KR20250076198A - Ruthenium-supported alumina catalyst, method of manufacturing the same and continuous tetrahydrofuran dimethanol(thfdm) manufacturing apparatus using the same - Google Patents

Abstract

A ruthenium-supported alumina catalyst, a method for producing the same, and a continuous tetrahydrofuran dimethanol (THFDM) producing apparatus using the same are disclosed. The catalyst of the present invention comprises a support comprising alumina (Al ₂ O ₃ ); and ruthenium (Ru) supported on the support; and can obtain tetrahydrofuran dimethanol (THFDM) in high yield by hydrogenation of 5-hydroxymethylfurfural (HMF) using a high-concentration 5-hydroxymethylfurfural (HMF) solution.

Description

{RUTHENIUM-SUPPORTED ALUMINA CATALYST, METHOD OF MANUFACTURING THE SAME AND CONTINUOUS TETRAHYDROFURAN DIMETHANOL(THFDM) MANUFACTURING APPARATUS USING THE SAME}

The present invention relates to a ruthenium-supported alumina catalyst, a method for producing the same, and a continuous tetrahydrofuran dimethanol (THFDM) production device using the same.

Starting with the establishment of an industrial production system after World War II, plastics based on various resins began to be mass-produced as consumer goods. In particular, since the late 1970s, plastics have surpassed the production of steel, and recently, over 300 million tons of plastics have been produced and consumed worldwide. However, since plastics are produced using naphtha from the petroleum refining process, the depletion of petroleum resources and carbon dioxide emissions have become a problem. In addition, since they are used as the main material for disposable products and are discarded immediately after use, a large amount of plastics are discarded. Since they do not decompose for a long time, landfilling is difficult, and when incinerated, carcinogens such as dioxins are emitted into the atmosphere, causing environmental problems. Therefore, research on alternative materials is continuously being conducted.

As a substitute for plastics, scientists are working hard to develop bioplastic materials using starch or cellulose in plants. For example, 5-hydroxymethylfurfural (HMF) is produced from carbohydrates or cellulose in the presence of an acid catalyst, and 5-hydroxymethylfurfural (HMF) is classified as one of 10 biomass-based compounds with significant industrial applications.

2,5-Furandimethanol (FDM), 2,5-Tetrahydrofuran dimethanol (THF-DM), and 2,5-dimethylfuran can be produced through the catalytic hydrogenation of HMF. The 2,5-FDM and 2,5-Tetrahydrofuran dimethanol have excellent potential as they can be used in various fields such as the production of resins, polymers, and chemical fibers with various properties. Therefore, a method for hydrogenating HMF using a metal complex and a metal-supported catalyst to selectively produce 2,5-FDM and 2,5-Tetrahydrofuran dimethanol from HMF in various environments has been actively studied.

When HMF is hydrogenated, a mixture of 2,5-furandimethanol (FDM), 2,5-tetrahydrofuran dimethanol (THF-DM), and 2,5-dimethylfuran is obtained, but there is a problem that an energy-intensive purification process is additionally required to obtain any one of them. Therefore, research is needed to selectively produce the target product in high yield during the hydrogenation reaction of HMF.

The purpose of the present invention is to provide a catalyst capable of selectively producing high-purity tetrahydrofuran dimethanol (THFDM) with a high yield during the hydrogenation reaction of HMF.

Another object of the present invention is to provide a continuous reaction device and production method capable of selectively producing high-purity tetrahydrofuran dimethanol (THFDM) using a reaction solution containing a high concentration of HMF as a substrate.

According to one aspect of the present invention, a catalyst is provided, which comprises a support comprising alumina (Al ₂ O ₃ ); and ruthenium (Ru) supported on the support.

Additionally, the catalyst may be used for producing tetrahydrofuran dimethanol (THFDM) by hydrogenating 5-hydroxymethylfurfural (HMF).

Additionally, the alumina may include γ-Al ₂ O ₃ .

According to another aspect of the present invention, a continuous tetrahydrofuran dimethanol production device (10) is provided, which includes: a 5-hydroxymethylfurfural supply unit (100) that continuously supplies 5-hydroxymethylfurfural (HMF) and a solvent to a reaction unit; a hydrogen supply unit (200) that continuously supplies hydrogen to a reaction unit (300); and a reaction unit (300) that hydrogenates 5-hydroxymethylfurfural using a catalyst to produce tetrahydrofuran dimethanol (THFDM) and continuously discharges the same to the outside.

Additionally, in the reaction section (300), the weight ratio of the solvent and 5-hydroxymethylfurfural (HMF) may be 99:1 to 85:15.

Additionally, in the reaction section (300), the weight ratio of the solvent and 5-hydroxymethylfurfural (HMF) may be 92:8 to 88:12.

Additionally, the solvent may include at least one selected from the group consisting of methanol, 2-propanol, 2-methoxyethanol, ethanol, n-propanol, n-butanol, dimethoxyethane, and 1,2-dimethoxypropane.

Additionally, the solvent may include 2-methoxyethanol.

Additionally, the temperature of the reaction section may be 90 to 180°C, preferably 90 to 110°C.

Additionally, the pressure of the reaction section may be 30 to 100 bar, preferably 80 to 100 bar.

According to another aspect of the present invention, a method for producing a catalyst is provided, comprising: (a) preparing a first mixture by mixing and stirring a ruthenium precursor, alumina, and a solvent; and (b) introducing a reducing agent into the first mixture and reacting the mixture to prepare a second mixture including a ruthenium-supported alumina catalyst.

Additionally, the catalyst may be used for producing tetrahydrofuran dimethanol (THFDM) by hydrogenating 5-hydroxymethylfurfural (HMF).

Additionally, the alumina may include γ-Al ₂ O ₃ .

Additionally, the solvent of step (a) may include water.

Additionally, the reducing agent of step (b) may include NaBH ₄ .

In addition, the method for producing the catalyst may include, after step (b), (c) a step of separating, washing, and drying the catalyst from the second mixture; and (d) a step of producing the dried catalyst into pellets having a size of 180 to 280 μm.

Additionally, the washing in step (c) can be performed using at least one selected from the group consisting of water and C1 to C4 alcohols.

The present invention can provide a catalyst capable of selectively producing high-purity tetrahydrofuran dimethanol (THFDM) with a high yield during the hydrogenation reaction of HMF.

In addition, the present invention can provide a continuous reaction device and a production method capable of selectively producing high-purity tetrahydrofuran dimethanol (THFDM) using a reaction solution containing a high concentration of HMF as a substrate.

Since these drawings are for reference in explaining exemplary embodiments of the present invention, the technical ideas of the present invention should not be interpreted as limited to the attached drawings.
FIG. 1 is a flow chart showing a method for producing an alumina catalyst loaded with ruthenium according to Example 1 of the present invention.
FIG. 2 is a schematic diagram showing a continuous tetrahydrofuran dimethanol (THFDM) production device for producing 2,5-tetrahydrofuran dimethanol (THFDM) according to Examples 2 to 6 of the present invention.
FIG. 3 is an NMR analysis graph of tetrahydrofuran dimethanol (THFDM) according to one embodiment of the present invention.
FIG. 4a is a graph showing the yield of THFDM over time in Example 6-1 of the present invention, FIG. 4b is a graph showing the yield of THFDM over time in Example 6-2 of the present invention, and FIG. 4c is a graph showing the yield of THFDM over time in Example 6-3 of the present invention.

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

However, the following description is not intended to limit the present invention to specific embodiments, and if it is determined that a detailed description of a related known technology may obscure the gist of the present invention when explaining the present invention, the detailed description is omitted.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, it should be understood that the terms "comprises" or "has" and the like are intended to specify the presence of a feature, number, step, operation, component or combination thereof described in the specification, but do not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components or combinations thereof.

Also, terms including ordinal numbers such as first, second, etc., which will be used hereinafter, may be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as the second component, and similarly, the second component may also be referred to as the first component.

Additionally, when it is said that a component is "formed on" or "laminated on" another component, it should be understood that it may be formed or laminated directly on the entire surface or one side of the other component, but there may also be other components present in between.

Hereinafter, a method for high-speed cell culture using a conductive scaffold and electrical stimulation 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 defined only by the scope of the claims described below.

According to one aspect of the present invention, a catalyst is provided, which comprises a support comprising alumina (Al ₂ O ₃ ); and ruthenium (Ru) supported on the support.

Additionally, the catalyst may be used for producing tetrahydrofuran dimethanol (THFDM) by hydrogenating 5-hydroxymethylfurfural (HMF).

Additionally, the alumina may include γ-Al ₂ O ₃ .

According to another aspect of the present invention, a continuous tetrahydrofuran dimethanol production device (10) is provided, which includes: a 5-hydroxymethylfurfural supply unit (100) that continuously supplies 5-hydroxymethylfurfural (HMF) and a solvent to a reaction unit; a hydrogen supply unit (200) that continuously supplies hydrogen to a reaction unit (300); and a reaction unit (300) that hydrogenates 5-hydroxymethylfurfural using a catalyst to produce tetrahydrofuran dimethanol (THFDM) and continuously discharges the same to the outside.

Additionally, in the reaction section (300), the weight ratio of the solvent and 5-hydroxymethylfurfural (HMF) may be 99:1 to 85:15.

Additionally, in the reaction section (300), the weight ratio of the solvent and 5-hydroxymethylfurfural (HMF) may be 92:8 to 88:12.

Additionally, the solvent may include at least one selected from the group consisting of methanol, 2-propanol, 2-methoxyethanol, ethanol, n-propanol, n-butanol, dimethoxyethane, and 1,2-dimethoxypropane.

Additionally, the solvent may include 2-methoxyethanol.

In addition, the temperature of the reaction section may be 90 to 180°C, preferably 90 to 110°C. Here, if the temperature of the reaction section is less than 90°C, an intermediate substance, furandimethanol (FDM), is generated, which is undesirable, and if it exceeds 180°C, a humic substance is generated, which is undesirable.

In addition, the pressure of the reaction section may be 30 to 100 bar, preferably 80 to 100 bar. Here, if the pressure of the reaction section is less than 30 bar, furandimethanol (FDM), which is an intermediate substance, is generated, which is undesirable, and if it exceeds 100 bar, a hydrodeoxygenation reaction occurs, which is undesirable, which is undesirable, since a side reaction product is generated.

According to another aspect of the present invention, a method for producing a catalyst is provided, comprising: (a) preparing a first mixture by mixing and stirring a ruthenium precursor, alumina, and a solvent; and (b) introducing a reducing agent into the first mixture and reacting the mixture to prepare a second mixture including a ruthenium-supported alumina catalyst.

Additionally, the catalyst may be used for producing tetrahydrofuran dimethanol (THFDM) by hydrogenating 5-hydroxymethylfurfural (HMF).

Additionally, the alumina may include γ-Al ₂ O ₃ .

Additionally, the solvent of step (a) may include water.

Additionally, the reducing agent of step (b) may include NaBH ₄ .

In addition, the method for producing the catalyst may include, after step (b), (c) a step of separating, washing, and drying the catalyst from the second mixture; and (d) a step of producing the dried catalyst into pellets having a size of 180 to 280 μm.

Additionally, the washing in step (c) can be performed using at least one selected from the group consisting of water and C1 to C4 alcohols.

[Example]

Hereinafter, preferred embodiments of the present invention will be described. However, these are provided for illustrative purposes only and the scope of the present invention is not limited thereby.

Example 1: 3 wt% Ru/γ-Al ₂ O ₃ Catalyst manufacturing

FIG. 1 is a flow chart showing a method for preparing a ruthenium-supported alumina catalyst according to Example 1 of the present invention. Referring to FIG. 1, 0.4275 g of RuCl ₃ .xH ₂ O, which is a ruthenium precursor, 5 g of γ-Al ₂ O ₃ and 100 ml of ultrapure water, which is a solvent, were placed in a 250 ml round-bottom flask and stirred at room temperature for one day to prepare a first mixture. A nitrogen line was inserted into the first mixture, and bubbling was performed for 1 hour to remove oxygen in the first mixture and the round-bottom flask was filled with nitrogen. Thereafter, 0.775 g of NaBH ₄ was dissolved in a small amount of ultrapure water to prepare a second solvent, and the second solvent was injected into the round-bottom flask filled with nitrogen, followed by stirring for another day to prepare a second mixture. Thereafter, the precipitate (catalyst) and the supernatant formed in the second mixture were separated using a glass filter, and the separated precipitate (catalyst) was washed with water and methanol three or more times to remove impurities, thereby producing a catalyst from which impurities were removed. The washed catalyst was dried at 60° C. and then stored under a nitrogen atmosphere to produce a 3 wt% Ru/γ-Al ₂ O ₃ , which is an alumina catalyst supporting ruthenium. The Ru/γ-Al ₂ O ₃ was compressed using a pelletizer, and then screened to a size of 180 to 280 μm using a sieve.

Example 2: Preparation of 2,5-tetrahydrofuran dimethanol (THFDM) according to solvent

Example 2-1: Methanol (MeOH)

FIG. 2 is a schematic diagram showing a continuous tetrahydrofuran dimethanol (THFDM) production apparatus for producing 2,5-tetrahydrofuran dimethanol (THFDM) according to Examples 2 to 6 of the present invention. Referring to FIG. 2, the outer diameter of the reaction section is 1/2 inch, and the length is 5 cm. A 1 wt% HMF solution, in which HMF as a raw material is mixed with 2-methoxyethanol as a solvent, is sent from the raw material supply section to the reaction section at 0.1 ml/min, and hydrogen is sent from the hydrogen supply section to the reaction section at 30 ml/min, and in the reaction section, the 1 wt% HMF solution, hydrogen, and 1 g of Ru/γ-Al ₂ O ₃ having 3 wt% Ru as a catalyst according to Example 1 are mixed to produce a mixed solution. At this time, the pressure of the reaction section was maintained constant at 85 bar, the weight hourly space velocity (WHSV) was 2 h ^-1 , and the reaction was conducted at a reaction temperature of 170 ℃ for 36 hours to produce tetrahydrofuran dimethanol (THFDM).

Example 2-2: 2-Propanol (IPA)

Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 2-1, except that 2-propanol was used as a solvent and the reaction was carried out for 24 hours instead of using methanol as a solvent and reacting for 36 hours.

Example 2-3: 2-Methoxyethanol (MEG)

Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 2-1, except that 2-methoxyethanol was used as a solvent and the reaction was carried out for 72 hours instead of using methanol as a solvent and reacting for 36 hours.

Example 3: Preparation of 2,5-tetrahydrofuran dimethanol (THFDM) according to reaction temperature

Example 3-1: Reaction temperature 170 ℃

The outer diameter of the reaction section is 1/2 inch, and the length is 5 cm. A 1 wt% HMF solution, in which HMF as a raw material is mixed with 2-methoxyethanol as a solvent, was supplied from the raw material supply section to the reaction section at a rate of 0.1 ml/min, and hydrogen was supplied from the hydrogen supply section to the reaction section at a rate of 10 ml/min. In the reaction section, the 1 wt% HMF solution, hydrogen, and 1.35 g of Ru/γ-Al ₂ O ₃ with 3 wt% Ru as a catalyst according to Example 1 were mixed to prepare a mixed solution. At this time, the pressure of the reaction section was maintained constant at 85 bar, the WHSV (weight hourly space velocity) was 1.5 h ^-1 , and the reaction was conducted at a reaction temperature of 170 °C for 20 hours to produce tetrahydrofuran dimethanol (THFDM).

Example 3-2: Reaction temperature 160 ℃

Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 3-1, except that the reaction temperature was 160°C instead of 170°C.

Example 3-3: Reaction temperature 140 ℃

Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 3-1, except that the reaction temperature was 140°C instead of 170°C.

Example 3-4: Reaction temperature 120 ℃

Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 3-1, except that the reaction temperature was 120°C instead of 170°C.

Example 3-5: Reaction temperature 100 ℃

Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 3-1, except that the reaction temperature was 100 ℃ instead of 170 ℃.

Example 4: Preparation of 2,5-tetrahydrofuran dimethanol (THFDM) under pressure

Example 4-1: Pressure 85 bar

The outer diameter of the reaction section is 1/2 inch, and the length is 5 cm. A 1 wt% HMF solution, in which HMF as a raw material is mixed with 2-methoxyethanol as a solvent, was supplied from the raw material supply section to the reaction section at a rate of 0.1 ml/min, and hydrogen was supplied from the hydrogen supply section to the reaction section at a rate of 10 ml/min. In the reaction section, the 1 wt% HMF solution, hydrogen, and 1.35 g of Ru/γ-Al ₂ O ₃ having 3 wt% Ru as a catalyst according to Example 1 were mixed to prepare a mixed solution. At this time, the pressure of the reaction section was maintained constant at 85 bar, the WHSV (weight hourly space velocity) was 1.5 h ^-1 , and the reaction was conducted at a reaction temperature of 100 °C for 20 hours to produce tetrahydrofuran dimethanol (THFDM).

Example 4-2: Pressure 70 bar

Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 4-1, except that the process was performed at 70 bar instead of 85 bar.

Example 4-3: Pressure 55 bar

Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 4-1, except that the process was performed at 55 bar instead of 85 bar.

Example 4-4: Pressure 40 bar

Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 4-1, except that the process was performed at 40 bar instead of 85 bar.

Example 5: Preparation of tetrahydrofuran dimethanol (THFDM) according to weight hourly space velocity (WHSV)

Example 5-1: WHSV = 1 h ^-1

The outer diameter of the reaction section is 1/2 inch and the length is 5 cm. A 1 wt% HMF solution, in which HMF as a raw material is mixed with 2-methoxyethanol as a solvent, was sent from the raw material supply section to the reaction section at 0.1 ml/min, and hydrogen was sent from the hydrogen supply section to the reaction section at 10 ml/min. In the reaction section, the 1 wt% HMF solution, hydrogen, and 2 g of Ru/γ-Al ₂ O ₃ with 3 wt% Ru as a catalyst according to Example 1 were mixed to prepare a mixed solution. At this time, the pressure of the reaction section was maintained constant at 85 bar, the WHSV (weight hourly space velocity) was 1 h ^-1 , and the reaction was conducted at a reaction temperature of 100 ℃ for 82 hours to produce tetrahydrofuran dimethanol (THFDM).

Example 5-2: WHSV = 2 h ^-1

Tetrahydrofuran dimethanol ⁽ THFDM) was prepared in the same manner as in Example 5-1, except that instead of using a 1 wt% HMF solution and reacting for 82 hours at a WHSV of 1 h ^-1 , a 2 wt% HMF solution was used and reacted for 20 hours at a WHSV of 2 h -1 .

Example 5-3: WHSV = 3 h ^-1

Tetrahydrofuran dimethanol ⁽ THFDM) was prepared in the same manner as in Example 5-1, except that instead of using a 1 wt% HMF solution and reacting for 82 hours at a WHSV of 1 h ^-1 , a 3 wt% HMF solution was used and reacted for 20 hours at a WHSV of 3 h -1 .

Example 6: Preparation of 2,5-tetrahydrofuran dimethanol (THFDM) according to HMF concentration

Example 6-1: HMF concentration 2 wt%

The outer diameter of the reaction section is 1/2 inch, and the length is 5 cm. A 2 wt% HMF solution, in which HMF as a raw material is mixed with 2-methoxyethanol as a solvent, was sent from the raw material supply section to the reaction section at a rate of 0.1 ml/min, and hydrogen was sent from the hydrogen supply section to the reaction section at a rate of 10 ml/min. In the reaction section, the 2 wt% HMF solution, hydrogen, and 2 g of Ru/γ-Al ₂ O ₃ with 3 wt% Ru as a catalyst according to Example 1 were mixed to prepare a mixed solution. At this time, the pressure of the reaction section was maintained constant at 85 bar, the WHSV (weight hourly space velocity) was 2 h ^-1 , and the reaction was conducted at a reaction temperature of 100 ℃ for 20 hours to produce tetrahydrofuran dimethanol (THFDM).

Example 6-2: HMF concentration 5 wt%

Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 6-1, except that instead of using a 2 wt% HMF solution, the flow rate of the HMF solution was 0.1 ml/min, and the reaction was carried out for 20 hours, a 5 wt% HMF solution was used, the flow rate of the HMF solution was 0.04 ml/min, and the reaction was carried out for 54 hours.

Example 6-3: HMF concentration 10 wt%

Tetrahydrofuran dimethanol (THFDM) was produced in the same manner as in Example 6-1, except that instead of using a reactor having a reactor length of 5 cm, using a 2 wt% HMF solution, using a HMF solution flow rate of 0.1 ml/min, using 2 g of a catalyst, keeping the pressure constant at 20 bar, reacting for 20 hours with a WHSV of 2 h ^-1 , a reactor having a reactor length of 20 cm, using a 10 wt% HMF solution, using a HMF solution flow rate of 0.03 ml/min, using 10 g of a catalyst, keeping the pressure constant at 95 bar, reacting for 18 hours with a WHSV of 0.6 h ^-1 .

Table 1 below summarizes the reaction conditions for producing 2,5-tetrahydrofuran dimethanol (THFDM) according to Examples 2 to 6.

division HMF concentration
(wt%) HMF flow rate
(ml/min) Hydrogen flow rate
(ml/min) Ru loading concentration (wt%) Catalyst amount
(g) Solvent type Reaction temperature
(℃) Reaction pressure
(bar) Reaction time
(h) WHSV
(h ^-1 ) Example 2-1 1 0.1 30 3 1 MeOH 170 85 36 2 Example 2-2 1 0.1 30 3 1 IPA 170 85 24 2 Example 2-3 1 0.1 30 3 1 MEG 170 85 72 2 Example 3-1 1 0.1 10 3 1.35 MEG 170 85 20 1.5 Example 3-2 1 0.1 10 3 1.35 MEG 160 85 20 1.5 Example 3-3 1 0.1 10 3 1.35 MEG 140 85 20 1.5 Example 3-4 1 0.1 10 3 1.35 MEG 120 85 20 1.5 Example 3-5 1 0.1 10 3 1.35 MEG 100 85 20 1.5 Example 4-1 1 0.1 10 3 1.35 MEG 100 85 20 1.5 Example 4-2 1 0.1 10 3 1.35 MEG 100 70 20 1.5 Example 4-3 1 0.1 10 3 1.35 MEG 100 55 20 1.5 Example 4-4 1 0.1 10 3 1.35 MEG 100 40 20 1.5 Example 5-1 1 0.1 10 3 2 MEG 100 85 82 1 Example 5-2 2 0.1 10 3 2 MEG 100 85 20 2 Example 5-3 3 0.1 10 3 2 MEG 100 85 20 3 Example 6-1 2 0.1 10 3 2 MEG 100 85 20 2 Example 6-2 5 0.04 10 3 2 MEG 100 85 54 2 Example 6-3 10 0.03 10 3 10 MEG 100 95 18 0.6

In Table 1 above, MeOH stands for methanol, IPA stands for 2-propanol, MEG stands for 2-methoxyethanol, HMF stands for 5-hydroxymethylfurfural, and WHSV stands for weight hourly space velocity.

[Example]

Conversion, Yield and Selectivity Analysis: High Performance Liquid Chromatography (HPLC)

After the reactions of Examples 2 to 6 were completed and the mixture was cooled to room temperature, the resulting mixture was transferred to a vial and quantitatively analyzed using high-performance liquid chromatography (HPLC). The analysis was performed using high-performance liquid chromatography (HPLC) equipment (Agilent Technologies 1200 series, Bio-Rad Aminex HPX-87 H pre-packed column, and UV-detector), and the conversion of 5-hydroxymethylfurfural (HMF), the yield of 2,5-furandimethanol (FDM), and the yield of tetrahydrofuran dimethanol (THFDM) were measured using the HPLC equipment, and calculated using the following equations 1 to 3.

In addition, the contact time between the substrate HMF and the catalyst in the continuous reaction was controlled by changing the weight hourly space velocity (WHSV), and the WHSV was calculated using the following equation 4.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

Test Example 1: NMR (nuclear magnetic resonance) analysis

FIG. 3 is an NMR analysis graph of tetrahydrofuran dimethanol (THFDM) according to Example 5-2 of the present invention. Referring to FIG. 3, after the hydrogenation reaction of HMF, the product that showed only the solvent and THFDM without any byproducts in the HPLC analysis was collected. The solvent was completely removed from the product using a vacuum distillation device at 150°C and 450 mbar to obtain a high-viscosity liquid. It was confirmed that the high-viscosity liquid produced high-purity (97.8%) THFDM through NMR analysis and the following equation 5.

[Formula 5]

Test Example 2: Comparison of tetrahydrofuran dimethanol (THFDM) yields according to solvent types

Table 2 below is a table showing the conversion rate of 5-hydroxymethylfurfural (HMF), the yield of tetrahydrofuran dimethanol (THFDM), and the yield of 2,5-furandimethanol (FDM) according to Examples 2-1 to 2-3 of the present invention. Referring to Table 2, the HMF conversion rate, THFDM yield, and FDM yield according to the solvent could be known.

division menstruum HMF Conversion Rate (%) THFDM yield (%) FDM Yield (%) Reaction time (h) Example 2-1 Methanol (MeOH) 90 ~ 100 20 ~ 30 1.5 ~ 6 36 Example 2-2 2-Propanol (IPA) Over 98 20 ~ 40 0 ~ 3 24 Example 2-3 2-Methoxyethanol (MEG) 100 60 ~ 76 less than 2 72

Experimental Example 3: Comparison of tetrahydrofuran dimethanol (THFDM) yield according to reaction temperature

Table 3 below shows the conversion rate of 5-hydroxymethylfurfural (HMF), the yield of tetrahydrofuran dimethanol (THFDM), and the yield of 2,5-furandimethanol (FDM) according to Examples 3-1 to 3-5 of the present invention. Referring to Table 3, the HMF conversion rate, THFDM yield, and FDM yield according to the reaction temperature could be known.

division Reaction temperature (℃) HMF Conversion Rate (%) THFDM yield (%) FDM Yield (%) Reaction time (h) Example 3-1 170 100 64 ~ 78 less than 1 20 Example 3-2 160 100 66 ~ 75 less than 1 20 Example 3-3 140 100 66 ~ 75 less than 1 20 Example 3-4 120 100 80 ~ 85 less than 1 20 Example 3-5 100 100 88 ~ 96 0 20

Experimental Example 4: Comparison of tetrahydrofuran dimethanol (THFDM) yield according to reaction pressure

Table 4 below shows the conversion rate of 5-hydroxymethylfurfural (HMF), the yield of tetrahydrofuran dimethanol (THFDM), and the yield of 2,5-furandimethanol (FDM) according to Examples 4-1 to 4-4 of the present invention. Referring to Table 4, the HMF conversion rate, THFDM yield, and FDM yield according to the reaction pressure could be known.

division Reaction pressure (bar) HMF Conversion Rate (%) THFDM yield (%) FDM Yield (%) Reaction time (h) Example 4-1 85 100 88 ~ 96 0 20 Example 4-2 70 100 66 ~ 75 15 ~ 20 20 Example 4-3 55 91 ~ 95 54 ~ 61 18 ~ 24 20 Example 4-4 40 80 ~ 85 48~56 30 ~ 38 20

Test Example 5: Comparison of tetrahydrofuran dimethanol (THFDM) yields according to WHSV

Table 5 below shows the conversion rate of 5-hydroxymethylfurfural (HMF), the yield of tetrahydrofuran dimethanol (THFDM), and the yield of 2,5-furandimethanol (FDM) according to Examples 5-1 to 5-3 of the present invention. Referring to Table 5, the HMF conversion rate, THFDM yield, and FDM yield according to WHSV were known.

division HMF concentration (wt%) WHSV(h ^-1 ) HMF Conversion Rate (%) THFDM yield (%) FDM Yield (%) Reaction time (h) Example 5-1 1 1 100 86 ~ 100 0 82 Example 5-2 2 2 100 88 ~ 96 0 20 Example 5-3 3 3 100 87 ~ 90 0.1 ~ 2 20

Experimental Example 6: Comparison of tetrahydrofuran dimethanol (THFDM) yield according to HMF concentration

Table 6 below is a table showing the conversion rate of 5-hydroxymethylfurfural (HMF), the yield of tetrahydrofuran dimethanol (THFDM), and the yield of 2,5-furandimethanol (FDM) according to Examples 6-1 to 6-3 of the present invention. Referring to Table 6, the HMF conversion rate, THFDM yield, and FDM yield according to the HMF concentration could be known.

division HMF concentration (wt%) WHSV(h ^-1 ) HMF Conversion Rate (%) THFDM yield (%) FDM Yield (%) Reaction time (h) Example 6-1 2 2 100 88 ~ 96 0 20 Example 6-2 5 2 100 85 ~ 95 0 ~ 0.1 54 Example 6-3 10 0.6 100 86 ~ 97 0 ~ 0.3 18

Experimental Example 7: Comparison of THFDM yields according to HMF concentration and time

Test Example 7-1: Comparison of THFDM yields with HMF concentration of 2 wt% and time

Fig. 4a is a graph showing the yield of THFDM over time in Example 6-1 of the present invention. Referring to Fig. 4a, it was found that the yield was consistently 87.5 to 96.2% for 2 to 20 hours.

Test Example 7-2: Comparison of yields of THFDM with HMF concentration of 5 wt% and time

Fig. 4b is a graph showing the yield of THFDM over time in Example 6-2 of the present invention. Referring to Fig. 4b, it was found that the yield was consistently 84.6 to 96.2% for 2 to 54 hours.

Test Example 7-3: Comparison of THFDM yields with HMF concentration of 10 wt% and time

Fig. 4c is a graph showing the yield of THFDM over time in Example 6-3 of the present invention. Referring to Fig. 4c, it was found that the yield was consistently 86.1 to 97.1% for 2 to 18 hours.

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

10: Continuous tetrahydrofuran dimethanol production device
100: 5-Hydroxymethylfurfural supply unit
200: Hydrogen supply unit
300: Reaction section

Claims (17)

A support comprising alumina (Al ₂ O ₃ ); and
Ruthenium (Ru) supported on the above support;
A catalyst containing: In the first paragraph,
A catalyst for use in the hydrogenation reaction of 5-hydroxymethylfurfural (HMF) to produce tetrahydrofuran dimethanol (THFDM). In the first paragraph,
A catalyst characterized in that the alumina comprises γ-Al ₂ O ₃ . A 5-hydroxymethylfurfural supply unit (100) that continuously supplies 5-hydroxymethylfurfural (HMF) and a solvent to the reaction unit below;
A hydrogen supply unit (200) that continuously supplies hydrogen to the reaction unit (300); and
A reaction unit (300) for producing tetrahydrofuran dimethanol (THFDM) by hydrogenating 5-hydroxymethylfurfural using a catalyst according to claim 1 and continuously discharging it to the outside;
A continuous tetrahydrofuran dimethanol manufacturing device (10). In paragraph 4,
A continuous tetrahydrofuran dimethanol production device, characterized in that the weight ratio of the solvent and 5-hydroxymethylfurfural (HMF) in the above reaction section (300) is 99:1 to 85:15. In paragraph 5,
A continuous tetrahydrofuran dimethanol production device, characterized in that the weight ratio of the solvent and 5-hydroxymethylfurfural (HMF) in the above reaction section (300) is 92:8 to 88:12. In paragraph 4,
A continuous tetrahydrofuran dimethanol production device, characterized in that the solvent comprises at least one selected from the group consisting of methanol, 2-propanol, 2-methoxyethanol, ethanol, n-propanol, n-butanol, dimethoxyethane, and 1,2-dimethoxypropane. In Article 7,
A continuous tetrahydrofuran dimethanol production device, characterized in that the solvent contains 2-methoxyethanol. In paragraph 4,
A continuous tetrahydrofuran dimethanol production device, characterized in that the temperature of the above reaction section is 90 to 180°C. In paragraph 4,
A continuous tetrahydrofuran dimethanol production device, characterized in that the pressure of the above reaction section is 30 to 100 bar. (a) preparing a first mixture by mixing and stirring a ruthenium precursor, alumina, and a solvent; and
(b) a step of adding a reducing agent to the first mixture and reacting the mixture to produce a second mixture containing a ruthenium-supported alumina catalyst;
A method for producing a catalyst comprising: In Article 11,
A method for producing a catalyst, wherein the catalyst is used for producing tetrahydrofuran dimethanol (THFDM) by hydrogenating 5-hydroxymethylfurfural (HMF). In Article 11,
A method for producing a catalyst, characterized in that the alumina comprises γ-Al ₂ O ₃ . In Article 11,
A method for producing a catalyst, characterized in that the solvent in step (a) contains water. In Article 11,
A method for producing a catalyst, characterized in that the reducing agent of step (b) comprises NaBH ₄ . In Article 11,
The method for manufacturing the above catalyst comprises the steps (b) and thereafter:
(c) a step of separating, washing and drying the catalyst from the second mixture; and
(d) A method for producing a catalyst, characterized by comprising the step of producing a dried catalyst into pellets having a size of 180 to 280 μm. In Article 16,
A method for producing a catalyst, characterized in that the washing in step (c) is performed using at least one selected from the group consisting of water and C1 to C4 alcohols.