WO2020101234A1 - Method for preparing 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol from 5-hydroxymethylfurfural - Google Patents

Abstract

The present invention relates to a method for preparing furan-based compounds, comprising a step of preparing one or more furan-based compounds selected from the group consisting of 2,5-furandimethanol (FDM) and 2,5-5etrahydrofuran dimethanol (THF-DM) by hydrogenating 5-hydroxymethylfurfural (HMF) by using hydrogen (H₂) and a catalyst, wherein the catalyst comprises a support having a spinel structure in which noble metal nanoparticles are supported. Therefore, 2,5-FDM and 2,5-THF-DM can be selectively and respectively obtained in high yields of 90% or more in a single container.

Description

Method for preparing 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol from 5-hydroxymethylperfural

The present invention relates to a method for producing 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol from 5-hydroxymethylperfural, and more specifically, to support a spinel structure supporting precious metal nanoparticles. 5-Hydroxymethylfurfural (HMF) to 2,5-furandimethanol (FDM) and 2,5-tetrahydrofuran dimethanol (2,5) -Tetrahydrofuran dimethanol, THF-DM) relates to a method for selectively producing at least one furan-based compound selected from the group consisting of.

As the industrial production system was established from the start of World War II, plastics based on various resins began to be mass-produced as consumer goods. In particular, from the late 1970s, more than 300 million tons of plastic has been produced and consumed worldwide, exceeding steel production. However, since plastic is produced using naphtha from the oil refining process, depletion of petroleum resources and carbon dioxide emissions are a problem, and as it is used as the main material for disposable products, it is used for a long time before being discarded immediately after using the product. When it is difficult to incinerate due to incorrosion, carcinogens such as dioxin are released into the atmosphere, causing environmental problems, and research on alternative materials has been continuously conducted.

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

2,5-furandimethanol (FDM), 2,5-tetrahydrofuran dimethanol (2,5-Tetrahydrofuran dimetanol, THF-DM), and 2,5 through catalytic hydrogenation of HMF -Dimethylfuran (2,5-dimethylfuran) can be prepared. The 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol can be used in various aspects such as the production of resins, polymers, and chemical fibers having various properties, and thus has great potential. 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.

When using a metal-carrying catalyst in which platinum is supported on a carbon carrier, 2,5-furandimethane having a purity of 90 to 98% is produced, but commercialization is almost impossible because platinum is expensive. When nickel, cobalt, copper, ruthenium or palladium other than platinum is used as a metal-carrying catalyst supported on a carbon carrier, there is a disadvantage that the yield of 2,5-furandimethane is very low. When preparing 2,5-furandidimane and 2,5-tetrahydrofuran dimethanol selectively in the prior art using catalysts other than the catalysts described above, 2,5-furandidimethanol and 2,5-tetrahydrofuran Only one of dimethanol can be obtained with a high yield of 90% or more.

Thus, 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol can be selectively obtained in a single container, and 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol are respectively 90%. A process that can be obtained with the above high yield is required.

The object of the present invention is selected from the group consisting of 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol from 5-hydroxymethylperfural using a spinel-structured support carrying precious metal nanoparticles as a catalyst. It is to provide a method for producing a furan-based compound capable of selectively obtaining 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol in a single container by preparing one or more furan-based compounds.

In addition, it is to provide a method for producing a furan-based compound capable of obtaining 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol in high yields of 90% or more, respectively.

According to an aspect of the present invention, (a) 5-hydroxymethylfurfural (5-Hydroxymethylfurfural, HMF) hydrogenation reaction using a catalyst with hydrogen (H ₂ ) 2,5-furandimethane (2,5 -Furandimethanol, FDM) and 2,5-tetrahydrofuran dimethanol (2,5-Tetrahydrofuran dimethanol, THF-DM) comprising the step of preparing a furan-based compound comprising at least one selected from the group consisting of, and The catalyst is to provide a method for producing a furan-based compound, which comprises a spinel-structured support carrying noble metal nanoparticles.

In addition, the method for producing the furan-based compound after the step (a), (b) separating the 2,5-furan dimethanol or 2,5-tetrahydrofuran dimethanol; further comprises, The isolated 2,5-furan dimethanol or 2,5-tetrahydrofuran dimethanol will contain 0.1 to 20 ppm cobalt (Co), 0.1 to 60 ppm manganese (Mn), and 0.1 to 5 ppm ruthenium (Ru). Can be.

In addition, the support of the spinel structure is MnCo ₂ O ₄ , CoMn ₂ O ₄ , ZnAl ₂ O ₄ , FeAl ₂ O ₄ , CuFe ₂ O ₄ , ZnMn ₂ O ₄ , MnFe ₂ O ₄ , Fe ₃ O ₄ , TiFe ₂ It may include one or more selected from the group consisting of O ₄ , ZnFe ₂ O ₄ , Mg ₂ SiO ₄ , Fe ₂ SiO ₄ .

In addition, the noble metal nanoparticles may include one or more selected from the group consisting of platinum, palladium, and ruthenium.

In addition, the catalyst may be a MnCo ₂ O ₄ support having a spinel structure carrying ruthenium nanoparticles.

In addition, the step of preparing the furan-based compound is the reaction time, the pressure of the hydrogen, and the molar ratio (mol / mol) of 5-hydroxymethylperfural (HMF / Ru) to ruthenium (Ru) of the catalyst By controlling one or more reaction conditions selected from the group consisting of 2,5-furandimethane and 2,5-tetrahydrofuran dimethanol, any one selected from the group consisting of 90% or higher yield and 90% or higher selectivity It may be a step of manufacturing with (selectivity).

In addition, in the step of preparing the furan-based compound, the reaction time is 2.5 to 3.5 hr, the pressure of the hydrogen is 5 to 6 MPa, and the molar ratio (mol / mol) of HMF / Ru is adjusted to 30 to 40 to 2,5- It may be a step of preparing furan dimethanol as a main product.

In addition, in the step of preparing the furan-based compound, the reaction time is 15.5 to 16.5 hr, the pressure of the hydrogen is 6.5 to 9.5 MPa, and the molar ratio (mol / mol) of HMF / Ru is adjusted to 45 to 105 to 2,5. -Tetrahydrofuran may be a step of preparing methane as the main product.

In addition, the temperature of the step of preparing the furan-based compound may be 70 to 150 ℃.

In addition, the precious metal nanoparticles may be 1 to 10% by weight based on the catalyst weight.

In addition, the precious metal nanoparticles may be 3 to 5% by weight based on the catalyst weight.

In addition, the precious metal nanoparticles may be 4% by weight based on the catalyst weight.

In addition, the step of preparing the furan-based compound may be a step performed in a single container.

In addition, the 5-hydroxymethylperfural may be derived from biomass including one or more selected from the group consisting of cellulose and polysaccharides.

In addition, the method for producing the furan-based compound is performed by a solution reaction using a solvent, and the solvent is methanol, ethanol, n-propanol, iso-propanol, butanol, pentanol, tetrahydrofuran, methyl tertiary butyl ether, hexane And it may include one or more selected from the group consisting of pentane.

In addition, the solvent may be methanol.

In addition, the average particle diameter (D ₅₀ ) of the support having the spinel structure may be 2.0 to 4.0 μm.

The method for producing a furan-based compound of the present invention uses 2,5-furandimethanol and 2, in a single container by hydrogenation of 5-hydroxymethylperfural using a spinel-structured support carrying precious metal nanoparticles as a catalyst. 5-Tetrahydrofuran dimethanol can be optionally obtained.

In addition, 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol can be obtained in high yields of 90% or more, respectively.

Since these drawings are for reference to explain exemplary embodiments of the present invention, the technical spirit of the present invention should not be limited to the accompanying drawings.

1 shows a schematic diagram of the conversion reaction of 5-hydroxymethylperfural.

Figure 2 shows the aspects of the hydrogenation product of 5-hydroxymethylperfural according to the reaction conditions.

Figure 3 shows the XRD pattern of the spinel structure of the support prepared according to Preparation Example 1.

4 shows an SEM photograph of a spinel-structured support prepared according to Preparation Example 1.

Figure 5 shows a SEM picture that can identify a number of pores in the support of the spinel structure prepared according to Preparation Example 1.

FIG. 6 shows an SEM photograph of a microsphere of a spinel-structured support prepared according to Preparation Example 1.

Figure 7 shows the XPS of the support of the spinel structure of the precious metal nanoparticles prepared according to Preparation Example 2.

8 shows a high performance liquid chromatogram of a reaction mixture comprising 2,5-tetrahydrofuran dimethanol prepared according to Example 2.

FIG. 9 shows the ¹ H-NMR spectrum of 2,5-tetrahydrofuran dimethanol prepared according to Example 2 and subsequently purified and commercially available reagent 2,5-tetrahydrofuran dimethanol.

FIG. 10 shows the ¹³ C-NMR spectrum of 2,5-tetrahydrofuran dimethanol prepared according to Example 2 and subsequently purified and commercially available reagent 2,5-tetrahydrofuran dimethanol.

FIG. 11 is a schematic diagram showing the conversion rate of 5-hydroxymethylperfural and the yield of 2,5-furandiethanol according to the number of catalyst reuses when preparing 2,5-furandimethane according to Example 1.

FIG. 12 is a schematic diagram of 5-hydroxymethylperfuran conversion and 2,5-tetrahydrofuran dimethanol yield according to the number of catalyst reuses when preparing 2,5-tetrahydrofuran dimethanol according to Example 2.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains may easily practice.

However, the following description is not intended to limit the present invention to specific embodiments, and when it is determined that a detailed description of known technologies related to the present invention may obscure the subject matter of the present invention, the detailed description will be omitted. .

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

Further, 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. The terms are used only for the purpose of distinguishing one component from other components. For example, the first component may be referred to as a second component without departing from the scope of the present invention, and similarly, the second component may be referred to as a first component.

Also, when a component is referred to as being “formed” or “stacked” on another component, it may be formed or stacked directly attached to the front or one side of the surface of the other component, but may be intermediate. It should be understood that there may be other components in the.

1 shows a schematic diagram of the conversion reaction of 5-hydroxymethylperfural.

1, 2,5-furandimethanol and 2,5-tetrahydrofuran dimethanol can be selectively obtained from 5-hydroxymethylperfural.

Hereinafter, using the support of the spinel structure carrying the noble metal nanoparticles of the present invention as a catalyst, hydrogenation of 5-hydroxymethylperfural to 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol A method of preparing at least one furan-based compound selected from the group consisting will be described in detail. However, this is provided as an example, and the present invention is not limited thereby, and the present invention is merely defined by the scope of claims to be described later.

Figure 2 shows the aspects of the hydrogenation product of 5-hydroxymethylperfural according to the reaction conditions.

Referring to Figure 2, the present invention is (a) 5-hydroxymethyl perfural (5-Hydroxymethylfurfural, HMF) hydrogenation reaction using hydrogen (H ₂ ) and a catalyst to 2,5-furandiethanol (2, 5-Furandimethanol, FDM) and 2,5-tetrahydrofuran dimethanol (2,5-Tetrahydrofuran dimethanol, THF-DM) comprising the step of preparing a furan-based compound comprising at least one selected from the group consisting of, The catalyst provides a method for producing a furan-based compound, which comprises a spinel-structured support carrying noble metal nanoparticles.

In addition, the method for producing the furan-based compound after the step (a), (b) separating the 2,5-furan dimethanol or 2,5-tetrahydrofuran dimethanol; further comprises, The isolated 2,5-furan dimethanol or 2,5-tetrahydrofuran dimethanol will contain 0.1 to 20 ppm cobalt (Co), 0.1 to 60 ppm manganese (Mn), and 0.1 to 5 ppm ruthenium (Ru). Can be.

In addition, the support of the spinel structure is MnCo ₂ O ₄ , CoMn ₂ O ₄ , ZnAl ₂ O ₄ , FeAl ₂ O ₄ , CuFe ₂ O ₄ , ZnMn ₂ O ₄ , MnFe ₂ O ₄ , Fe ₃ O ₄ , TiFe ₂ O ₄ , ZnFe ₂ O ₄ , Mg ₂ SiO ₄ , Fe ₂ SiO ₄ It may include one or more selected from the group consisting of, preferably selected from the group consisting of MnCo ₂ O ₄ and CoMn ₂ O ₄ It may contain one or more, more preferably MnCo ₂ O ₄ .

In addition, the precious metal may include one or more selected from the group consisting of platinum, palladium, and ruthenium, and preferably ruthenium.

The particle size of the noble metal nanoparticles may be 5 to 15 nm, and the noble metal nanoparticles of the 5 to 15 nm size may be efficiently contained in the support of the spinel structure. In addition, since noble metal particles can be uniformly dispersed in a structure in which a number of microspheres possessed by a spinel support are integrated, it is possible to induce a stable hydrogenation reaction of a furan compound.

In addition, the catalyst may be a MnCo ₂ O ₄ support having a spinel structure carrying ruthenium nanoparticles.

In addition, the step of preparing the furan-based compound is the reaction time, the pressure of the hydrogen, and the molar ratio (mol / mol) of 5-hydroxymethylperfural (HMF / Ru) to ruthenium (Ru) of the catalyst By controlling one or more reaction conditions selected from the group consisting of 2,5-furandimethane and 2,5-tetrahydrofuran dimethanol, any one selected from the group consisting of 90% or higher yield and 90% or higher selectivity It may be a step of manufacturing with (selectivity).

In addition, in the step of preparing the furan-based compound, the reaction time is 2.5 to 3.5 hr, the pressure of the hydrogen is 5 to 6 MPa, and the molar ratio (mol / mol) of HMF / Ru is adjusted to 30 to 40 to 2,5- It may be a step in which furan dimethanol is prepared as a main product. When the reaction time is less than 2.5hr, the pressure of hydrogen is less than 5MPa and the molar ratio of HMF / Ru is less than 30, the yield of 2,5-furandimethane is low, the reaction time is 3.5hr, the pressure of hydrogen is 6MPa, and HMF / Ru When the molar ratio exceeds 40, the incidence of by-product 2,5-tetrahydrofuran dimethanol may increase, which is not preferable.

In addition, in the step of preparing the furan-based compound, the reaction time is 15.5 to 16.5 hr, the pressure of the hydrogen is 6.5 to 9.5 MPa, and the molar ratio (mol / mol) of HMF / Ru is adjusted to 45 to 105 to 2,5 -Tetrahydrofuran may be a step of preparing methane as the main product. When the reaction time is 15.5h, the pressure of hydrogen is less than 6.5MPa, and the HMF / Ru molar ratio is less than 45, the yield of 2,5-tetrahydrofuran dimethanol is low, the reaction time 16.5h, the pressure of hydrogen 9.5MPa, HMF / If the Ru molar ratio exceeds 105, the incidence of by-products may increase, which is not preferable.

In addition, the reaction temperature of the step of preparing the furan-based compound may be 70 to 150 ° C, preferably 80 to 120 ° C, more preferably 90 to 110 ° C, even more preferably 95 to 105 ° C have. When the reaction temperature is less than 80 ° C, the yield of the furan-based compound is low, and when it exceeds 150 ° C, a side reaction occurs and the catalyst is decomposed at a high temperature to 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol. It is not preferable because it is difficult to prepare a furan-based compound containing one or more selected from the group consisting of.

In addition, the precious metal nanoparticles may be 1 to 10% by weight based on the catalyst weight, preferably 3 to 5% by weight, more preferably 4% by weight. If the noble metal nanoparticles are contained in less than 1% by weight, the yield of the furan-based compound may be lowered, and when it is included in 10% by weight or more, the furan-based compound may be rapidly hydrogenated to cause problems in process stability, and the noble metal particles Excessive use of is undesirable as it can affect the price increase of the catalyst.

In addition, the step of preparing the furan-based compound may be a step performed in a single container.

In addition, the HMF may be derived from biomass containing at least one selected from the group consisting of cellulose and polysaccharides.

In addition, the method for producing the furan-based compound is performed by a solution reaction using a solvent, and the solvent is methanol, ethanol, n-propanol, iso-propanol, butanol, pentanol, tetrahydrofuran, methyl tertiary butyl ether, hexane And it may include one or more selected from the group consisting of pentane, preferably may include methanol.

In addition, the average particle diameter (D ₅₀ ) of the support having the spinel structure may be 2.0 to 4.0 μm.

[Example]

Hereinafter, a preferred embodiment of the present invention will be described. However, this is for illustrative purposes, and the scope of the present invention is not limited thereby.

Manufacturing example  1: Cobalt-manganese based Spinel  Structure support

Dissolve commercially available (CH ₃ COO) ₂ Co.4H ₂ O 6.53 mol and Mn (CH ₃ COO) ₂ · 4H ₂ O 3.26 mol (Co: Mn molar ratio 2: 1) in 40 L of water, The mixture was homogenized by stirring for 30 minutes, and at the same time, an aqueous solution in which 5 kg of (NH ₄ ) ₂ SO ₄ was dissolved in 40 L of water was prepared. After slowly mixing the two solutions, the mixture was stirred for 4 hours, and the NH ₄ HCO ₃ supersaturated aqueous solution (~ 5 kg) was slowly mixed into the solution, followed by stirring for 6 hours.

The pale pink precipitate was collected by filtration, washed with distilled water and anhydrous ethanol, and then dried at 60 ° C. for 12 hours. The obtained carbonate precursor (MnCo ₂ CO ₃ ) is calcined in an air (20% O ₂ , 80% N ₂ ) atmosphere at 425 ° C. (2 ° C./min) for 8 hours, and then naturally cooled to room temperature over 8 hours to cobalt- A manganese-based spinel structure support (MnCo ₂ O ₄ ) was prepared.

Manufacturing example  2: Ruthenium nanoparticles Loaded  Cobalt-manganese based Spinel  Structure support

MnCo ₂ O ₄ prepared according to Preparation Example 1 in a 5L 2-neck flask 500g of particles, RuCl ₃ ㆍ 3H ₂ O 43.2g and 2L of distilled water were added and immersed in a cooling bath and stirred in a nitrogen atmosphere for 12 hours. While stirring the obtained mixture, NaBH ₄ aqueous solution (10 times of RuCl ₃ ㆍ 3H ₂ O) was added dropwise, followed by stirring at 500 rpm for 1 day at room temperature in a nitrogen atmosphere to reduce Ru (III) to Ru (0). Thereafter, the catalyst was recovered through filtration, washed with ethanol, and dried at 65 ° C. for 1 day in vacuum to support a cobalt-manganese-based spinel structure supporting ruthenium nanoparticles (Ru / MnCo ₂ O ₄ , Ru 4wt%) Was prepared.

Example  1: FDM As the main product  Produce

100 mL of a high pressure stainless steel reactor equipped with a magnetic stirrer and an electric heater was loaded with 1.0 g (8.0 mmol) of 5-hydroxymethylperfural, 30 mL of methanol as a solvent, and ruthenium nanoparticles prepared according to Preparation Example 2 as a catalyst. A mixture was prepared by mixing 0.4 g of a cobalt-manganese-based spinel structure support (Ru / MnCo ₂ O ₄ , Ru 4wt%). At this time, the molar ratio (HMF / Ru) of ruthenium nanoparticles and 5-hydroxymethylperfural is 33.6.

After purging hydrogen at a pressure of 0.55 MPa in the reactor in which the mixture was present, the atmosphere was evacuated three times. Thereafter, the mixture was stirred at 600 rpm, heated to 100 ° C, and the hydrogen pressure was raised to 5.5 MPa, and then reacted for 3 hours while maintaining the pressure at 5.5 MPa to prepare 2,5-furandiethanol (FDM) as a main product.

Example  2: THF -DM As the main product  Produce

100 mL of a high-pressure stainless steel reactor equipped with a magnetic stirrer and an electric heater was loaded with 1.0 g (8.0 mmol) of 5-hydroxymethylperfural, 30 mL of methanol as a solvent, and ruthenium nanoparticles prepared according to Preparation Example 2 as a catalyst. A mixture was prepared by mixing 0.40 g of a cobalt-manganese-based spinel structure support (Ru / MnCo ₂ O ₄ , Ru 4wt%). At this time, the molar ratio (HMF / Ru) of ruthenium nanoparticles and 5-hydroxymethylperfural is 50.

The mixture was purged with hydrogen at a pressure of 0.55 MPa and the atmosphere was evacuated three times. Thereafter, the mixture was stirred at 650 rpm, heated to 100 ° C., and the carbon dioxide pressure was raised to 8.2 MPa, and then reacted for 16 hours while maintaining the pressure at 8.2 MPa, and 2,5-tetrahydrofuran dimethanol (THF-DM) was used as the main product. It was prepared.

Example  3: THF -DM As the main product  Produce

THF-DM was prepared as a main product in the same manner as in Example 2, except that the reaction temperature was performed at 80 ° C instead of 100 ° C.

Example  4: THF -DM As the main product  Produce

THF-DM was prepared as the main product in the same manner as in Example 2, except that the reaction temperature was performed at 120 ° C instead of 100 ° C.

Example  5: THF -DM As the main product  Produce

THF-DM was prepared as the main product in the same manner as in Example 2, except that the reaction pressure was performed at 5.5 MPa instead of 8 MPa.

Example  6: THF -DM As the main product  Produce

THF-DM was prepared as the main product in the same manner as in Example 2, except that the reaction pressure was performed at 6.8 MPa instead of 8 MPa.

Example  7: THF -DM As the main product  Produce

THF-DM was prepared as the main product in the same manner as in Example 2, except that the reaction pressure was performed at 8.85 MPa instead of 8 MPa.

Example  8: THF -DM As the main product  Produce

Instead of using a catalyst of 0.40 g to make the molar ratio (HMF / Ru) of ruthenium nanoparticles and 5-hydroxymethylperfural to 50, instead of using a catalyst of 0.27 g to make an HMF / Ru molar ratio of 75, In the same manner as in Example 2, THF-DM was prepared as the main product.

Example  9: THF -DM As the main product  Produce

Except that the molar ratio (HMF / Ru) of ruthenium nanoparticles and 5-hydroxymethylperfural was set to 50 using 0.40 g of the catalyst, and the HMF / Ru molar ratio was set to 100 using 0.20 g of the catalyst. In the same manner as in Example 2, THF-DM was prepared as the main product.

Table 1 below summarizes the reaction conditions for the preparation of furan compounds according to Examples 1 to 9.

division	Main product	HMF amount (mmol)	Catalyst amount (g)	HMF / Ru molar ratio (mol / mol)	Solvent amount (mL)	Reaction temperature (℃)	Reaction pressure (MPa)	Reaction time (h)
Example 1	2,5-furandiethanol	8.0	0.40	33.6	20	100	5.5	3
Example 2	2,5-tetrahydrofuran dimethanol	8.0	0.40	50	20	100	8.2	16
Example 3	2,5-tetrahydrofuran dimethanol	8.0	0.40	50	30	80	8	16
Example 4	2,5-tetrahydrofuran dimethanol	8.0	0.40	50	30	120	8	16
Example 5	2,5-tetrahydrofuran dimethanol	8.0	0.40	50	30	100	5.5	16
Example 6	2,5-tetrahydrofuran dimethanol	8.0	0.40	50	30	100	6.8	16
Example 7	2,5-tetrahydrofuran dimethanol	8.0	0.40	50	30	100	8.85	16
Example 8	2,5-tetrahydrofuran dimethanol	8.0	0.27	75	30	100	8	16
Example 9	2,5-tetrahydrofuran dimethanol	8.0	0.20	100	30	100	8	16

[Test Example]

Spinel  Check the structure of the support structure

Figure 3 shows the XRD pattern of the cobalt-manganese-based spinel structure support (MnCo ₂ O ₄ ) prepared according to Preparation Example 1, Figure 4 is a cobalt-manganese-based spinel structure support according to Preparation Example 1 ( SEM image of MnCo ₂ O ₄ ). FIG. 5 is a SEM image of confirming a number of pores on a support (MnCo ₂ O ₄ ) of a cobalt-manganese-based spinel structure prepared according to Preparation Example 1, and FIG. 6 is a cobalt-manganese base prepared according to Preparation Example 1 The SEM photograph of the microspheres of the spinel structure support (MnCo ₂ O ₄ ) is shown.

Referring to Figure 3, it can be seen that MnCo ₂ O ₄ was synthesized well.

4 to 6, it can be seen that MnCo ₂ O ₄ as a spinel structure has an average particle diameter (D ₅₀ ) of 2.0 to 4.0 μm, and the structure is a structure in which a large number of microspheres of 30 to 60 nm are integrated. Can be. In addition, the cobalt-manganese-based spinel structure support (MnCo ₂ O ₄ ) prepared according to Preparation Example 1 of the present invention has a unique structure and size, so that when the precious metal nanoparticles are reduced and included in the support, the nano It can be seen that the particles have an efficient structure that can be formed evenly distributed in the support.

Ruthenium nanoparticles Supported Spinel  Check the structure of the support structure

7 is an X-ray photoelectron spectroscopy (XPS) of a spinel-structured support (Ru / MnCo ₂ O ₄ , Ru 4wt%) carrying ruthenium nanoparticles prepared according to Preparation Example 2.

Referring to FIG. 7, it can be confirmed that Co, Mn, O, and Ru are present in (a) of FIG. 7, and (d) it can be confirmed that O atoms are present in the spinel lattice from the 1s spectrum of O, In f), it can be confirmed that Ru is a metal particle since the maximum value of the peak of 3P _3/2 of Ru is present in the 3d region of Ru at 455 to 480 eV.

2,5- Furandimethanol  Separation tablets

In a reaction mixture containing 2,5-furandimethane prepared according to Example 1 (including unreacted HMF and product FDM), methanol was evaporated at 45 ° C, and evaporated at 60 ° C for 1 hour to give a concentrated mixed liquid. It was prepared. After adding silica to the concentrated mixed liquid and sufficiently stirring, a small amount of acetone was added to sufficiently absorb the mixed liquid and stirred for one day. After evaporating acetone again, the eluent (ethyl acetate: hexane = 1: 2) was added to the silica absorbed by the mixed liquid, followed by separation and purification through a column.

2,5- Tetrahydrofuran Dimethanol  Separation tablets

In a reaction mixture comprising 2,5-tetrahydrofuran dimethanol prepared according to Example 2 (including unreacted HMF, intermediate FDM and product THF-DM), methanol was evaporated at 45 ° C. and further at 60 ° C. for another hour. Evaporation gave a concentrated mixed liquid. After adding silica to the concentrated mixed liquid and sufficiently stirring, a small amount of acetone was added to sufficiently absorb the mixed liquid and stirred for one day. After evaporating acetone again, the eluent (ethyl acetate: hexane = 1: 2) was added to the silica absorbed by the mixed liquid, followed by separation and purification through a column.

8 shows a high performance liquid chromatogram of a reaction mixture comprising 2,5-tetrahydrofuran dimethanol prepared according to Example 2.

Referring to FIG. 8, it can be seen that the first 5-hydroxymethylperfural is separated and then separated in the order of 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol.

Then, TLC (Thin-layer chromatography) analysis of 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol was performed. At this time, 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol were not read by TLC (Thin-layer chromatography) using a UV lamp, so a KMnO ₄ solution was used. In addition, dilute 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol solutions were measured after concentration because they were unreadable in the KMnO ₄ solution.

From the time when all 2,5-furan dimethanol was separated by TLC analysis, 2,5-tetrahydrofuran dimethanol was collected and eluent was evaporated to separate and purified 2,5-tetrahydrofuran dimethanol. Got.

Separately purified 2,5- Tetrahydrofuran Dimethanol  Structure check

FIG. 9 shows the ¹ H-NMR spectrum (DMSO-d ₆ ) of 2,5-tetrahydrofuran dimethanol prepared according to Example 2 and subsequently purified and commercially available reagent 2,5-tetrahydrofuran dimethanol , Figure 10 shows the ¹³ C-NMR spectrum of 2,5-tetrahydrofuran dimethanol prepared according to Example 2 and then purified separately and commercially available reagent 2,5-tetrahydrofuran dimethanol.

9 to 10, it can be confirmed that the reactant prepared according to Example 2 and then separated and purified is 2,5-tetrahydrofuran dimethanol.

Conversion rate, yield and Selectivity  analysis: HPLC

After the reactions of Examples 1 to 9 were terminated, it was waited until it reached room temperature, and the resulting mixture was transferred to a vial and quantitatively analyzed using high performance liquid chromatography (HPLC). Analysis was performed using a high performance liquid chromatography (HPLC) instrument (Agilent Technologies 1200 series, Bio-Rad Aminex HPX-87 H pre-packed column, and UV-detector), and H ₂ SO ₄ (0.0005M) in water was mobile phase. It was used as. In addition, the conversion method of 5-hydroxymethylperfural (HMF), the yield and selectivity of 2,5-furandimethane (FDM), and the yield and selectivity calculation method of 2,5-tetrahydrofuran dimethanol (THF-DM) It may be using the following equations 1 to 5.

[Equation 1]

Conversion rate of HMF [%] = (number of moles of reaction of HMF) / (number of moles of HMF injected) x 100

[Equation 2]

FDM yield [%] = (Actual FDM generated moles) / (Theoretical FDM generated moles) × 100

[Equation 3]

FDM selectivity [%] = (FDM yield) / (HMF conversion) × 100

[Equation 4]

Yield of THFDM [%] = (Actual THFDM production moles) / (Theoretical THFDM production moles) × 100

[Equation 5]

Selectivity of THFDM [%] = (Yield of THFDM) / (HMF conversion) × 100

C _HMF in Tables 2 to 5 below represents the conversion rate of 5-hydroxymethylperfural, Y _FDM is the yield of 2,5-furandimethane, and Y _{THF -DM} is the yield of 2,5-tetrahydrofuran dimethanol Indicates.

Product changes according to reaction conditions

When the same catalyst was used, the change of the product according to the reaction conditions was studied and the results are shown in Table 2.

division	product	Reaction time (h)	Reaction pressure (H 2 , MPa)	HMF / Ru molar ratio	C HMF (%)	yield(%)	Selectivity (%)
Example 1	FDM	3	5.5	33.6	97	92.2	95.0
Example 2	THF-DM	16	8.2	50	98.7	97.3	99.0

According to Table 2, it can be seen that the yields of FDM and THF-DM are affected by adjusting reaction conditions. It can be seen that the yields of FDM and THF-DM are 92.2% and 97.3%, respectively. In addition, since FDM is an intermediate, it can be confirmed that a long reaction time is required to form THF-DM by HMF hydrogenation.

Conversion rate and yield according to the number of catalyst reuse

FIG. 11 is a schematic diagram of HMF conversion and FDM yield according to the number of catalyst reuses when manufacturing FDM according to Example 1, and FIG. 12 is HMF conversion and THF according to catalyst reuse frequency when manufacturing THF-DM according to Example 2 -It is a diagram of DM yield. At this time, the catalyst was simply recovered by filtration and reused.

11 to 12, it can be seen that the yields of FDM and THF-DM are not significantly reduced while the catalyst is reused four times continuously. Therefore, it can be confirmed that the Ru (4.0wt%) / MnCo ₂ O ₄ catalyst is structurally stable and practically strong.

Conversion and yield depending on reaction temperature

When THF-DM was prepared from HMF, the conversion of HMF and the yield of THF-DM according to the reaction temperature were studied and the results are shown in Table 3.

division	Reaction temperature (℃)	C HMF	Y THF -DM	Y FDM
Example 2	100	98.7	97.3	1.4
Example 3	80	77	71.6	5.4
Example 4	120	99.1	97.2	1.8

According to Table 3, HMF 1.0g (8.0mmol), catalyst (Ru (4.0wt%) / MnCo ₂ O ₄ ) 0.40g, HMF / Ru molar ratio 50, methanol (solvent) 30mL, reaction time 16h, reaction pressure When HMF was hydrogenated under the same conditions of 8 MPa and a stirring speed of 600 rpm, it can be seen that the THF-DM yield of Example 2 performed at a reaction temperature of 100 ° C was the highest at 97.3%.

Conversion rate and yield depending on reaction pressure

When THF-DM was prepared from HMF, the conversion of HMF and the yield of THF-DM according to the reaction pressure were studied and the results are shown in Table 4.

division	Reaction pressure (MPa)	C HMF	Y THF -DM	Y FDM
Example 2	8.2	98.7	97.3	1.4
Example 5	5.5	79.1	71.5	7.5
Example 6	6.8	81	77.9	3.1
Example 7	8.85	99	97.5	1.5

According to Table 4, HMF 1.0g (8.0mmol), catalyst (Ru (4.0wt%) / MnCo ₂ O ₄ ) 0.40g, HMF / Ru molar ratio 50, methanol (solvent) 30mL, reaction time 16h, reaction temperature When HMF was hydrogenated under the same conditions of 100 ° C. and a stirring speed of 600 rpm, it can be seen that the yield of Example 7 in which the reaction pressure was performed at 9 MPa was the highest at 97.5%.

HMF / Ru  Conversion rate and yield according to mole ratio

When THF-DM was prepared from HMF, the conversion of HMF and the conversion of THF-DM according to the HMF / Ru molar ratio were studied and the results are shown in Table 5.

division	HMF / Ru molar ratio	C HMF	Y THF -DM	Y FDM
Example 2	50	98.7	97.3	1.4
Example 8	75	91.4	89.9	1.5
Example 9	100	84.5	80.5	4

According to Table 5, HMF 1.0g (8.0mmol), catalyst (Ru (4.0wt%) / MnCo ₂ O ₄ ) 0.40g, methanol (solvent) 30mL, reaction time 16h, reaction temperature 100 ℃, reaction pressure 8MPa, When HMF was hydrogenated under the same conditions of a stirring speed of 600 rpm, it was confirmed that the yield of Example 2 performed at a HMF / Ru molar ratio of 50 was the highest at 97.3%.

Separated FDM and THF -DM cobalt (Co) manganese (Mn) and ruthenium ( Ru ) Content analysis

Cobalt (Co), manganese (Mn) and 2,5-tetrahydrofuran dimethanol prepared according to Example 1 and then separated and purified according to Example 2 and then purified separately according to Example 2 and The ruthenium (Ru) content was analyzed using an inductively coupled plasma mass spectrometer (ICP-MS) and the results are shown in Table 6.

division	Cobalt content (ppm)	Manganese content (ppm)	Ruthenium content (ppm)
Example 1	4	11	0.7
Example 2	10	25	2

According to Table 6 above, a small amount of cobalt in 2,5-furandimethanol prepared according to Example 1 and then purified after purification and 2,5-tetrahydrofuran diethanol prepared according to Example 2 and subsequently purified, It can be seen that manganese and ruthenium are included.

The scope of the present invention is indicated by the following claims rather than the above detailed description, and it should be interpreted that all changes or modified forms derived from the meaning and scope of the claims and equivalent concepts thereof are included in the scope of the present invention. do.

The method for producing a furan-based compound of the present invention uses 2,5-furandimethanol and 2, in a single container by hydrogenation of 5-hydroxymethylperfural using a spinel-structured support carrying precious metal nanoparticles as a catalyst. 5-Tetrahydrofuran dimethanol can be optionally obtained.

In addition, 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol can be obtained in high yields of 90% or more, respectively.

Claims (17)

1. (a) 5-Hydroxymethylfurfural (HMF) is hydrogenated using hydrogen (H ₂ ) and a catalyst to react with 2,5-furandimethanol (FDM) and 2, Comprising the steps of preparing a furan-based compound comprising at least one selected from the group consisting of 5-tetrahydrofuran dimethanol (2,5-Tetrahydrofuran dimethanol, THF-DM),

   The catalyst is to include a support of a spinel structure carrying the noble metal nanoparticles,

   Method for producing furan-based compound.
2. According to claim 1,

   The method for producing the furan-based compound

   After the step (a), (b) separating the 2,5-furan dimethanol or 2,5-tetrahydrofuran dimethanol; further comprising,

   The isolated 2,5-furan dimethanol or 2,5-tetrahydrofuran dimethanol contains 0.1 to 20 ppm of cobalt (Co), 0.1 to 60 ppm of manganese (Mn), and 0.1 to 5 ppm of ruthenium (Ru) Method of producing a furan-based compound, characterized in that.
3. According to claim 1,

   The support of the spinel structure is MnCo ₂ O ₄ , CoMn ₂ O ₄ , ZnAl ₂ O ₄ , FeAl ₂ O ₄ , CuFe ₂ O ₄ , ZnMn ₂ O ₄ , MnFe ₂ O ₄ , Fe ₃ O ₄ , TiFe ₂ O ₄ , ZnFe ₂ O ₄ , Mg ₂ SiO ₄ , Fe ₂ SiO ₄ Method of producing a furan-based compound, characterized in that it comprises at least one selected from the group consisting of.
4. According to claim 1,

   Method for producing a furan-based compound, characterized in that the noble metal nanoparticles include at least one selected from the group consisting of platinum, palladium, and ruthenium.
5. According to claim 1,

   Method for producing a furan-based compound, characterized in that the catalyst is a MnCo ₂ O ₄ support having a spinel structure carrying ruthenium nanoparticles.
6. According to claim 1,

   The step of preparing the furan-based compound consists of a reaction time, the pressure of the hydrogen, and a molar ratio (mol / mol) of 5-hydroxymethylperfural (HMF / Ru) to ruthenium (Ru) of the catalyst One or more selected from the group consisting of 2,5-furan dimethanol and 2,5-tetrahydrofuran dimethanol by adjusting one or more reaction conditions selected from 90% yield and selectivity of 90% or more Method for producing a furan-based compound, characterized in that the step of manufacturing.
7. According to claim 1,

   In the step of preparing the furan-based compound, the reaction time is 2.5 to 3.5 hr, the hydrogen pressure is 5 to 6 MPa, and the molar ratio (mol / mol) of HMF / Ru is adjusted to 30 to 40 to 2,5-furandi Method for producing a furan-based compound, characterized in that the step of preparing methanol as a main product.
8. According to claim 1,

   In the step of preparing the furan compound, the reaction time is 15.5 to 16.5 hr, the pressure of the hydrogen is 6.5 to 9.5 MPa, and the molar ratio (mol / mol) of HMF / Ru is adjusted to 45 to 105 to 2,5-tetra. Method for producing a furan-based compound, characterized in that the step of producing a hydrofuran dimethanol as a main product.
9. According to claim 1,

   Method of producing a furan-based compound, characterized in that the reaction temperature of the step of preparing the furan-based compound is 70 to 150 ℃.
10. According to claim 1,

    Method for producing a furan-based compound, characterized in that the precious metal nanoparticles are 1 to 10% by weight based on the catalyst weight.
11. The method of claim 10,

    Method of producing a furan-based compound, characterized in that the precious metal nanoparticles are 3 to 5% by weight based on the catalyst weight.
12. The method of claim 11,

    Method for producing a furan-based compound, characterized in that the precious metal nanoparticles are 4% by weight based on the catalyst weight.
13. According to claim 1,

    Method for producing a furan-based compound, characterized in that the step of preparing the furan-based compound is a step performed in a single container.
14. According to claim 1,

    Method for producing a furan-based compound, characterized in that the 5-hydroxymethylperfural is derived from biomass containing at least one selected from the group consisting of cellulose and polysaccharides.
15. According to claim 1,

    The method for producing the furan-based compound is performed by a solution reaction using a solvent,

    The solvent is methanol, ethanol, n-propanol, iso-propanol, butanol, pentanol, tetrahydrofuran, methyl tert-butyl ether, hexane and pentane Furan-based compound characterized in that it comprises at least one member selected from the group consisting of Method of manufacturing.
16. The method of claim 15,

    Method for producing a furan-based compound, characterized in that the solvent is methanol.
17. According to claim 1,

    Method of manufacturing a furan-based compound, characterized in that the average particle diameter (D ₅₀ ) of the support of the spinel structure is 2.0 to 4.0 μm.

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