon dioxide and 2-Furoic acid obtained by oxidizing perfural during mass production. Since (FDCA) is manufactured, an effect of reducing manufacturing cost can be obtained.

In addition, it is possible to obtain an advantage that can be manufactured in an environmentally friendly and large quantity without using a toxic reactant.

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

1 is a flow chart showing a method for producing 2,5-furandicarboxylic acid.
Figure 2 is a structural formula showing a Cs [Triazolide] catalyst.
Figure 3 is a structural formula showing a Cs [Amino-Triazolide] catalyst.
4 is a structural formula showing a Cs [BenzoTriazolide] catalyst.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be implemented in various different forms, and thus is not limited to the embodiments described herein. In addition, in order to clearly describe the present invention in the drawings, parts irrelevant to the description are omitted, and like reference numerals are assigned to similar parts throughout the specification.

Throughout the specification, when a part is "connected (connected, contacted, coupled)" with another part, it is not only "directly connected" but also "indirectly connected" with another member in between. "It also includes the case where it is. Also, when a part “includes” a certain component, this means that other components may be further provided instead of excluding other components, unless otherwise stated.

The terms used herein are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “include” or “have” are intended to indicate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, and that one or more other features are present. It should be understood that the existence or addition possibilities of fields or numbers, steps, operations, components, parts or combinations thereof are not excluded in advance.

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

1 is a flow chart showing a method for producing 2,5-furandicarboxylic acid.

Referring to FIG. 1, the method for preparing 2,5-furandicarboxylic acid (FDCA: 2,5-furandicarboxylic acid) of the present invention is a mixture by mixing a catalyst containing 2-Furoic acid (FA) and triazolide It may be characterized in that it comprises the step of forming (S100) and injecting carbon dioxide into the mixture to generate a reactant (S200).

First, a mixture containing 2-Furoic acid (FA) and triazolide is mixed to form a mixture (S100).

The step of forming the mixture may be characterized by a solvent-free reaction.

The 2-Furoic acid (FA) can be obtained by oxidizing perfural, a representative material of pentose sugar having high industrial utility.

In addition, the catalyst comprising the triazolide may be characterized in that it is an M triazolide catalyst.

M of the M triazole may be characterized in that it contains an alkali metal, for example, the catalyst comprising the triazole is Li [triazolide], Na [triazolide], K [triazolide], Rb [ triazolide], Cs [triazolide], Cs [Benzotriazolide] or Cs [Amino-triazolide].

For example, the catalyst including triazole may include a Cs [triazolide] catalyst of the following [Formula 1].

[Formula 1]

In addition, the reaction temperature in the step of forming the mixture may be characterized in that it is 100 ℃ to 300 ℃.

When the reaction temperature is 100 ° C to 300 ° C, it is an optimal reaction temperature, and if it deviates, the reactivity of the catalyst may decrease.

In addition, the 2-Furoic acid (FA) may be characterized in that the catalyst is 0.5mmol to 0.7mmol based on 1mmol.

When the methanol and base are catalysts based on 1 mmol, if the catalyst is less than 0.5 mmol or exceeds 0.7 mmol, FA activation rate or FDCA yield may drop.

Then, carbon dioxide is injected into the mixture to generate a reactant (S200).

The step of injecting the carbon dioxide to generate a reactant may include injecting carbon dioxide at a first pressure and injecting carbon dioxide at a second pressure.

For example, the first pressure is characterized in that 10psi to 90psi, the second pressure may be characterized in that 200psi to 600psi.

When the first reaction pressure is less than 10 psi, there may be a problem that the FDCA yield is lowered, and when it exceeds 90 psi, there is a problem that the FDCA yield is lowered as the hydrolysis reaction of the product FDCA becomes dominant by water formed as a by-product. You can not be windy.

In addition, when the second reaction pressure is less than 200 psi, the yield may decrease, and when it exceeds 600 psi, yield improvement cannot be expected with unnecessary pressure.

In addition, the reaction time of the method for preparing the 2,5-furandicarboxylic acid may be characterized in that it is 24 hours or more.

The reaction time exceeds 24 hours, the longer the DMC yield may increase.

For example, if the reaction time is 12 hours, the FA conversion rate may be 55.2%, the FDCA yield may be 16.8%, and when the reaction time is 24 hours, the conversion rate of FA is 52.6%, and the yield of FDCA is 42.1%. It can be seen that the FDCA yield increased.

In addition, the stirring speed in the stirring step may be characterized in that it is 300rpm to 1000rpm.

In addition, the 2,5-furandicarboxylic acid production method described above can produce a high yield of 2,5-furandicarboxylic acid.

In addition, it is used to synthesize 2,5-furandicarboxylic acid from pentasaccharide and carbon dioxide, and can provide a catalyst for producing 2,5-furandicarboxylic acid, which comprises M triazole.

The use of the catalyst can provide a process that saves energy, cost and time without using toxic reactants.

Therefore, 2-Furoic acid (FA) and carbon dioxide react with the catalyst containing the triazole fluoride to easily produce 2,5-furandicarboxylic acid in a single container.

The method for producing 2,5-furandicarboxylic acid of the present invention is limited in securing raw materials in the conventional method, and the hexahedral 5-hydroxymethylfurfural (HMF: 5-hydroxylfurfural) is present in the presence of a precious metal catalyst in the air or pure oxygen. In the method that was produced through an oxidation reaction using an explosive oxidizing agent as described above, the acid exchange process is avoided and 2-Furoic acid (FA) obtained by oxidizing perfural, a representative material of industrially useful pentose, is reacted with carbon dioxide. It provides a technique for preparing a salt compound of 2,5-furandicarboxylic acid and 2,5-furandicarboxylic acid (FDCA).

In addition, by using 2-Furoic acid (FA) and carbon dioxide obtained by oxidizing the five-carbon perfural, a sustainable raw material is used and reacted in a solvent-free condition to shorten the process of two or more steps in the prior art.

Therefore, it is possible to provide a large amount of 2,5-furandicarboxylic acid salt compound and 2,5-furandicarboxylic acid (FDCA) in a simpler process than in the prior art by direct reaction in a single container.

Figure 2 is a structural formula showing a Cs [Triazolide] catalyst.

Figure 3 is a structural formula showing a Cs [Amino-Triazolide] catalyst.

4 is a structural formula showing a Cs [BenzoTriazolide] catalyst.

2 to 4, it may be a structural formula of a catalyst comprising the triazole hydride of the present invention.

Preparation Example 1

1) A mixture was prepared by mixing 5 mmol of 2-Furoic acid (FA) and 8 mmol of Cs [Triazolide] catalyst in a solvent-free 100 m high pressure stainless steel reactor equipped with a magnetic stirrer and an electric heater.

2) The mixture was purged of carbon dioxide into the reactor at 80 psi pressure.

3) The atmosphere was evacuated three times from the mixture.

4) Stirred at 500 rpm, heated to 200 ° C. temperature, and raised the carbon dioxide pressure to 300 psi.

5) 2,5-furandicarboxylic acid (FDCA: 2,5-furandicarboxylic acid) and FDCA salt were prepared by reacting for 24 hours while maintaining the carbon dioxide pressure at 300 psi.

6) After the reaction was completed, wait until it was at room temperature, and the resulting mixture was transferred to a vial to calculate the conversion of FA to GD-FID and the yield of furandicarboxylic acid (FDCA: 2,5-furandicarboxylic acid).

In addition, the yield calculation method of the furandicarboxylic acid (FDCA: 2,5-furandicarboxylic acid) of Preparation Example 1 6) may be the following equation.

[Mathematics]

For example, the theoretically substituted furan dicarboxylic acid (FDCA: 2,5-furandicarboxylic acid) predicted number of moles and the number of furan dicarboxylic acids (FDCA: 2,5-furandicarboxylic acid) produced through Preparation Example 1 By substitution, the yield of furandicarboxylic acid (FDCA: 2,5-furandicarboxylic acid) can be confirmed.

[Reaction formula]

The reaction scheme is a reaction scheme showing a process for preparing a salt of furandicarboxylic acid (FDCA: 2,5-furandicarboxylic acid).

Referring to the above reaction formula, Cs [Triazolide] catalyst (Catalyst) and 2-Furoic acid (FA) are mixed in a solventless reaction to prepare a mixture, and when CO ₂ is injected into the mixture, 2-Furoic by the catalyst and base The reaction between acid (FA) and carbon dioxide allows simple FDCA and furandicarboxylic acid (FDCA: 2,5-furandicarboxylic acid) salt preparation in a single container.

In addition, M of the reaction formula may be Cs, K, Na.

Preparation Example 2

1) FDCA and FDCA salt were prepared in the same manner as in Preparation Example 1, except that a Cs ₂ CO ₃ reagent was used instead of the Cs [Triazolide] catalyst.

Preparation Example 3

1) FDCA and FDCA salt were prepared in the same manner as in Preparation Example 1, except that an Amino-triazolide catalyst was used instead of the Cs [Triazolide] catalyst.

Preparation Example 4

1) FDCA and FDCA salt were prepared in the same manner as in Preparation Example 1, except that a Benzotriazolide catalyst was used instead of the Cs [Triazolide] catalyst.

Preparation Example 5

1) FDCA and FDCA salt were prepared in the same manner as in Preparation Example 1, except that formate was used instead of the Cs [Triazolide] catalyst.

Hereinafter, [Table 1] to [Table 3] show the conversion rate of 2-Furoic acid (FA) and the yield of 2,5-furandicarboxylic acid (FDCA: 2,5-furandicarboxylic acid) by varying the reaction conditions of the preparation examples. It is a comparison table.

In addition, C of [Table 1] to [Table 3] represents the conversion rate Y and the yield.

Table 1 is a comparison table of the conversion of 2-Furoic acid (FA) and the yield of 2,5-furandicarboxylic acid (FDCA: 2,5-furandicarboxylic acid) according to the catalyst.

catalyst C _FA ,
(%) Y _{FDCA salt} ,
(%) Preparation Example 1 55.2 16.8 Preparation Example 2 75.6 19.0 Preparation Example 3 62.1 22.4 Preparation Example 4 68.7 14.7 Preparation Example 5 30.4 7.5

Referring to Table 1, Comparative Example 1 to Preparation Example 5 were tested under the same reaction conditions (FA 5 mmol, catalyst 8 mmol, reaction temperature 200 ° C., reaction pressure 300 psi, reaction time 12 hours), and Preparation Example 3 It can be seen that the FDCA yield of is the highest with 22.4%.

Table 2 is a comparison table of the conversion of 2-Furoic acid (FA) and the yield of 2,5-furandicarboxylic acid (FDCA: 2,5-furandicarboxylic acid) according to the reaction time.

catalyst Reaction time
(h) C _FA ,
(%) Y _{FDCA salt} ,
(%) Preparation Example 1 12 55.2 16.8 Preparation Example 1 24 52.6 42.1

Referring to Table 2, when the FDCA was prepared under the same conditions other than the reaction time, the conversion rate of FA in the 24-hour reaction was not significantly different from that of the 12-hour reaction. have.

Therefore, it can be seen that the longer the reaction time, the higher the FDCA yield.

Table 3 is a comparison table of the conversion of 2-Furoic acid (FA) and the yield of 2,5-furandicarboxylic acid (FDCA: 2,5-furandicarboxylic acid) according to the reaction pressure.

catalyst Reaction pressure
(psi) C _FA ,
(%) Y _{FDCA salt} ,
(%) Preparation Example 1 300 55.6 42.1 Preparation Example 1 800 54.8 44.6

Referring to Table 3, when the FDCA was prepared under the same conditions in addition to the reaction pressure, when the reaction pressure was 800 psi, the conversion rate of FA was 54.8%, and the FDCA yield was 44.6%. have.

Therefore, when the size of the reaction pressure is 300 psi or more, it may not have a significant effect on the FDCA yield.

According to an embodiment of the present invention, 2-Furoic acid and carbon dioxide can be directly reacted in a simple process in a single container to produce a high yield of 2,5-furandicarboxylic acid.

In addition, 2,5-furandicarboxylic acid is produced using materials such as 2-Furoic acid obtained by oxidizing perfural, a representative material of cheap and abundant carbon dioxide and pentose in mass production, thereby reducing manufacturing cost. Can get

In addition, it is possible to obtain an advantage that can be manufactured in an environmentally friendly and large quantity without using a toxic reactant.

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

The above description of the present invention is for illustration only, and those skilled in the art to which the present invention pertains can understand that the present invention can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the above-described embodiments are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all modifications or variations derived from the meaning and scope of the claims and their equivalent concepts should be interpreted to be included in the scope of the present invention.

Claims (9)

Forming a mixture by mixing a catalyst comprising 2-Furoic acid (FA) and triazolide; And
Including the step of injecting carbon dioxide into the mixture to produce a reactant;
2,5-furandicarboxylic acid production method characterized in that the catalyst comprising the triazolide is an M triazolide catalyst, and M of the M triazole is an alkali metal. According to claim 1,
The step of forming the mixture is a 2,5-furandicarboxylic acid production method, characterized in that the solvent-free reaction. delete According to claim 1,
The catalyst comprising the triazolide is characterized by including Li [triazolide], Na [triazolide], K [triazolide], Rb [triazolide], Cs [triazolide], Cs [Benzotriazolide] or Cs [Amino-triazolide] 2,5-furandicarboxylic acid production method. According to claim 1,
2,5-furandicarboxylic acid production method characterized in that the reaction temperature in the step of forming the mixture is 100 ℃ to 300 ℃. According to claim 1,
The 2-Furoic acid (FA) is a 2,5-furandicarboxylic acid production method characterized in that the catalyst is 0.5mmol to 0.7mmol based on 1mmol. According to claim 1,
The step of injecting the carbon dioxide to produce a reactant
Injecting carbon dioxide into the mixture at a first pressure;
Stirring the mixture injected with carbon dioxide at the first pressure; And
Injecting carbon dioxide into the stirred mixture at a second pressure; 2,5-furandicarboxylic acid production method characterized in that it comprises a. The method of claim 7,
The first pressure is characterized in that 10psi to 90psi, the second pressure is 2,5-furandicarboxylic acid production method characterized in that 200psi to 600psi. delete

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