Ruthenium-supported alumina catalyst, producing method therefor, and continuous tetrahydrofuran dimethanol (THFDM) producing apparatus using same

Abstract

Disclosed are a ruthenium-supported alumina catalyst, a producing method therefor, and a continuous tetrahydrofuran dimethanol (THFDM) producing apparatus using same. The catalyst of the present invention comprises: a support containing alumina (Al2O3): and ruthenium (Ru) supported on the support, and enables high-yield acquisition of tetrahydrofuran dimethanol (THFDM) by a hydrogenation reaction of 5-hydroxymethylfurfural (HMF) using a highly concentrated 5-hydroxymethylfurfural (HMF) solution.

Description

Ruthenium-supported alumina catalyst, its preparation method, and continuous tetrahydrofuran dimethanol (THFDM) production device using the same

[0001] 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.

[0002] With the establishment of industrial production systems following World War II, plastics based on various resins began to be mass-produced as consumer goods. Since the late 1970s, plastics have surpassed steel production, and currently, over 300 million tons are produced and consumed worldwide. However, because plastics are produced using naphtha derived from petroleum refining, petroleum resource depletion and carbon dioxide emissions are problematic. Furthermore, because they are the primary material for disposable products, they are often discarded immediately after use, resulting in a large volume of plastic waste. Because plastics do not decompose over a long period of time, landfilling them is difficult. Incineration releases carcinogens, including dioxins, into the atmosphere, posing environmental problems. Therefore, research into alternative materials is ongoing.

[0003] As a substitute for plastic, scientists are focusing their efforts on developing bioplastic materials derived from plant starch or cellulose. For example, 5-hydroxymethylfurfural (HMF) is produced from carbohydrates or cellulose in the presence of an acid catalyst. It is classified as one of ten biomass-derived compounds with significant industrial applications.

[0004] Through the catalytic hydrogenation of HMF, 2,5-furandimethanol (FDM), 2,5-tetrahydrofuran dimethanol (THF-DM), and 2,5-dimethylfuran can be produced. The 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol have great potential as they can be used in various fields such as the production of resins, polymers, and chemical fibers with various properties. Therefore, a hydrogenation method of HMF that can selectively produce 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol from HMF using a metal complex and a metal-supported catalyst in various environments has been actively studied.

[0005] 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 in 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 HMF hydrogenation reaction.

[0006] The purpose of the present invention is to provide a catalyst capable of selectively producing high-purity tetrahydrofuran dimethanol (THFDM) in high yield during hydrogenation of HMF.

[0007] 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.

[0008] According to one aspect of the present invention, a catalyst is provided, comprising: a support comprising alumina (Al2O3); and ruthenium (Ru) supported on the support.

[0009] Additionally, the catalyst may be used to produce tetrahydrofuran dimethanol (THFDM) by hydrogenating 5-hydroxymethylfurfural (HMF).

[0010] Additionally, the alumina may include γ-Al2O3.

[0011] According to another aspect of the present invention, a continuous tetrahydrofuran dimethanol production device (10) is provided, comprising: a 5-hydroxymethylfurfural supply unit (100) for continuously supplying 5-hydroxymethylfurfural (HMF) and a solvent to the following reaction unit; a hydrogen supply unit (200) for continuously supplying hydrogen to the following reaction unit (300); and a reaction unit (300) for hydrogenating 5-hydroxymethylfurfural using a catalyst to produce tetrahydrofuran dimethanol (THFDM) and continuously discharging it to the outside.

[0012] Additionally, in the reaction section (300), the weight ratio of the solvent and 5-hydroxymethylfurfural (HMF) may be 99:1 to 85:15.

[0013] Additionally, in the reaction section (300), the weight ratio of the solvent and 5-hydroxymethylfurfural (HMF) may be 92:8 to 88:12.

[0014] 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.

[0015] Additionally, the solvent may include 2-methoxyethanol.

[0016] Additionally, the temperature of the reaction section may be 90 to 180°C, preferably 90 to 110°C.

[0017] Additionally, the pressure of the reaction section may be 30 to 100 bar, preferably 80 to 100 bar.

[0018] According to another aspect of the present invention, a method for preparing a catalyst is provided, comprising: (a) preparing a first mixture by mixing and stirring a ruthenium precursor, alumina, and a solvent; and (b) preparing a second mixture including a ruthenium-supported alumina catalyst by adding a reducing agent to the first mixture and reacting the mixture.

[0019] Additionally, the catalyst may be used to produce tetrahydrofuran dimethanol (THFDM) by hydrogenating 5-hydroxymethylfurfural (HMF).

[0020] Additionally, the alumina may include γ-Al2O3.

[0021] Additionally, the solvent of step (a) may include water.

[0022] Additionally, the reducing agent of step (b) may include NaBH4.

[0023] In addition, the method for manufacturing 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 manufacturing the dried catalyst into pellets having a size of 180 to 280 μm.

[0024] 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.

[0025] The present invention can provide a catalyst capable of selectively producing high-purity tetrahydrofuran dimethanol (THFDM) in high yield during a hydrogenation reaction of HMF.

[0026] 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.

[0027] These drawings are for reference in explaining exemplary embodiments of the present invention, and therefore, the technical idea of ​​the present invention should not be interpreted as being limited to the attached drawings.

[0028] FIG. 1 is a flowchart showing a method for manufacturing a ruthenium-supported alumina catalyst according to Example 1 of the present invention.

[0029] 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.

[0030] Figure 3 is an NMR analysis graph of tetrahydrofuran dimethanol (THFDM) according to one embodiment of the present invention.

[0031] 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.

[0032] 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.

[0033] However, the following description is not intended to limit the present invention to a specific embodiment, and when explaining the present invention, if it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description is omitted.

[0034] The terminology used herein is for the purpose of describing specific 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, the terms "comprises" or "has" and the like are intended to indicate the presence of a feature, number, step, operation, component, or combination thereof described in the specification, but should be understood to not preclude the presence or addition of one or more other features, numbers, steps, operations, components, or combinations thereof.

[0035] Additionally, terms including ordinal numbers, such as "first," "second," etc., which will be used hereinafter, may be used to describe various components, but these components are not limited by these terms. These terms are used solely to distinguish one component from another. For example, without departing from the scope of the present invention, a first component could be referred to as a second component, and similarly, a second component could also be referred to as a first component.

[0036] 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.

[0037] Hereinafter, a ruthenium-supported alumina catalyst, a method for producing the same, and a continuous tetrahydrofuran dimethanol (THFDM) production device using the same will be described in detail. However, these are provided as examples, and the present invention is not limited thereto, and the present invention is defined solely by the scope of the claims set forth below.

[0038] According to one aspect of the present invention, a catalyst is provided, comprising: a support comprising alumina (Al2O3); and ruthenium (Ru) supported on the support.

[0039] Additionally, the catalyst may be used to produce tetrahydrofuran dimethanol (THFDM) by hydrogenating 5-hydroxymethylfurfural (HMF).

[0040] Additionally, the alumina may include γ-Al2O3.

[0041] According to another aspect of the present invention, a continuous tetrahydrofuran dimethanol production device (10) is provided, comprising: a 5-hydroxymethylfurfural supply unit (100) for continuously supplying 5-hydroxymethylfurfural (HMF) and a solvent to the following reaction unit; a hydrogen supply unit (200) for continuously supplying hydrogen to the following reaction unit (300); and a reaction unit (300) for hydrogenating 5-hydroxymethylfurfural using a catalyst to produce tetrahydrofuran dimethanol (THFDM) and continuously discharging it to the outside.

[0042] Additionally, in the reaction section (300), the weight ratio of the solvent and 5-hydroxymethylfurfural (HMF) may be 99:1 to 85:15.

[0043] Additionally, in the reaction section (300), the weight ratio of the solvent and 5-hydroxymethylfurfural (HMF) may be 92:8 to 88:12.

[0044] 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.

[0045] Additionally, the solvent may include 2-methoxyethanol.

[0046] 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.

[0047] 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, an intermediate substance, furandimethanol (FDM), is generated, which is undesirable, and if it exceeds 100 bar, a hydrodeoxygenation reaction occurs, which is undesirable because a side product is generated.

[0048] According to another aspect of the present invention, a method for preparing a catalyst is provided, comprising: (a) preparing a first mixture by mixing and stirring a ruthenium precursor, alumina, and a solvent; and (b) preparing a second mixture including a ruthenium-supported alumina catalyst by adding a reducing agent to the first mixture and reacting the mixture.

[0049] Additionally, the catalyst may be used for producing tetrahydrofuran dimethanol (THFDM) by hydrogenating 5-hydroxymethylfurfural (HMF).

[0050] Additionally, the alumina may include γ-Al2O3.

[0051] Additionally, the solvent of step (a) may include water.

[0052] Additionally, the reducing agent of step (b) may include NaBH4.

[0053] In addition, the method for manufacturing 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 manufacturing the dried catalyst into pellets having a size of 180 to 280 μm.

[0054] 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.

[0055] [Explanation of symbols]

[0056] 10: Continuous tetrahydrofuran dimethanol production device

[0057] 100: 5-hydroxymethylfurfural supply unit

[0058] 200: Hydrogen supply unit

[0059] 300: Reaction section

[0060] [Example]

[0061] 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.

[0062] Example 1: Preparation of 3 wt% Ru / γ-Al2O3 catalyst

[0063] FIG. 1 is a flowchart 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 RuCl3.xH2O, which is a ruthenium precursor, 35 g of γ-Al2O, 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 NaBH4 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. Afterwards, the precipitate (catalyst) and 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-Al2O3, which is an alumina catalyst loaded with ruthenium, and the Ru / γ-Al2O3 was compressed using a pelletizer and then screened to a size of 180 to 280 μm using a sieve.

[0064] Example 2: Preparation of 2,5-tetrahydrofurandimethanol (THFDM) according to solvent

[0065] Example 2-1: Methanol (MeOH)

[0066] Figure 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. Referring to Figure 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 supplied from the raw material supply section to the reaction section at 0.1 ml / min, hydrogen is supplied from the hydrogen supply section to the reaction section at 30 ml / min, and a mixture solution is prepared by mixing the 1 wt% HMF solution, hydrogen, and 1 g of Ru / γ-Al2O3 with 3 wt% Ru as a catalyst according to Example 1 in the reaction section. At this time, the pressure of the reaction section is maintained constant at 85 bar, and the WHSV (weight hourly space velocity) is 2 h -1 And, tetrahydrofuran dimethanol (THFDM) was produced by reacting at a reaction temperature of 170 ℃ for 36 hours.

[0067] Example 2-2: 2-Propanol (IPA)

[0068] Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 2-1, except that 2-propanol was used as the solvent and the reaction was carried out for 24 hours instead of using methanol as the solvent and reacting for 36 hours.

[0069] Example 2-3: 2-methoxyethanol (MEG)

[0070] 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 carrying out the reaction for 36 hours.

[0071] Example 3: Preparation of 2,5-tetrahydrofuran dimethanol (THFDM) according to reaction temperature

[0072] Example 3-1: Reaction temperature 170 ℃

[0073] The outer diameter of the reaction section is 1 / 2 inch and the length is 5 cm. A 1 wt% HMF solution, in which the raw material HMF is mixed with the solvent 2-methoxyethanol, is supplied from the raw material supply section to the reaction section at 0.1 ml / min, and hydrogen is supplied from the hydrogen supply section to the reaction section at 10 ml / min. In the reaction section, the 1 wt% HMF solution, hydrogen, and 1.35 g of Ru / γ-Al2O3 with 3 wt% Ru, a catalyst according to Example 1, are mixed to prepare a mixed solution. At this time, the pressure of the reaction section is maintained constant at 85 bar, and the WHSV (weight hourly space velocity) is 1.5 h -1 And, tetrahydrofuran dimethanol (THFDM) was produced by reacting at a reaction temperature of 170 ℃ for 20 hours.

[0074] Example 3-2: Reaction temperature 160 ℃

[0075] 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.

[0076] Example 3-3: Reaction temperature 140 ℃

[0077] 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.

[0078] Example 3-4: Reaction temperature 120 ℃

[0079] 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.

[0080] Example 3-5: Reaction temperature 100 ℃

[0081] Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 3-1, except that the reaction temperature was 100°C instead of 170°C.

[0082] Example 4: Preparation of 2,5-tetrahydrofuran dimethanol (THFDM) under pressure

[0083] Example 4-1: Pressure 85 bar

[0084] The outer diameter of the reaction section is 1 / 2 inch and the length is 5 cm. A 1 wt% HMF solution, in which the raw material HMF is mixed with the solvent 2-methoxyethanol, is supplied from the raw material supply section to the reaction section at 0.1 ml / min, and hydrogen is supplied from the hydrogen supply section to the reaction section at 10 ml / min. In the reaction section, the 1 wt% HMF solution, hydrogen, and 1.35 g of Ru / γ-Al2O3 with 3 wt% Ru, a catalyst according to Example 1, are mixed to prepare a mixed solution. At this time, the pressure of the reaction section is maintained constant at 85 bar, and the WHSV (weight hourly space velocity) is 1.5 h -1 And, tetrahydrofuran dimethanol (THFDM) was produced by reacting at a reaction temperature of 100 ℃ for 20 hours.

[0085] Example 4-2: Pressure 70 bar

[0086] Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 4-1, except that the pressure was 70 bar instead of 85 bar.

[0087] Example 4-3: Pressure 55 bar

[0088] Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 4-1, except that the pressure was 55 bar instead of 85 bar.

[0089] Example 4-4: Pressure 40 bar

[0090] Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 4-1, except that the pressure was 40 bar instead of 85 bar.

[0091] Example 5: Preparation of tetrahydrofuran dimethanol (THFDM) according to weight hourly space velocity (WHSV)

[0092] Example 5-1: WHSV = 1 h -1

[0093] 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 supplied from the raw material supply section to the reaction section at 0.1 ml / min, hydrogen is supplied from the hydrogen supply section to the reaction section at 10 ml / min, and in the reaction section, the 1 wt% HMF solution, hydrogen, and 2 g of Ru / γ-Al2O3 with 3 wt% Ru as a catalyst according to Example 1 are mixed to prepare a mixed solution. At this time, the pressure of the reaction section is maintained constant at 85 bar, and the WHSV (weight hourly space velocity) is 1 h -1 And, tetrahydrofuran dimethanol (THFDM) was produced by reacting at a reaction temperature of 100 ℃ for 82 hours.

[0094] Example 5-2: WHSV = 2 h -1

[0095] 1 wt% HMF solution was used and WHSV was 1 h -1 Instead of reacting for 82 hours, a 2 wt% HMF solution was used and the WHSV was 2 h -1 Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 5-1, except that the reaction was carried out for 20 hours.

[0096] Example 5-3: WHSV = 3 h -1

[0097] 1 wt% HMF solution was used and WHSV was 1 h -1 Instead of reacting for 82 hours, a 3 wt% HMF solution was used and the WHSV was 3 h -1 Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 5-1, except that the reaction was carried out for 20 hours.

[0098] Example 6: Preparation of 2,5-tetrahydrofuran dimethanol (THFDM) according to HMF concentration

[0099] Example 6-1: HMF concentration 2 wt%

[0100] 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, is supplied from the raw material supply section to the reaction section at 0.1 ml / min, hydrogen is supplied from the hydrogen supply section to the reaction section at 10 ml / min, and in the reaction section, the 2 wt% HMF solution, hydrogen, and 2 g of Ru / γ-Al2O3 with 3 wt% Ru as a catalyst according to Example 1 are mixed to prepare a mixed solution. At this time, the pressure of the reaction section is maintained constant at 85 bar, and the WHSV (weight hourly space velocity) is 2 h -1 And, tetrahydrofuran dimethanol (THFDM) was produced by reacting at a reaction temperature of 100 ℃ for 20 hours.

[0101] Example 6-2: HMF concentration 5 wt%

[0102] Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 6-1, except that instead of using a 2 wt% HMF solution and reacting for 20 hours at a flow rate of 0.1 ml / min, a 5 wt% HMF solution was used and reacted for 54 hours at a flow rate of 0.04 ml / min.

[0103] Example 6-3: HMF concentration 10 wt%

[0104] A reactor with a reactor length of 5 cm was used, a 2 wt% HMF solution was used, the flow rate of the HMF solution was 0.1 ml / min, 2 g of catalyst was used, the pressure was kept constant at 20 bar, and the reaction was carried out for 20 hours, and the WHSV was 2 h -1 Instead, a reactor with a reactor length of 20 cm was used, a 10 wt% HMF solution was used, the flow rate of the HMF solution was 0.03 ml / min, 10 g of catalyst was used, the pressure was kept constant at 95 bar, and the reaction was carried out for 18 hours, and the WHSV was 0.6 h -1 Tetrahydrofuran dimethanol (THFDM) was prepared in the same manner as in Example 6-1 except that

[0105] Table 1 below summarizes the reaction conditions for producing 2,5-tetrahydrofurandimethanol (THFDM) according to Examples 2 to 6.

[0106] Classification 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 2-110.13031MeOH17085362 Example 2-210.13031IPA17085242 Example 2-310.13031MEG17085722 Example 3-110.11031.35MEG17085201.5 Example 3-210.11031.35MEG16085201.5 Example 3-310.11031.35MEG14085201.5 Example 3-410.11031.35MEG12085201.5 Example 3-510.11031.35MEG10085201.5 Example 4-110.11031.35MEG10085201.5 Example 4-210.11031.35MEG10070201.5 Example 4-310.11031.35MEG10055201.5 Example 4-410.11031.35MEG10040201.5 Example 5-110.11032MEG10085821 Example 5-220.11032MEG10085202 Example 5-330.11032MEG10085203 Example 6-120.11032MEG10085202 Example 6-250.041032MEG10085542 Example 6-3100.0310310MEG10095180.6

[0107] In Table 1 above, MeOH represents methanol, IPA represents 2-propanol, MEG represents 2-methoxyethanol, HMF represents 5-hydroxymethylfurfural, and WHSV represents weight hourly space velocity.

[0108] [Example Exam]

[0109] Conversion, Yield, and Selectivity Analysis: High-Performance Liquid Chromatography (HPLC)

[0110] After the reactions of Examples 2 to 6 were completed, the mixture was transferred to a vial and quantitatively analyzed using high-performance liquid chromatography (HPLC) until it reached room temperature. 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.

[0111] 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.

[0112] [Formula 1]

[0113]

[0114] [Formula 2]

[0115]

[0116] [Formula 3]

[0117]

[0118] [Formula 4]

[0119]

[0120] Test Example 1: NMR (nuclear magnetic resonance) analysis

[0121] Figure 3 is an NMR analysis graph of tetrahydrofuran dimethanol (THFDM) according to Example 5-2 of the present invention. Referring to Figure 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 product was subjected to a vacuum distillation device at 150°C and 450 mbar to remove all the solvent, thereby obtaining a high-viscosity liquid. It was confirmed that the high-viscosity liquid produced high-purity (97.8%) THFDM was produced through NMR analysis and the following equation 5.

[0122] [Formula 5]

[0123]

[0124] Test Example 2: Comparison of tetrahydrofuran dimethanol (THFDM) yields according to solvent type

[0125] Table 2 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 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 were known.

[0126] Solvent HMF Conversion (%) THFDM Yield (%) FDM Yield (%) Reaction Time (h) Example 2-1 Methanol (MeOH) 90 ~ 100 20 ~ 30 1.5 ~ 636 Example 2-2 2-Propanol (IPA) More than 98 20 ~ 400 ~ 324 Example 2-3 2-Methoxyethanol (MEG) 100 60 ~ 76 2 Less than 72

[0127] Experimental Example 3: Comparison of tetrahydrofuran dimethanol (THFDM) yields according to reaction temperature

[0128] 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 were known.

[0129] Classification Reaction temperature (℃) HMF conversion rate (%) THFDM yield (%) FDM yield (%) Reaction time (h) Example 3-1 170 100 64 ~ 781 Less than 20 Example 3-2 160 100 66 ~ 751 Less than 20 Example 3-3 140 100 66 ~ 751 Less than 20 Example 3-4 120 100 80 ~ 851 Less than 20 Example 3-5 100 100 88 ~ 960 20

[0130] Experimental Example 4: Comparison of tetrahydrofuran dimethanol (THFDM) yield according to reaction pressure

[0131] 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 were known.

[0132] Classification Reaction pressure (bar) HMF conversion rate (%) THFDM yield (%) FDM yield (%) Reaction time (h) Example 4-185 10088 ~ 96020 Example 4-270 10066 ~ 7515 ~ 2020 Example 4-35591 ~ 9554 ~ 6118 ~ 2420 Example 4-44080 ~ 8548 ~ 5630 ~ 3820

[0133] Test Example 5: Comparison of tetrahydrofuran dimethanol (THFDM) yields according to WHSV

[0134] 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.

[0135] Classification HMF concentration (wt%) WHSV (h -1 )HMF conversion rate (%)THFDM yield (%)FDM yield (%)Reaction time (h)Example 5-11110086 ~ 100082Example 5-22210088 ~ 96020Example 5-33310087 ~ 900.1 ~ 220

[0136] Experimental Example 6: Comparison of tetrahydrofuran dimethanol (THFDM) yield according to HMF concentration

[0137] Table 6 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 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 were known.

[0138] Classification HMF concentration (wt%) WHSV (h -1 )HMF conversion rate (%)THFDM yield (%)FDM yield (%)Reaction time (h)Example 6-12210088 ~ 96020Example 6-25210085 ~ 950 ~ 0.154Example 6-3100.610086 ~ 970 ~ 0.318

[0139] Test Example 7: Comparison of THFDM yield according to HMF concentration and time

[0140] 7-1: Comparison of yields of THFDM with HMF concentration of 2 wt% and time

[0141] Figure 4a is a graph showing the yield of THFDM over time in Example 6-1 of the present invention. Referring to Figure 4a, it can be seen that the yield was consistently 87.5 to 96.2% for 2 to 20 hours.

[0142] Test Example 7-2: Comparison of yields of THFDM at 5 wt% HMF concentration and over time

[0143] Figure 4b is a graph showing the yield of THFDM over time in Example 6-2 of the present invention. Referring to Figure 4b, it can be seen that the yield was consistently 84.6 to 96.2% for 2 to 54 hours.

[0144] Test Example 7-3: Comparison of yields of THFDM at 10 wt% HMF concentration and over time

[0145] Figure 4c is a graph showing the yield of THFDM over time in Example 6-3 of the present invention. Referring to Figure 4c, it can be seen that the yield was consistently 86.1 to 97.1% for 2 to 18 hours.

[0146] 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.

Claims

1. Alumina (Al 2 O 3 ) including a support; and Ruthenium (Ru) supported on the above support; A catalyst containing:

2. In paragraph 1, A catalyst for use in the hydrogenation reaction of 5-hydroxymethylfurfural (HMF) to produce tetrahydrofuran dimethanol (THFDM).

3. In paragraph 1, The above alumina is γ-Al 2 O 3 A catalyst characterized by comprising: 4.5-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).

5. 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.

6. 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.

7. 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.

8. In paragraph 7, A continuous tetrahydrofuran dimethanol production device, characterized in that the solvent contains 2-methoxyethanol.

9. In paragraph 4, A continuous tetrahydrofuran dimethanol production device, characterized in that the temperature of the above reaction section is 90 to 180°C.

10. In paragraph 4, A continuous tetrahydrofuran dimethanol production device, characterized in that the pressure of the above reaction section is 30 to 100 bar. 11.(a) a step of 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:

12. In paragraph 11, A method for producing a catalyst, wherein the catalyst is used for producing tetrahydrofuran dimethanol (THFDM) by hydrogenating 5-hydroxymethylfurfural (HMF).

13. In paragraph 11, The above alumina is γ-Al 2 O 3 A method for producing a catalyst, characterized by including a.

14. In paragraph 11, A method for producing a catalyst, characterized in that the solvent in step (a) contains water.

15. In paragraph 11, The reducing agent in step (b) is NaBH 4 A method for producing a catalyst, characterized by including a.

16. In paragraph 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.

17. In paragraph 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.

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