KR20230037271A - Catalyst for tetrahydrofuran-2,5-dicarboxylic acid and method of preparing tetrahydrofuran-2,5-dicarboxylic acid - Google Patents

Abstract

Disclosed are a catalyst for preparing tetrahydrofuran-2,5-dicarboxylic acid and a method for preparing tetrahydrofuran-2,5-dicarboxylic acid using the same. The catalyst includes a support in which ruthenium nanoparticles are supported, whereby tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) from 2,5-furandicarboxylic acid (FDCA) can be obtained in excellent yield, and the catalyst can be reused.

Description

Catalyst for the production of tetrahydrofuran-2,5-dicarboxylic acid and method for producing tetrahydrofuran-2,5-dicarboxylic acid using the same ,5-DICARBOXYLIC ACID}

The present invention relates to a catalyst for producing tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) and a method for producing tetrahydrofuran-2,5-dicarboxylic acid using the catalyst, and relates to a support on which ruthenium nanoparticles are supported. By using a catalyst containing a, it is possible to obtain tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) from 2,5-furandicarboxylic acid (FDCA) in excellent yield, and a reusable catalyst and It relates to a method for producing tetrahydrofuran-2,5-dicarboxylic acid using the same.

Adipic acid (AA) is widely used as an important monomer in the production of nylon-66, and is also used in the production of polyurethanes, resins, plasticizers, food and pharmaceutical additives.

Conventionally, adipic acid was prepared through a chemical synthesis process using cyclohexanone as an intermediate from benzene obtained in a crude oil refining process. However, this method has problems in that a large amount of by-products harmful to the environment such as instability of oil price, use of toxic substance benzene, and nitrogen oxides (NOx) may be generated.

Therefore, many research efforts are being made to develop an eco-friendly and efficient catalytic conversion route for producing adipic acid from biomass-derived chemicals that can replace petroleum-based precursors.

Among them, a number of studies on the production of adipic acid from 2,5-furandicarboxylic acid (FDCA) have been conducted. When adipic acid is produced from 2,5-furandicarboxylic acid in a one-step process, a precious metal is required as a catalyst, high temperature and high pressure are required, and adipic acid selectivity is not high.

Therefore, after preparing an intermediate between 2,5-furandicarboxylic acid and adipic acid, it is necessary to study a method for preparing adipic acid using the same.

An object of the present invention is to solve the above problems, and tetrahydrofuran-2,5-dicarboxylic acid, which is an intermediate between 2,5-furandicarboxylic acid and adipic acid, , THFDCA) to provide a method for producing.

Another object of the present invention is to provide a reusable catalyst with high 2,5-furandicarboxylic acid conversion and tetrahydrofuran-2,5-dicarboxylic acid selectivity.

According to one aspect of the invention, the support; A catalyst for preparing tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) comprising; and ruthenium nanoparticles supported on the support is provided.

In addition, the support may include at least one selected from the group consisting of aluminum oxide, titanium oxide, zirconium oxide, manganese oxide, cobalt oxide, and activated carbon.

In addition, the support may include aluminum oxide.

In addition, the amount of the ruthenium nanoparticles may be 1 to 10 parts by weight based on 100 parts by weight of the support.

In addition, the catalyst may be a catalyst used to produce tetrahydrofuran-2,5-dicarboxylic acid by reducing a furan-based compound containing a carboxyl group (-COOH).

In addition, the furan-based compound including the carboxyl group (-COOH) may be 2,5-furandicarboxylic acid (FDCA).

In addition, the catalyst for producing tetrahydrofuran-2,5-dicarboxylic acid may be reusable.

According to another aspect of the present invention, (a) tetrahydrofuran-2,5 represented by structural formula 2 by hydrogenating a furan-based compound represented by structural formula 1 in Scheme 1 using hydrogen (H ₂ ) and a catalyst; -Producing a dicarboxylic acid; wherein the catalyst includes a support on which ruthenium nanoparticles are supported, and a method for producing tetrahydrofuran-2,5-dicarboxylic acid is provided.

[Scheme 1]

In addition, the support may include at least one selected from the group consisting of aluminum oxide, titanium oxide, zirconium oxide, manganese oxide, cobalt oxide, and activated carbon.

In addition, the support may include aluminum oxide.

In addition, the hydrogenation reaction may be carried out at a temperature of 30 to 100 ℃.

In addition, the catalyst may be 50 to 100 parts by weight based on 100 parts by weight of the furan-based compound.

In addition, the hydrogenation reaction may further include a solvent.

Also, the solvent may include water.

In addition, the furan-based compound may be 0.1 to 15 parts by weight based on 100 parts by weight of the solvent.

In addition, the hydrogenation reaction may be performed at a hydrogen pressure of 200 to 1,000 psi.

In addition, in the method for producing tetrahydrofuran-2,5-dicarboxylic acid, prior to step (a), (a') a reducing agent is added to a mixture containing a support and a ruthenium precursor, and the reaction is performed on the support and the support. Preparing a catalyst comprising ruthenium nanoparticles supported on; may further include.

In addition, the reducing agent may include at least one selected from the group consisting of sodium borohydride (NaBH ₄ ) and ascorbic acid.

In addition, the method for producing tetrahydrofuran-2,5-dicarboxylic acid, after step (a), (b) reuses the catalyst to obtain the furan-based compound represented by Structural Formula 1 and the hydrogen (H ₂ ) to prepare tetrahydrofuran-2,5-dicarboxylic acid represented by Structural Formula 2 by a hydrogenation reaction; may further include.

In addition, the step (b) may be repeated 1 to 10 times.

The catalyst for producing tetrahydrofuran-2,5-dicarboxylic acid of the present invention has excellent tetrahydrofuran-2,5-dicarboxylic acid selectivity and can be reused.

The method for producing tetrahydrofuran-2,5-dicarboxylic acid of the present invention has excellent selectivity from 2,5-furandicarboxylic acid by using a catalyst including a support on which ruthenium nanoparticles are supported. 2,5-dicarboxylic acids can be prepared.

Since these drawings are for reference in explaining exemplary embodiments of the present invention, the technical spirit of the present invention should not be construed as being limited to the accompanying drawings.
1 is an HR-TEM image of catalysts prepared according to Examples 1 to 6.
Figure 2 is a graph showing the results of FDCA hydrogenation reaction according to the reaction temperature using the catalyst of Example 1.
3 is a graph showing the FDCA hydrogenation reaction results according to the reaction time using the catalyst of Example 1.
4 is a graph showing the results of FDCA hydrogenation reaction according to hydrogen pressure using the catalyst of Example 1.
5 is a graph showing the results of FDCA hydrogenation reaction according to FDCA concentration using the catalyst of Example 1.
6 is a graph showing the results of FDCA hydrogenation reaction when the reaction time is changed according to the FDCA concentration using the catalyst of Example 1.
7 is a graph showing the results of FDCA hydrogenation when the catalyst of Example 1 was used 1 to 4 times.

Since the present invention can apply various transformations and have various embodiments, specific embodiments are exemplified and described in detail in the detailed description. However, it should be understood that this is not intended to limit the present invention to specific embodiments, and includes all transformations, equivalents or substitutes included in the spirit and scope of the present invention. In describing the present invention, if it is determined that a detailed description of related known technologies may obscure the gist of the present invention, the detailed description will be omitted.

Also, terms including ordinal numbers such as first and second to be used below may be used to describe various components, but the components are not limited by the terms. These terms are only used for the purpose of distinguishing one component from another. For example, a first element may be termed a second element, and similarly, a second element may be termed a first element, without departing from the scope of the present invention.

Also, when a component is referred to as “on another component,” “formed on another component,” “located on another component,” or “layered on another component,” the other It should be understood that although it may be directly attached to the front surface or one side of the component, it may be positioned or laminated, but other components may further exist in the middle.

Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

Hereinafter, the catalyst for preparing tetrahydrofuran-2,5-dicarboxylic acid and the method for preparing tetrahydrofuran-2,5-dicarboxylic acid using the same according to the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

The present invention is a support; It provides a catalyst for producing tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) comprising; and ruthenium nanoparticles supported on the support.

In addition, the support may include at least one selected from the group consisting of aluminum oxide, titanium oxide, zirconium oxide, manganese oxide, cobalt oxide, and activated carbon, preferably aluminum oxide.

In addition, the amount of the ruthenium nanoparticles may be 1 to 10 parts by weight based on 100 parts by weight of the support. When the ruthenium nanoparticles are less than 1 part by weight, when hydrogenation of 2,5-furandicarboxylic acid (FDCA) is performed using the catalyst, the FDCA conversion rate is low and tetrahydrofuran-2,5-dicarboxylic acid It is not preferable because it is difficult to manufacture (THFDCA), and when it exceeds 10 parts by weight, the amount supported on the support is small compared to the amount of ruthenium used, so it is not preferable because it is inefficient.

In addition, the catalyst may be a catalyst used for producing tetrahydrofuran-2,5-dicarboxylic acid by reducing a furan-based compound containing a carboxyl group (-COOH), and the carboxyl group (-COOH ) The furan-based compound containing may be 2,5-furandicarboxylic acid (FDCA).

The present invention (a) produces tetrahydrofuran-2,5-dicarboxylic acid represented by Structural Formula 2 by hydrogenating a furan-based compound represented by Structural Formula 1 in Scheme 1 using hydrogen (H ₂ ) and a catalyst. It provides a method for preparing tetrahydrofuran-2,5-dicarboxylic acid, comprising a support on which the ruthenium nanoparticles are supported.

[Scheme 1]

In addition, the support may include at least one selected from the group consisting of aluminum oxide, titanium oxide, zirconium oxide, manganese oxide, cobalt oxide, and activated carbon, preferably aluminum oxide.

In addition, the hydrogenation reaction may be carried out at a temperature of 30 to 100 °C, preferably 30 to 80 °C, more preferably 50 °C. When the hydrogenation reaction is performed at less than 30 ° C., it is not preferable because the conversion rate of furandicarboxylic acid (FDCA) is low and it is difficult to prepare tetrahydrofuran-2,5-dicarboxylic acid (THFDCA). When carried out in excess, the furan ring of furandicarboxylic acid (FDCA) is ring-opened to form 2-hydroxyadipic acid (HAA) or adipic acid (AA), which is undesirable.

In addition, the catalyst may be 50 to 100 parts by weight based on 100 parts by weight of the furan-based compound. When the amount of the catalyst is less than 50 parts by weight, the conversion rate of furandicarboxylic acid (FDCA) is low and it is difficult to prepare tetrahydrofuran-2,5-dicarboxylic acid (THFDCA), which is not preferable. When the amount exceeds 100 parts by weight, It is not preferable because the increase in the yield of tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) compared to the amount of catalyst is insignificant and inefficient.

In addition, the hydrogenation reaction may further include a solvent, and the solvent may include water.

In addition, the furan-based compound may be 0.1 to 15 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the solvent. When the amount of the furan-based compound is less than 0.1 parts by weight, the amount of tetrahydrofuran-2,5-dicarboxylic acid obtained is undesirably small, and when it exceeds 15 parts by weight, the reaction time takes a long time and the amount of required catalyst increases. It is undesirable because it can affect the price increase of the catalytic process and is not economical.

In addition, the hydrogenation reaction may be performed at a hydrogen pressure of 200 to 1,000 psi, preferably at a hydrogen pressure of 400 to 600 psi. When the hydrogenation reaction is performed at a hydrogen pressure of less than 200 psi, it is not preferable because the conversion rate of furandicarboxylic acid (FDCA) is low and it is difficult to prepare tetrahydrofuran-2,5-dicarboxylic acid (THFDCA). When carried out at a hydrogen pressure higher than psi, excessive use of hydrogen may affect the price increase of the catalytic process, which is undesirable because it is not economical.

In addition, in the method for producing tetrahydrofuran-2,5-dicarboxylic acid, prior to step (a), (a') a reducing agent is added to a mixture containing a support and a ruthenium precursor, and the reaction is performed on the support and the support. Preparing a catalyst comprising ruthenium nanoparticles supported on; may further include.

In addition, the reducing agent may include at least one selected from the group consisting of sodium borohydride (NaBH ₄ ) and ascorbic acid, preferably NaBH ₄ .

In addition, the method for producing tetrahydrofuran-2,5-dicarboxylic acid, after step (a), (b) reuses the catalyst to obtain the furan-based compound represented by Structural Formula 1 and the hydrogen (H ₂ ) to prepare tetrahydrofuran-2,5-dicarboxylic acid represented by Structural Formula 2 by a hydrogenation reaction; may further include.

In addition, the step (b) may be repeated 1 to 10 times.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples. However, this is for illustrative purposes and the scope of the present invention is not limited thereby.

[Preparation of catalyst for producing tetrahydrofuran-2,5-dicarboxylic acid (THFDCA)]

Example 1: Ru/Al ₂ O ₃

1 g of the support (Al ₂ O ₃ ) and 0.085 g of RuCl ₃ ㆍxH ₂ O were put together in a 100 mL round bottom flask containing ~20 mL of distilled water (DI water) and stirred for 12 hours to obtain a reaction mixture. manufactured. Subsequently, an aqueous solution of NaBH ₄ (10 times higher in molar ratio than RuCl ₃ .xH ₂ O) was added dropwise to the reaction mixture at room temperature for one day with constant stirring to prepare a catalyst. Finally, the obtained catalyst was isolated by filtration, washed with ethanol 5 times (100 mL), and dried under vacuum for 12 hours to prepare a Ru/Al ₂ O ₃ catalyst.

Examples 2 to 6

A catalyst was prepared under the same conditions as in Example 1, but the composition of the catalyst prepared with a different type of support is shown in Table 1 below.

catalyst support Example 1 2.0 wt % Ru/Al ₂ O ₃ Al ₂ O ₃ Example 2 2.8 wt % Ru/ZrO ₂ ZrO ₂ Example 3 1.8 wt % Ru/TiO ₂ TiO ₂ Example 4 2.9 wt % Ru/MnO ₂ MnO ₂ Example 5 3.3 wt% Ru/CoO CoO Example 6 5.0 wt% Ru/C C

[Hydrogenation reaction from FDCA to THFDCA]

Reaction Example 1

Hydrogenation of 2,5-furandicarboxylic acid (FDCA) was carried out in a stainless steel autoclave reactor equipped with an agitator, thermocouple and pressure regulator.

0.202 g of FDCA, 0.1635 g of the catalyst prepared according to Example 1 (Ru/Al ₂ O ₃ ) and 20 mL of water were added to the reactor. After purging the reactor with H ₂ three times to remove air at room temperature, the reactor was additionally charged with 450 psi of H ₂ at 50 °C and maintained for a reaction time (4 hours). After the reaction, the reactor was cooled to room temperature and then opened under reduced pressure. The above reaction may be carried out with reference to Scheme 2 below.

[Scheme 2]

Reaction Examples 2 to 6

The experiment was conducted under the same conditions as in Reaction Example 1 but with a different catalyst, and the experimental conditions are shown in Table 2 below.

reaction Catalyst used content FDCA concentration
(wt%) hydrogen
enter
(psi) reaction
temperature
(℃) reaction
hour
(h) FDCA (g) Catalyst (g) Solvent (mL) Reaction Example 1 Example 1 0.202 0.1635 20 One 450 50 4 Reaction Example 2 Example 2 0.202 0.1635 20 One 450 50 4 Reaction Example 3 Example 3 0.202 0.1635 20 One 450 50 4 Reaction Example 4 Example 4 0.202 0.1635 20 One 450 50 4 Reaction Example 5 Example 5 0.202 0.1635 20 One 450 50 4 Reaction Example 6 Example 6 0.202 0.1635 20 One 450 50 4

Reaction Examples 7 to 12

The experiment was conducted under the same conditions as in Reaction Example 1, but with different catalysts and reaction temperatures, and the experimental conditions are shown in Table 3 below.

reaction Catalyst used content FDCA concentration
(wt%) hydrogen
enter
(psi) reaction
temperature
(℃) reaction
hour
(h) FDCA (g) Catalyst (g) Solvent (mL) Reaction Example 7 Example 1 0.202 0.1635 20 One 450 80 4 Reaction Example 8 Example 2 0.202 0.1635 20 One 450 80 4 Reaction Example 9 Example 3 0.202 0.1635 20 One 450 80 4 Reaction Example 10 Example 4 0.202 0.1635 20 One 450 80 4 Reaction Example 11 Example 5 0.202 0.1635 20 One 450 80 4 Reaction Example 12 Example 6 0.202 0.1635 20 One 450 80 4

Reaction Examples 13 to 18

The experiment was conducted under the same conditions as in Reaction Example 1, but with different catalysts and reaction temperatures, and the experimental conditions are shown in Table 4 below.

reaction Catalyst used content FDCA concentration
(wt%) hydrogen
enter
(psi) reaction
temperature
(℃) reaction
hour
(h) FDCA (g) Catalyst (g) Solvent (mL) Reaction Example 13 Example 1 0.202 0.1635 20 One 450 30 4 Reaction Example 14 Example 2 0.202 0.1635 20 One 450 30 4 Reaction Example 15 Example 3 0.202 0.1635 20 One 450 30 4 Reaction Example 16 Example 4 0.202 0.1635 20 One 450 30 4 Reaction Example 17 Example 5 0.202 0.1635 20 One 450 30 4 Reaction Example 18 Example 6 0.202 0.1635 20 One 450 30 4

Reaction Examples 7, 13 and 19

The experiment was conducted under the same conditions as in Reaction Example 1, but the reaction temperature was different, and the experimental conditions are shown in Table 5 below.

reaction Catalyst used content FDCA concentration
(wt%) hydrogen
enter
(psi) reaction
temperature
(℃) reaction
hour
(h) FDCA (g) Catalyst (g) Solvent (mL) Reaction Example 1 Example 1 0.202 0.1635 20 One 450 50 4 Reaction Example 7 Example 1 0.202 0.1635 20 One 450 80 4 Reaction Example 13 Example 1 0.202 0.1635 20 One 450 30 4 Reaction Example 19 Example 1 0.202 0.1635 20 One 450 40 4

Reaction Examples 20 to 22

The experiment was conducted under the same conditions as in Reaction Example 1, but the reaction time was different, and the experimental conditions are shown in Table 6 below.

reaction Catalyst used content FDCA concentration
(wt%) hydrogen
enter
(psi) reaction
temperature
(℃) reaction
hour
(h) FDCA (g) Catalyst (g) Solvent (mL) Reaction Example 1 Example 1 0.202 0.1635 20 One 450 50 4 Reaction Example 20 Example 1 0.202 0.1635 20 One 450 50 One Reaction Example 21 Example 1 0.202 0.1635 20 One 450 50 2 Reaction Example 22 Example 1 0.202 0.1635 20 One 450 50 6

Reaction Examples 23 to 25

The experiment was conducted under the same conditions as in Reaction Example 1, but the hydrogen pressure was varied, and the experimental conditions are shown in Table 7 below.

reaction Catalyst used content FDCA concentration
(wt%) hydrogen
enter
(psi) reaction
temperature
(℃) reaction
hour
(h) FDCA (g) Catalyst (g) Solvent (mL) Reaction Example 1 Example 1 0.202 0.1635 20 One 450 50 4 Reaction Example 23 Example 1 0.202 0.1635 20 One 250 50 4 Reaction Example 24 Example 1 0.202 0.1635 20 One 350 50 4 Reaction Example 25 Example 1 0.202 0.1635 20 One 550 50 4

Reaction Examples 26 and 27

The experiment was conducted under the same conditions as in Reaction Example 1, but with different FDCA concentrations, and the experimental conditions are shown in Table 8 below.

reaction Catalyst used content FDCA concentration
(wt%) hydrogen
enter
(psi) reaction
temperature
(℃) reaction
hour
(h) FDCA (g) Catalyst (g) Solvent (mL) Reaction Example 1 Example 1 0.202 0.1635 20 One 450 50 4 Reaction Example 26 Example 1 0.839 0.679 16 5 450 50 4 Reaction Example 27 Example 1 1.11 0.898 10 10 450 50 4

Reaction Examples 28 and 29

The experiment was conducted under the same conditions as in Reaction Example 1, but the experiment was conducted with different FDCA concentrations and reaction times, and the experimental conditions are shown in Table 9 below.

reaction Catalyst used content FDCA concentration
(wt%) hydrogen
enter
(psi) reaction
temperature
(℃) reaction
hour
(h) FDCA (g) Catalyst (g) Solvent (mL) Reaction Example 1 Example 1 0.202 0.1635 20 One 450 50 4 Reaction Example 28 Example 1 1.053 0.85 20 5 450 50 8 Reaction Example 29 Example 1 2.222 1.79 20 10 450 50 20

[Test Example]

Test Example 1: HR-TEM analysis

1 is an HR-TEM image of catalysts prepared according to Examples 1 to 6.

According to FIG. 1 , it can be confirmed that the ruthenium nanoparticles are well supported on each support (Al ₂ O ₃ , ZrO ₂ , TiO ₂ , MnO ₂ , CoO and C).

Test Example 2: Confirmation of THFDCA selectivity according to support

The liquid product obtained according to the reaction example was quantified using HPLC using a Biorad HPX-87 column and 0.0025 M sulfuric acid as a mobile phase at a flow rate of 0.6 mL/min to calculate the FDCA conversion rate and THFDCA selectivity of the product. At this time, product identification was performed using LC-MS. FDCA conversion rate, THFDCA selectivity, HAA selectivity and AA selectivity were calculated as shown in Equations 1 to 4 below. The calculation was performed in the same way in Test Examples 3 to 7 below.

The FDCA is 2,5-furandicarboxylic acid, the THFDCA is tetrahydrofuran-2,5-dicarboxylic acid, and the HAA is 2-hydroxyadipic acid, the AA is adipic acid.

[Equation 1]

[Equation 2]

[Equation 3]

[Equation 4]

Table 10 below summarizes the FDCA conversion rate, THFDCA selectivity, HAA selectivity and AA selectivity according to the support at reaction temperatures of 80 ° C, 50 ° C and 30 ° C.

reaction temperature
(℃) catalyst FDCA Conversion Rate (%) THFDCA selectivity (%) HAA selectivity (%) AA selectivity (%) 80 Example 1 (Ru/Al ₂ O ₃ ) 99.9 76.6 20.2 - Example 2 (Ru/ZrO ₂ ) 99.9 60.3 28.2 3 Example 3 (Ru/TiO ₂ ) 99.9 75.9 20.7 - Example 4 (Ru/MnO ₂ ) 83.1 56.8 40.0 - Example 5 (Ru/CoO) 99.9 84.3 15.7 - Example 6 (Ru/C) 99.9 65.3 18.7 7.8 50 Example 1 (Ru/Al ₂ O ₃ ) 99.9 85.4 14.5 - Example 2 (Ru/ZrO ₂ ) 47.0 81.9 16.4 - Example 3 (Ru/TiO ₂ ) 82.0 84.6 15.1 - Example 4 (Ru/MnO ₂ ) 0.5 - - - Example 5 (Ru/CoO) 77.1 70.7 27.6 - Example 6 (Ru/C) 92.0 70.2 29.7 - 30 Example 1 (Ru/Al ₂ O ₃ ) 38.1 83.5 16.5 - Example 2 (Ru/ZrO ₂ ) 35.0 80.8 17.4 - Example 3 (Ru/TiO ₂ ) 30.8 84.1 14.9 - Example 4 (Ru/MnO ₂ ) - - - - Example 5 (Ru/CoO) 13.8 63.8 34.1 - Example 6 (Ru/C) 35.0 81.4 17.4 -

According to Table 10, complete conversion of FDCA was achieved in most of the catalysts except for Ru/MnO ₂ at a reaction temperature of 80 °C, and it was confirmed that the primary products formed were THFDCA and HAA. The formation of AA was observed in the hydrogenation reaction of FDCA at 80 °C, and it was confirmed that AA was not formed at low temperature reactions (50 °C and 30 °C).

In addition, it can be confirmed that the HAA selectivity decreases at a lower temperature compared to the reaction at 80 ° C., indicating that the ring opening of the furan ring is strongly advantageous when the FDCA hydrogenation reaction is performed at a high temperature.

At 50 °C, almost complete conversion of FDCA (99.9% and 92.0%, respectively) was observed in Example 1 (Ru/Al ₂ O ₃ ) and Example 6 (Ru/C), which is similar to Example 1 in FDCA hydrogenation. (Ru/Al ₂ O ₃ ) and Example 6 (Ru/C) show high activity. However, it can be confirmed that Example 1 (Ru/Al ₂ O ₃ ) showed a high selectivity of 85.4% for THFDCA, but Ru/C showed a selectivity for THFDCA of 70.2%.

In addition, in Example 1 (Ru/Al ₂ O ₃ ), the THFDCA selectivity was maintained as high as 83.5% even when the FDCA hydrogenation reaction was performed at 30 ° _{C. 3} ) can be confirmed.

Table 11 below summarizes the results of ICP-AES analysis of the solution after the first use of Ru/support (oxide) catalyst at different reaction temperatures (80 °C, 50 °C and 30 °C).

reaction temperature
(℃) catalyst Ru (ppm) Al (ppm) Zr (ppm) Ti (ppm) Mn (ppm) Co (ppm) 80 Example 1 1.5 156.6 - - - - Example 2 1.2 - 10.1 - - - Example 3 5.1 - - 0.1 - - Example 4 0.7 - - - 3222.3 - Example 5 0.2 - - - - 3891.6 50 Example 1 4.2 37.3 - - - - Example 2 5.3 - 8.0 - - - Example 3 10.4 - - 0.8 - - Example 4 0.8 - - - 1773.0 - Example 5 0 - - - - 4212.1 30 Example 1 6.5 68.8 - - - - Example 2 2.1 - 6.9 - - - Example 3 9.5 - - 0.02 - - Example 4 4.7 - - - 2194.3 - Example 5 0.02 - - - - 2772.1

According to Table 11, it can be confirmed that the leaching of Ru is negligible in most catalysts at different reaction temperatures.

However, significant leaching of Mn and Co can be confirmed after the reaction even at a low temperature (30 °C). The low stability of Examples 4 (Ru/MnO ₂ ) and 5 (Ru/CoO) may explain the low selectivity of THFDCA at low temperatures.

On the other hand, it can be confirmed that the high stability of Example 1 (Ru/Al ₂ O ₃ ) can contribute to the high selectivity of THFDCA during the reaction in a water solvent.

Test Example 3: Analysis of conversion rate of FDCA and selectivity of THFDCA according to reaction temperature

Figure 2 is a graph showing the results of FDCA hydrogenation reaction according to the reaction temperature using the catalyst of Example 1.

According to FIG. 2, it can be confirmed that the conversion rate of FDCA increases from 38.1% to 99.9% by increasing the temperature from 30 ° C to 50 ° C, but the THFDCA selectivity shows little change from 83.5% to 85.4%.

The conversion rate of FDCA is maintained constant even when the temperature is raised to 80 ° C., but when the reaction temperature is increased from 50 ° C. to 80 ° C., it can be seen that the selectivity of THFDCA decreases and the selectivity of HAA increases. In addition, AA selectivity of 3% was confirmed at a temperature of 80 °C, indicating that more THFDCA was converted to HAA and AA, which are ring-opening products of the FDCA hydrogenation reaction.

According to Figure 2, it can be seen that the ring opening of FDCA does not occur below 80 ℃ accelerated by increasing the reaction temperature. Therefore, it can be confirmed that 50 ℃ in the present invention is the optimal reaction temperature for producing THFDCA through hydrogenation of FDCA.

Test Example 4: Analysis of conversion rate of FDCA and selectivity of THFDCA according to reaction time

3 is a graph showing the FDCA hydrogenation reaction results according to the reaction time using the catalyst of Example 1.

According to FIG. 3, it can be confirmed that FDCA is quickly converted to THFDCA with a selectivity of 78% when the hydrogenation reaction is performed for 1 hour. It can be confirmed that the conversion of FDCA gradually increases as the reaction time increases, and when the reaction is performed for 4 hours, it can be confirmed that the conversion to THFDCA is performed with a selectivity of 85.4%.

In addition, it can be confirmed that a longer reaction time (6 hours) strongly changes the product distribution. When the reaction was performed for 6 hours, the THFDCA selectivity decreased to 75.5%, while the HAA selectivity increased to 22.5%.

Therefore, it can be confirmed that 4 hours in the present invention is the optimal reaction time for preparing THFDCA through hydrogenation of FDCA.

Test Example 5: Analysis of conversion rate of FDCA and selectivity of THFDCA according to hydrogen pressure

4 is a graph showing the results of FDCA hydrogenation reaction according to hydrogen pressure using the catalyst of Example 1.

According to FIG. 4, it can be seen that the conversion rate of FDCA and the selectivity of THFDCA increase as the hydrogen pressure rises from 250 psi to 450 psi, indicating that FDCA has excellent conversion to THFDCA at a relatively moderate pressure (450 psi). indicate

In addition, when comparing the reactions performed at 450 psi and 550 psi, it can be seen that the conversion rate of FDCA remains constant and the selectivity of THFDCA does not change significantly.

Therefore, it can be confirmed that an appropriate hydrogen pressure of 450 psi maintains the reaction activity and suppresses complete hydrogenation of the furan ring.

Test Example 6: Analysis of conversion rate of FDCA and selectivity of THFDCA according to FDCA concentration

5 is a graph showing the FDCA hydrogenation reaction results according to the FDCA concentration using the catalyst of Example 1, and FIG. 6 is the FDCA hydrogenation reaction result when the reaction time is changed according to the FDCA concentration using the catalyst of Example 1 is the graph shown.

Referring to Figure 5, when the concentration of FDCA is increased from 1 wt% to 10 wt%, it can be seen that the conversion rate of FDCA is significantly reduced. Therefore, the reaction was performed for a longer reaction time (8 hours and 20 hours, respectively) in the presence of 5 wt% and 10 wt% of FDCA, respectively, and the results are shown in FIG. 6 .

According to FIG. 6, as expected, as the reaction time increases, the higher the FDCA concentration, the higher the FDCA conversion rate, and it can be seen that the THFDCA selectivity is also excellent.

Test Example 7: Analysis of conversion rate of FDCA and selectivity of THFDCA according to catalyst reuse

7 is a graph showing the results of FDCA hydrogenation when the catalyst of Example 1 was used 1 to 4 times.

According to FIG. 7 , it can be confirmed that the catalyst can be reused at least 4 times without significant loss of activity.

The scope of the present invention is indicated by the following claims rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts should be construed as being included in the scope of the present invention. do.

Claims (20)

support; and
Ruthenium nanoparticles supported on the support;
A catalyst for producing tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) comprising: According to claim 1,
The catalyst for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the support comprises at least one selected from the group consisting of aluminum oxide, titanium oxide, zirconium oxide, manganese oxide, cobalt oxide and activated carbon. According to claim 1,
A catalyst for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the support comprises aluminum oxide. According to claim 1,
A catalyst for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the ruthenium nanoparticles are 1 to 10 parts by weight based on 100 parts by weight of the support. According to claim 1,
Tetrahydrofuran-2, characterized in that the catalyst is a catalyst used for producing tetrahydrofuran-2,5-dicarboxylic acid by reducing a furan-based compound containing a carboxyl group (-COOH), Catalysts for the production of 5-dicarboxylic acids. According to claim 5,
A catalyst for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the furan-based compound is 2,5-furandicarboxylic acid (FDCA). According to claim 1,
A catalyst for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the catalyst for producing tetrahydrofuran-2,5-dicarboxylic acid is reusable. (a) preparing tetrahydrofuran-2,5-dicarboxylic acid represented by structural formula 2 by hydrogenating a furan-based compound represented by structural formula 1 in Scheme 1 using hydrogen (H ₂ ) and a catalyst; including,
Method for producing tetrahydrofuran-2,5-dicarboxylic acid, wherein the catalyst comprises a support on which ruthenium nanoparticles are supported:
[Scheme 1]

According to claim 8,
Method for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the support comprises at least one selected from the group consisting of aluminum oxide, titanium oxide, zirconium oxide, manganese oxide, cobalt oxide and activated carbon. . According to claim 9,
Method for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the support comprises aluminum oxide. According to claim 8,
Method for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the hydrogenation reaction is carried out at a temperature of 30 to 100 ℃. According to claim 8,
Method for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the catalyst is 50 to 100 parts by weight based on 100 parts by weight of the furan-based compound. According to claim 8,
Method for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the hydrogenation reaction further comprises a solvent. According to claim 13,
Method for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the solvent contains water. According to claim 13,
Method for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the furan-based compound is 0.1 to 15 parts by weight based on 100 parts by weight of the solvent. According to claim 8,
Method for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the hydrogenation reaction is carried out at a hydrogen pressure of 200 to 1,000 psi. According to claim 8,
The method for producing tetrahydrofuran-2,5-dicarboxylic acid before step (a),
(a') preparing a catalyst containing a support and ruthenium nanoparticles supported on the support by adding a reducing agent to a mixture containing a support and a ruthenium precursor and reacting thereon; tetrahydrofuran characterized in that it further comprises Method for producing -2,5-dicarboxylic acid. According to claim 17,
The method for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the reducing agent comprises at least one selected from the group consisting of sodium borohydride (NaBH ₄ ) and ascorbic acid. According to claim 8,
The method for producing tetrahydrofuran-2,5-dicarboxylic acid after step (a),
(b) preparing tetrahydrofuran-2,5-dicarboxylic acid represented by Structural Formula 2 by hydrogenation of the furan-based compound represented by Structural Formula 1 and the hydrogen (H ₂ ) by reusing the catalyst; ; Method for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that it further comprises. According to claim 19,
Method for producing tetrahydrofuran-2,5-dicarboxylic acid, characterized in that the step (b) is repeated 1 to 10 times.

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