KR102526165B1 - Spinel structure catalyst for preparing adipic acid and method of preparing adipic acid using same - Google Patents

Abstract

The present invention is a support of a spinel structure; and a transition metal supported on the support, and relates to a catalyst for use in producing adipic acid. The catalyst for producing adipic acid and the method for producing adipic acid using the catalyst of the present invention can obtain adipic acid from biomass, and can obtain a high yield of adipic acid by adjusting the shape of the catalyst.

Description

Spinel structure catalyst for producing adipic acid and method for producing adipic acid using the same

The present invention relates to a spinel structure catalyst for producing adipic acid and a method for producing adipic acid using the same, and more particularly, by using a catalyst including a spinel structure support, adipic acid can be obtained from biomass, , It relates to a catalyst capable of obtaining a high yield of adipic acid by controlling the shape of the catalyst and a method for producing adipic acid using the same.

Adipic acid is a key renewable component for making thermoplastics and coatings, nylon 6.6, and is the most important dicarboxylic acid in industrial observations. It is one of the organic acids obtained by hydrolysis of fat and is colorless in columnar crystals. 2.5 billion kg is produced every year, and it is mainly used as a precursor to make nylon, and is also widely used as a raw material for plastic plasticizers, dyes, and pharmaceuticals. It is also used as a powder for baking powder, an acidulant for cheese, candy, and jelly, a flavor enhancer for alcoholic beverages, and a pH adjusting agent for gel formation in jams and jellies. Adipic acid is chemically synthesized by oxidizing cyclohexane, and biologically it can be produced by hydrogenation after production of cis, cis-muconic acid from glucose by microbial fermentation.

Conventionally, adipic acid was prepared through a chemical synthesis process using cyclohexanone as an intermediate from benzene obtained in a crude oil refining process. However, this method has problems in that a large amount of by-products harmful to the environment such as instability of oil price, use of toxic substance benzene, and nitrogen oxides (NOx) may be generated. Therefore, a method for producing adipic acid using glucose that is less harmful to the environment has been proposed, but this also has the disadvantage of having a very complicated process. there was.

An object of the present invention is to provide a catalyst capable of obtaining adipic acid from biomass by using a catalyst including a spinel structured support and obtaining a high yield of adipic acid by controlling the shape of the catalyst, and to provide the same It is to provide a method for producing adipic acid using the present invention.

Another object of the present invention is to provide a catalyst for preparing adipic acid that can reduce catalyst cost and reuse by using a heterogeneous catalyst containing a transition metal and a method for producing adipic acid using the same.

According to one aspect of the present invention, the support of the spinel structure; and a transition metal supported on the support, and a catalyst for use in producing adipic acid is provided.

The support of the spinel structure may include MnCo ₂ O ₄ .

The support of the spinel structure may have an average particle size of 10 to 1,500 nm.

The support of the spinel structure may have any one shape selected from the group consisting of a sphere shape, a microbar shape, a cube shape, a nanorod shape, and combinations thereof.

The support of the spinel structure may have a microbar shape, and the support of the spinel structure of the microbar shape may have a length of 1 μm to 3 μm and a thickness of 0.1 μm to 1 μm.

The support of the spinel structure may have a nanorod shape, and the nanorod support may have a length of 0.1 μm to 2 μm and a thickness of 0.05 μm to 0.3 μm.

The transition metal may include at least one selected from the group consisting of ruthenium (Ru), platinum (Pt), palladium (Pd), rhenium (Re), and rhodium (Rh).

The transition metal may include ruthenium (Ru).

The transition metal may be 3 to 10% by weight based on the total weight of the catalyst.

The catalyst may be a catalyst used to produce adipic acid by reacting a furan-based compound containing a carboxylic acid group.

The furan-based compound may be 2,5-furandicarboxylic acid (FDCA).

The furan-based compound may be prepared from biomass.

The biomass may be high fructose corn syrup.

According to another aspect of the present invention, the step of producing adipic acid by hydrodeoxygenation of a furanic compound containing a carboxylic acid group with hydrogen in the presence of a catalyst A method for producing adipic acid is provided.

The catalyst is a spinel-structured support; and a transition metal supported on the support, and may be a catalyst for use in producing adipic acid.

The hydrodeoxygenation reaction may be performed at a hydrogen pressure of 200 to 1,000 psi.

The hydrodeoxygenation reaction may be performed at a temperature of 150 to 230 °C.

The hydrodeoxygenation reaction may be performed for 1 to 10 hours.

In the hydrodeoxygenation reaction, the content of the FDCA substrate may be 0.1 to 15% by weight.

According to another aspect of the present invention, adipic acid produced according to the method for producing adipic acid is provided.

The catalyst for producing adipic acid and the method for producing adipic acid using the catalyst of the present invention can obtain adipic acid from biomass, and can obtain a high yield of adipic acid by adjusting the shape of the catalyst.

In addition, the catalyst for producing adipic acid and the method for producing adipic acid using the catalyst of the present invention use a heterogeneous catalyst containing a transition metal, thereby reducing catalyst cost and reusing it.

1 is a reaction scheme showing a reaction for producing adipic acid from a furan-based compound of the present invention.
2A is Example 1, FIG. 2B is Example 2, FIG. 2C is Example 3, FIG. 2D is Example 4, FIG. 2E is Example 5, and FIG. 2F is FE-SEM images of catalysts according to Example 6 ( Left) and HR-TEM image (right).
3 is an XRD analysis graph of catalysts according to Examples 1 to 6;
4 is a graph of adipic acid yield according to hydrogen pressure.
5 is a graph of adipic acid yield according to reaction temperature.
6 is a graph of adipic acid yield according to reaction time.
7 is a graph of adipic acid yield according to FDCA substrate concentration.
8 is a graph of adipic acid yield according to the reaction using the catalysts of Examples 1 to 6.
9 is a graph of adipic acid yield according to the reaction using the catalysts of Comparative Examples 1 to 4 and Example 4.
10 is a graph of adipic acid yield according to the reaction using the catalysts of Comparative Examples 5 to 10 and Example 4.
11 is a graph of adipic acid yield according to the reaction using the catalysts of Comparative Examples 11 to 13 and Example 4.
12 is a graph of adipic acid yield according to the reaction using the catalysts of Comparative Examples 14 to 16 and Example 4.
Figure 13 is a graph of adipic acid yield according to the catalyst according to the reaction using the catalysts of Comparative Examples 17 to 21 and Example 4.

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

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

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

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

Hereinafter, a catalyst for use in the production of adipic acid and a method for producing adipic acid using the catalyst of the present invention will be described.

The present invention is a support of a spinel structure; and a transition metal supported on the support, and provides a catalyst for use in producing adipic acid.

The support of the spinel structure may include MnCo ₂ O ₄ .

The support of the spinel structure may have an average particle size of 10 to 1,500 nm.

The support of the spinel structure may have any one shape selected from the group consisting of a sphere shape, a microbar shape, a cube shape, a nanorod shape, and combinations thereof.

The support of the spinel structure may have a microbar shape, and the support of the spinel structure of the microbar shape may have a length of 1 μm to 3 μm and a thickness of 0.1 μm to 1 μm.

The support of the spinel structure may have a nanorod shape, and the nanorod support may have a length of 0.1 μm to 2 μm and a thickness of 0.05 μm to 0.3 μm.

The transition metal may include at least one selected from the group consisting of ruthenium (Ru), platinum (Pt), palladium (Pd), rhenium (Re), and rhodium (Rh), and preferably ruthenium (Ru) can include

The transition metal may be 3 to 10% by weight based on the total weight of the catalyst. If the transition metal is included in less than 3% by weight, the yield of adipic acid (AA) may be lowered, and if included in more than 10% by weight, the price of the catalyst may be increased, which may be uneconomical.

The catalyst may be a catalyst used to produce adipic acid by reacting a furan-based compound containing a carboxylic acid group.

The furan-based compound may be 2,5-furandicarboxylic acid (FDCA).

The furan-based compound may be prepared from biomass.

The biomass may be high fructose corn syrup.

The 2,5-furandicarboxylic acid (FDCA) is a furan-based compound containing two carboxylic acids obtained by oxidation of an aldehyde group and an alcohol group of HMF of 5-hydroxymethyl-2-furfural (HMF). Hydroxymethyl-2-furfural (HMF) can be obtained by dehydration of sugars, in particular hexose sugars such as fructose and glucose, which can be obtained by hydrolysis of cellulosic or polysaccharide containing biomass and possibly glucose It can also be obtained from fructose (high fructose corn syrup) obtained by its isomerization. That is, it can be said that the furan-based compound used in the present invention is obtained from cellulose or polysaccharide-containing biomass. This cellulosic or polysaccharide-containing biomass is an example of a widely available raw material in nature and is a renewable raw material for HMF and FDCA.

In addition, the present invention relates to the production of adipic acid comprising the step of preparing adipic acid by hydrodeoxygenating a furan-based compound containing a carboxylic acid group with hydrogen in the presence of a catalyst. A manufacturing method is provided.

The reaction can be carried out according to the reaction scheme of FIG. 1, and the yield of adipic acid is maximized by varying the reaction conditions such as catalyst, pressure, temperature, and time used in the method for producing adipic acid according to the present invention. .

The catalyst is a spinel-structured support; and a transition metal supported on the support, and may be a catalyst for use in producing adipic acid.

The hydrodeoxygenation reaction may be performed at a hydrogen pressure of 200 to 1,000 psi, preferably at a hydrogen pressure of 400 to 600 psi. If the hydrodeoxygenation reaction is performed at a hydrogen pressure of less than 200 psi, the yield of adipic acid (AA) may be lowered, and if it is performed at a hydrogen pressure of more than 1,000 psi, excessive use of hydrogen affects the price increase of the catalytic process It can be crazy, it can be uneconomical.

The hydrodeoxygenation reaction may be carried out at a temperature of 150 to 230 °C, preferably at a temperature of 190 to 220 °C. If the hydrodeoxygenation reaction is performed at a temperature of less than 150 ° C, the yield of adipic acid (AA) may be lowered, and if it is performed at a temperature of more than 230 ° C, it may affect the price increase of the catalytic process, which is not economical. can

The hydrodeoxygenation reaction may be performed for 1 to 10 hours, preferably for 1 to 5 hours. If the hydrodeoxygenation reaction is performed for less than 1 hour, the yield of adipic acid (AA) may be lowered, and if it is carried out for more than 10 hours, the yield of obtaining the C6 compound may be reduced due to the gasification reaction.

In the hydrodeoxygenation reaction, the content of the FDCA substrate may be 0.1 to 15% by weight. If the content of the FDCA substrate is less than 0.1% by weight, the amount of adipic acid obtainable may be low, and if it is greater than 15% by weight, the amount of catalyst required increases, which can affect the price increase of the catalytic process, which can be uneconomical there is.

Reaction Scheme 1 shows the reaction pathway of the reactant FDCA, and various compounds can be produced. FDCA is 2,5-furandicarboxylic acid, FCA is 2-furancarboxylic acid, THFDCA is tetrahydrofuran-2,5-furandicarboxylic acid -dicarboxylic acid), THFDiol is tetrahydrofurandiol, HAA is 2-hydroxyadipic acid, HVA is 5-hydroxyvaleric acid, DHAA is 5, 6-dihydroxyhexanoic acid (5,6-dihydroxyhexanoic acid), AA is adipic acid (adipic acid), HCA is hydrocaproic acid (hydroxycaproic acid). In Scheme 1 below, the number written on the right side of the compound is the mass value of the compound confirmed through mass spectroscopy.

[Scheme 1]

In addition, the present invention provides adipic acid prepared according to the method for producing adipic acid.

[Example]

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

[Preparation of spinel structured support]

Preparation Example 1: 12-13nm MnCo ₂ O ₄ sphere

Cobalt(II) acetate tetrahydrate (CH ₃ COO) ₂ Co 4H ₂ O) 65.3 mmol and manganese(II) acetate tetrahydrate (CH ₃ COO) ₂ Mn 4H ₂ O ) 32.6 mmol (molar ratio Co: Mn = 2: 1) was dissolved in 400 mL of water, and homogenized by stirring for 30 minutes (solution 1). And separately, 50 g of Ammonium sulfate is dissolved in 400 mL of water (Solution 2). The solutions 1 and 2 were slowly stirred and mixed for 4 hours to prepare a mixed solution, and an aqueous solution in which ammonium bicarbonate (NH ₄ HCO ₃ ) was sufficiently dissolved was slowly mixed with the mixed solution, stirred for 6 hours, and filtered to obtain a soft solution. A pink precipitate was obtained. The precipitate was washed with distilled water and anhydrous ethanol, and dried at 60 °C for 12 hours to obtain a carbonate precursor. The carbonate precursor was calcined at 450 °C (5 °C/min) in a furnace in an air atmosphere for 8 hours, and then slowly cooled naturally to room temperature to obtain a spinel structured MnCo ₂ O ₄ support (Particle size: 12-13 nm) was obtained.

Preparation Example 2: 60-90 nm MnCo ₂ O ₄ sphere

Cobalt(II) acetate tetrahydrate (CH ₃ COO) ₂ Co 4H ₂ O) 10 mmol and manganese(II) acetate tetrahydrate (CH ₃ COO) ₂ Mn 4H ₂ O ) 5 mmol (molar ratio Co: Mn = 2: 1) was dissolved in 10 mL of deionized water, 32 mmol of citric acid was added, and then neutralized with 25 wt% ammonia water to obtain a mixed solution. manufactured. 100 mL of anhydrous ethanol was added while magnetically stirring the mixed solution.

A gel-like precursor was obtained by evaporating water and ethanol from the mixed solution to which anhydrous ethanol was added at a temperature of 100° C. in an airing oven. The precursor was heat-treated at 600° C. for 18 hours in an air atmosphere to obtain a spinel-structured MnCo ₂ O ₄ support (Particle size: 60-90 nm).

Preparation Example 3: 15-17 nm MnCo ₂ O ₄ sphere

4 mL of aqueous ammonia (25 wt%) was added dropwise to a solution of 10 mmol cobalt(II) nitrate hexahydrate (Co(NO ₃ ) ₂ 6H ₂ O) at room temperature with constant stirring. Thereafter, a solution of 5 mmol of manganese(II) nitrate hexahydrate (Manganese(II) nitrate hexahydrate, Mn(NO ₃ ) ₂ 6H ₂ O) was added and stirred for 120 minutes to prepare a mixture. After heating the mixture at 180 °C for 40 minutes, it was calcined at 600 °C for 4 hours to obtain a spinel-structured MnCo ₂ O ₄ support (Particle size: 15-17 nm).

Preparation Example 4: MnCo ₂ O ₄ microbar

Cobalt(II) chloride hexahydrate (CoCl ₂ 6H ₂ O) and manganese(II) chloride tetrahydrate (MnCl ₂ 4H ₂ O) so that the molar ratio of Co:Mn is 2:1 were mixed and added dropwise to already preheated 0.4 M oxalic acid (50% excess) to form a precipitate, and the precipitate was left as it was for 24 hours under ambient conditions. Then, the precipitate was filtered and washed several times with deionized water and ethanol to obtain a precursor from which chlorine (Cl) and excess oxalic acid were removed. After drying the precursor in an oven at 90 ° C. for 8 hours, it was calcined in air at 400 ° C. for 4 hours to form a microbar-type MnCo ₂ O ₄ support (Length: 1.3-2.5 μm/ Thickness: 400-600 nm) was obtained.

Preparation Example 5: MnCo ₂ O ₄ nanocube

0.25 mmol manganese acetate tetrahydrate ((CH ₃ COOH) ₂ Mn 4H ₂ O), 0.5 mmol cobaltacetic acid tetrahydrate ((CH ₃ COO) ₂ Co 4H ₂ O) and 7.5 mmol urea (CO(NH ₂ ) ₂ ) was dissolved in a mixed solvent containing 10 mL of deionized water and 20 mL of ethylene glycol (EG) with magnetic stirring to obtain a transparent pink solution. The pink solution was then transferred to a 50 mL Teflon-lined stainless steel autoclave and heated in an oven at 150° C. for 5.5 hours. And after cooling to room temperature, centrifugation was performed to obtain a pink product, and the residue was removed by washing with deionized water and ethanol three times. The product from which the residue was removed was dried at 60 °C for 12 hours to obtain MnCo ₂ (CO ₃ ) ₃ . Finally, the MnCo ₂ (CO ₃ ) ₃ was annealed in air at a heating rate of 5 °C/min at 600 °C for 4 hours to obtain a nanocube-shaped MnCo ₂ O ₄ support (Particle size: 20-30 nm). ) was obtained.

Preparation Example 6: MnCo ₂ O ₄ nanorod

1.0 g of cetrimonium bromide (CTAB, ≥99%, Aldrich) was dissolved in 35 mL of cyclohexane (Kanto Chemical) and 1.5 mL (≥99%, Aldrich) of n-pentanol, and stirred for 30 minutes. Thereafter, 2.0 mL of a 1.0 M aqueous solution of oxalic acid (Junsei Chemical) was added, and stirred for an additional 1 hour until it became transparent to prepare a mixed solution.

and 0.05 M manganese nitrate hexahydrate (Mn(NO ₃ ) ₂ 6H ₂ O) (98 %, Aldrich) and 0.1 M cobalt nitrate hexahydrate (Co(NO ₃ ) ₂ 6H ₂ O) (≥98 %, Aldrich). ) was added to the mixed solution and stirred for 12 hours to obtain a product. The product was then thoroughly rinsed with anhydrous acetone and ethanol to remove the residue, and then dried in a vacuum freeze dryer to minimize nanorod aggregation. The dried product was heat-treated in an air atmosphere at 450 °C for 3 hours to obtain a nanorod-type MnCo ₂ O ₄ support (Length: 0.5-1.2 nm/ Thickness: 100-120 nm).

[Preparation of Catalyst for Adipic Acid Production]

Example 1: 4 wt % Ru/MnCo ₂ O ₄ sphere

A mixture containing 0.5 g of the spinel-structured MnCo ₂ O ₄ support and 0.05 g of RuCl ₃ 3H ₂ O prepared according to Preparation Example 1 was placed in a cooling bath with about 20 mL of water in a two-neck round bottom. Add to flask (100 mL). At this time, Ru is added so as to be 4.0% by weight based on the total catalyst. The mixture is stirred for 12 hours under N ₂ atmosphere. Subsequently, an aqueous solution of NaBH ₄ in an amount 10 times larger than that of RuCl ₃ .3H ₂ O was added dropwise into the flask while stirring constantly at room temperature for one day to obtain a catalyst. Finally, the catalyst was filtered, washed with ethanol, and dried under vacuum to obtain a ruthenium-supported catalyst (4 wt% Ru/MnCo ₂ O ₄ sphere) on a spinel-structured MnCo ₂ O ₄ support.

Examples 2 to 6

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

catalyst support Morphology particle size Example 1 4 wt% Ru/MnCo ₂ O ₄ sphere Preparation Example 1 Nanosized sphere aggregated to microsphere 12-13 nm Example 2 4 wt % Ru/MnCo ₂ O ₄ 60-90 nm Preparation Example 2 Sphere 60-90 nm Example 3 4 wt % Ru/MnCo ₂ O ₄ 15-17 nm Preparation Example 3 Sphere 15-17 nm Example 4 4 wt% Ru/MnCo ₂ O ₄ microbars Production Example 4 Microbar Length: 1.3-2.5 μm
Thickness: 400-600 nm Example 5 4 wt% Ru/MnCo ₂ O ₄ nanocubes Preparation Example 5 Cubic & sphere mixed 20-30 nm Example 6 4 wt% Ru/MnCo ₂ O ₄ nanorods Preparation Example 6 Nanorod Length: 0.5-1.2 nm
Thickness: 100-120nm

Comparative Examples 1 to 21

A catalyst was prepared under the same conditions as in Example 1, but the composition of the catalyst prepared by changing the type of support is shown in Table 2 below.

catalyst support spinel form Comparative Example 1 4 wt% Ru/TiO ₂ -ZrO ₂ TiO ₂ -ZrO ₂ - Comparative Example 2 4 wt % Ru/MoO ₃ MoO ₃ - Comparative Example 3 4 wt % Ru/γ-Al ₂ O ₃ γ-Al ₂ O ₃ - Comparative Example 4 4 wt% Ru/WO ₃ -ZrO ₂ WO ₃ -ZrO ₂ - Comparative Example 5 4 wt % Ru/MgCo ₂ O ₄ MgCo ₂ O ₄ ACo ₂ O ₄ Comparative Example 6 4 wt % Ru/TiCo ₂ O ₄ TiCo ₂ O ₄ Comparative Example 7 4 wt % Ru/FeCo ₂ O ₄ FeCo ₂ O Comparative Example 8 4 wt % Ru/CuCo ₂ O ₄ CuCo ₂ O ₄ Comparative Example 9 4 wt % Ru/ZnCo ₂ O ₄ ZnCo ₂ O ₄ Comparative Example 10 4 wt % Ru/CeCo ₂ O ₄ CeCo ₂ O ₄ Comparative Example 11 4 wt % Ru/MnCu ₂ O ₄ MnCu ₂ O ₄ MnB ₂ O ₄ Comparative Example 12 4 wt % Ru/MnNi ₂ O ₄ MnNi ₂ O ₄ Comparative Example 13 4 wt % Ru/MnCr ₂ O ₄ MnCr ₂ O ₄ Comparative Example 14 4 wt % Ru/FeAl ₂ O ₄ FeAl ₂ O ₄ AB ₂ O ₄ Comparative Example 15 4 wt% Ru/CuCr ₂ O ₄ CuCr ₂ O ₄ Comparative Example 16 4 wt % Ru/MgAl ₂ O ₄ MgAl ₂ O ₄ Comparative Example 17 4wt% Ru/MnO MnO - Comparative Example 18 4 wt % Ru/Mn ₂ O ₃ Mn ₂ O ₃ - Comparative Example 19 4 wt % Ru/Mn ₃ O ₄ Mn ₃ O ₄ - Comparative Example 20 4wt% Ru/CoO CoO - Comparative Example 21 4 wt % Ru/Co ₃ O ₄ Co ₃ O ₄ -

[Hydrodeoxygenation reaction from FDCA to AA (Adipic Acid)]

Reaction Example 1

A 100 mL stainless steel high-pressure reactor was equipped with a magnetic stirrer and an electric heater. A glass reactor was filled with 2,5-furandicarboxylic acid (FDCA) (0.4 mmol, 0.0625 g) and 20 mL of water as a solvent, and 0.05 g of catalyst was added so that the FDCA/ruthenium (Ru) molar ratio was 20, After mixing was performed at room temperature for at least 5 minutes while maintaining the stirring speed at 450 rpm, the hydrogen pressure in the reactor was set to 450 psi while hydrogen (H ₂ ) was continuously supplied into the reactor, and the reaction was carried out at 200 ° C. for 4 hours. made it During the reaction, the pressure was regulated by a back pressure regulator connected to the reservoir tank so that the pressure in the reactor could be kept constant. After the reaction, the reaction mixture was cooled to room temperature. The above reaction may be carried out with reference to Scheme 2 below.

[Scheme 2]

Reaction Examples 2 and 3

The experiment was conducted under the same conditions as in Reaction Example 1, but the hydrogen pressure was varied, and the experimental conditions are shown in Table 3 below.

reaction catalyst
(g) FDCA
(mmol) FDCA concentration
(wt%) FDCA/Ru
mole ratio hydrogen pressure
(psi) reaction temperature
(℃) reaction time
(h) Reaction Example 1 Example 1 0.4 0.3 20 450 200 4 Reaction Example 2 Example 1 0.4 0.3 20 220 200 4 Reaction Example 3 Example 1 0.4 0.3 20 900 200 4

Reaction Examples 4 to 6

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

reaction catalyst FDCA
(mmol) FDCA concentration
(wt%) FDCA/Ru molar ratio hydrogen pressure
(psi) reaction temperature
(℃) reaction time
(h) Reaction Example 4 Example 1 0.4 0.3 20 450 160 4 Reaction Example 5 Example 1 0.4 0.3 20 450 180 4 Reaction Example 6 Example 1 0.4 0.3 20 450 220 4

Reaction Examples 7 and 8

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

reaction catalyst FDCA
(mmol) FDCA concentration
(wt%) FDCA/Ru molar ratio hydrogen pressure
(psi) reaction temperature
(℃) reaction time
(h) Reaction Example 7 Example 1 0.4 0.3 20 450 200 2 Reaction Example 8 Example 1 0.4 0.3 20 450 200 8

Reaction Examples 9 to 11

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

reaction catalyst FDCA
(mmol) FDCA concentration
(wt%) FDCA/Ru molar ratio hydrogen pressure
(psi) reaction temperature
(℃) reaction time
(h) Reaction Example 9 Example 1 (0.5 g) 4mmol
(0.62g) 3 20 450 200 4 Reaction Example 10 Example 1 (0.85 g) 6.8 mmol
(1.06g) 5 20 450 200 4 Reaction Example 11 Example 1 (3.7 g) 14.7 mmol
(2.3g) 10 20 450 200 4

Reaction Examples 12 to 37

The experiment was conducted under the same conditions as in Reaction Example 1, but with different catalysts used, and the experimental conditions are shown in Table 7 below.

reaction catalyst FDCA
(mmol) FDCA concentration
(wt%) FDCA/Ru molar ratio hydrogen pressure
(psi) reaction temperature
(℃) reaction time
(h) Reaction Example 12 Example 2 0.4 0.3 20 450 200 4 Reaction Example 13 Example 3 0.4 0.3 20 450 200 4 Reaction Example 14 Example 4 0.4 0.3 20 450 200 4 Reaction Example 15 Example 5 0.4 0.3 20 450 200 4 Reaction Example 16 Example 6 0.4 0.3 20 450 200 4 Reaction Example 17 Comparative Example 1 0.4 0.3 20 450 200 4 Reaction Example 18 Comparative Example 2 0.4 0.3 20 450 200 4 Reaction Example 19 Comparative Example 3 0.4 0.3 20 450 200 4 Reaction Example 20 Comparative Example 4 0.4 0.3 20 450 200 4 Reaction Example 21 Comparative Example 5 0.4 0.3 20 450 200 4 Reaction Example 22 Comparative Example 6 0.4 0.3 20 450 200 4 Reaction Example 23 Comparative Example 7 0.4 0.3 20 450 200 4 Reaction Example 24 Comparative Example 8 0.4 0.3 20 450 200 4 Reaction Example 25 Comparative Example 9 0.4 0.3 20 450 200 4 Reaction Example 26 Comparative Example 10 0.4 0.3 20 450 200 4 Reaction Example 27 Comparative Example 11 0.4 0.3 20 450 200 4 Reaction Example 28 Comparative Example 12 0.4 0.3 20 450 200 4 Reaction Example 29 Comparative Example 13 0.4 0.3 20 450 200 4 Reaction Example 30 Comparative Example 14 0.4 0.3 20 450 200 4 Reaction Example 31 Comparative Example 15 0.4 0.3 20 450 200 4 Reaction Example 32 Comparative Example 16 0.4 0.3 20 450 200 4 Reaction Example 33 Comparative Example 17 0.4 0.3 20 450 200 4 Reaction Example 34 Comparative Example 18 0.4 0.3 20 450 200 4 Reaction Example 35 Comparative Example 19 0.4 0.3 20 450 200 4 Reaction Example 36 Comparative Example 20 0.4 0.3 20 450 200 4 Reaction Example 37 Comparative Example 21 0.4 0.3 20 450 200 4

[Test Example]

Test Example 1: SEM, TEM and XRD analysis

2A is Example 1, FIG. 2B is Example 2, FIG. 2C is Example 3, FIG. 2D is Example 4, FIG. 2E is Example 5, and FIG. 2F is FE-SEM images of catalysts according to Example 6 ( Left) and HR-TEM images (right), and FIG. 3 is an XRD analysis graph of catalysts according to Examples 1 to 6.

According to FIGS. 2A to 2F, Example 1 shows a micro-sized sphere form by aggregation of nano-sized spheres of about 12-13 nm, Example 2 shows a sphere shape of about 60-90 nm, and Example 3 shows a sphere shape of about 60-90 nm. It showed a spherical shape of about 15–17 nm. In addition, Example 4 was confirmed to be in the form of a microbar with a length of 1.3-2.5 μm and a thickness of about 400-600 nm, and Example 5 was in the form of a nanocube of about 20-30 nm in which a cubic structure and a sphere were mixed. showed Also, Example 6 was confirmed to have a nanorod shape having a length of 0.5-1.2 nm and a thickness of about 100-120 nm.

Also, according to FIG. 3, it is analyzed that all of the catalysts according to Examples 1 to 6 have a cubic phase.

Test Example 2: Adipic acid yield analysis according to reaction conditions

Figure 4 is a graph of adipic acid yield according to hydrogen pressure, Figure 5 is a graph of adipic acid yield according to reaction temperature, Figure 6 is a graph of adipic acid yield according to reaction time, Figure 7 is a graph of FDCA substrate concentration It is a graph of adipic acid yield. For product analysis after the reaction, HPLC (Agilent Technologies 1200 series, Bio-Rad Aminex HPX-87 H pre-packed column, and UV-detector, column mobile phase H ₂ SO ₄ (0.0005 M)) equipment was used. . FDCA conversion, AA yield, and AA selectivity were calculated as shown in Equations 1 to 3 below. The calculation was performed in the same way in Test Examples 3 and 4 below.

[Equation 1]

[Equation 2]

[Equation 3]

According to Figures 4 to 7, low pressure (about 220 psi) is advantageous for HAA production, but the yield of HAA is greatly reduced at hydrogen pressures of 450 and 900 psi. In addition, when the reaction temperature is increased, the yield of adipic acid (AA) increases and the yield of THFDCA decreases. In addition, when the reaction time was more than 4 hours, the yield of HAA decreased significantly, whereas the yield of AA increased significantly. However, if the reaction is carried out for up to 8 hours, other by-products may be formed, which is not preferable as an optimization condition.

Therefore, under the conditions of a hydrogen pressure of 450 psi, a reaction temperature of 200 ° C, a reaction time of 4 hours, and a FDCA substrate concentration of 0.3 wt%, the yield of adipic acid (AA) was 25.6%, indicating that this is the most optimal condition. there is.

Test Example 3: Adipic acid yield analysis according to the type of catalyst

8 is a graph of adipic acid yield according to the reaction using the catalysts of Examples 1 to 6.

According to FIG. 8, the reaction using the catalyst according to Example 4 (4 wt% Ru/MnCo ₂ O ₄ microbars) is compared to the reaction using the catalyst according to Example 1 (4 wt% Ru/MnCo ₂ O ₄ sphere). It can be seen that the yield of HAA decreased and the yield of adipic acid (AA) increased significantly, and the reaction using the catalyst according to Example 4 showed the highest yield of adipic acid (AA) at 35.4%.

Test Example 4: Adipic acid yield analysis according to the type of support

9 is a graph of adipic acid yield according to the reaction using the catalysts of Comparative Examples 1 to 4 and Example 4, and FIG. 10 is a graph of adipic acid yield according to the reaction using the catalysts of Comparative Examples 5 to 10 and Example 4. 11 is a graph of adipic acid yield according to the reaction using the catalysts of Comparative Examples 11 to 13 and Example 4, and FIG. 12 is a graph of adipic acid yield according to the reaction using the catalysts of Comparative Examples 14 to 16 and Example 4. It is a yield graph, and FIG. 13 is a graph of adipic acid yield according to the catalyst according to the reaction using the catalysts of Comparative Examples 17 to 21 and Example 4.

According to FIG. 9, the yield of adipic acid varies depending on the type of metal oxide support, and the yield of adipic acid was the highest in the reaction using the Ru/MnCo ₂ O ₄ microbars catalyst of the present invention.

10 to 12, the yield of adipic acid varies depending on the type of spinel support represented by ACo ₂ O ₄ , MnB ₂ O ₄ or AB ₂ O ₄ , and the Ru/MnCo ₂ O ₄ microbars of the present invention The adipic acid yield of the reaction using the catalyst was the highest.

In addition, according to FIG. 13, the yield of adipic acid varies depending on the type of oxide support including manganese (Mn) and cobalt (Co), and the reaction using the Ru/MnCo ₂ O ₄ microbars catalyst of the present invention Dipic acid yield was the highest.

In the above, the preferred embodiments of the present invention have been described, but those skilled in the art can add, change, delete or modify components within the scope not departing from the spirit of the present invention described in the claims. Various modifications and changes may be made to the present invention by addition or the like, which will also be included within the scope of the present invention. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form. The scope of the present invention is indicated by the following claims rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts should be construed as being included in the scope of the present invention. do.

Claims (20)

a support of a spinel structure containing MnCo ₂ O ₄ ; and
Including; transition metal supported on the support,
The support of the spinel structure is in the form of a microbar,
The support of the spinel structure in the form of a microbar has a length of 1 to 3 μm and a thickness of 0.1 to 1 μm,
The transition metal includes ruthenium (Ru),
A catalyst for use in the manufacture of adipic acid. delete According to claim 1,
Catalyst, characterized in that the support of the spinel structure has an average particle size (size) of 10 to 1,500 nm. delete delete delete delete delete According to claim 1,
Catalyst, characterized in that the transition metal is 3 to 10% by weight based on the total weight of the catalyst. According to claim 1,
The catalyst is characterized in that the catalyst used for producing adipic acid by reacting a furan-based compound containing a carboxylic acid group. According to claim 10,
Catalyst, characterized in that the furan-based compound is 2,5-furandicarboxylic acid (FDCA). According to claim 10,
A catalyst, characterized in that the furan-based compound is prepared from biomass. According to claim 12,
Catalyst, characterized in that the biomass is high fructose corn syrup. Hydrodeoxygenation of a furan-based compound containing a carboxylic acid group with hydrogen in the presence of the catalyst according to claim 1 to produce adipic acid; Manufacturing method of. delete According to claim 14,
The method for producing adipic acid, characterized in that the hydrodeoxygenation reaction is carried out at a hydrogen pressure of 200 to 1,000 psi. According to claim 14,
The method for producing adipic acid, characterized in that the hydrodeoxygenation reaction is carried out at a temperature of 150 to 230 ℃. According to claim 14,
A method for producing adipic acid, characterized in that the hydrodeoxygenation reaction is carried out for 1 to 10 hours. delete delete

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